Establishing A Groundwater Baseline For Unconventional Gas Projects in South Africa

ESTABLISHING A GROUNDWATER BASELINE
FOR UNCONVENTIONAL GAS PROJECTS

IN SOUTH AFRICA
Magiel Lourens
Submitted in fulfilment of the requirements for the degree
Master of Science
majoring in Geohydrology
at the Institute for Groundwater Studies

in the
Faculty of Natural and Agricultural Sciences
University of the Free State
Supervisor: Dr Francois Fourie

Co-supervisor: Dr Jennifer Pretorius
February 2017
DECLARATION
I, Magiel Lourens, declare that the masters degree research dissertation that I herewith submit for
the masters degree qualification Master of Science majoring in Geohydrology at the University of the
Free State is my independent work, and that I have not previously submitted it for a qualification at
another institution of higher education.
I, Magiel Lourens, hereby declare that I am aware that the copyright is vested in the University of the
Free State.
I, Magiel Lourens, hereby declare that all royalties as regards intellectual property that was developed
during the course of and/or in connection with the study at the University of the Free State will accrue
to the University.
Magiel Lourens Date: 30 / 01 / 2017
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ACKNOWLEDGEMENTS
I would hereby like to express my sincere gratitude to all who have motivated and helped me in the
completion of this thesis:
Francois Fourie, my supervisor, for agreeing to supervise this study and for your continuous
assistance, insight and attention to detail.
Jennifer Pretorius, my co-supervisor, for also agreeing to supervise this study, and for all your
personal input, advice and guidance and for supporting me and encouraging me.
My parents, Magiel and Gerda Lourens, for all your love and support, and for always believing in
me and encouraging me to work harder.
My girlfriend, Christelle van der Merwe, and all of my friends for supporting me and believing in
me.
My greatest thanks go to my heavenly Father for giving me the strength and commitment to
complete such a very difficult task.
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TABLE OF CONTENTS
DECLARATION ..........................................................................................................................II
ACKNOWLEDGEMENTS ............................................................................................................... III
TABLE OF C ONTENTS .................................................................................................................IV
LIST OF TABLES ....................................................................................................................... XII
LIST OF FIGURES ...................................................................................................................... XV
LIST OF ABBREVIATIONS AND AC RONYMS .....................................................................................XVIII
LIST OF MEASUREM ENT U NITS .................................................................................................... XX
GLOSSARY OF TERMS ............................................................................................................... XXI
ABSTRACT ........................................................................................................................... XXIII
OPSOMMING .......................................................................................................................XXIV
CHAPTER 1 INTRODUCTION ..................................................................................................... 1
1.1 GENERAL ............................................................................................................................................................. 1
1.2 BACKGROUND .................................................................................................................................................... 1
1.3 PROBLEM STATEMENT....................................................................................................................................... 2
1.4 AIMS AND OBJECTIVES OF THE STUDY ............................................................................................................. 2
1.4.1 Overall aim of the study ..................................................................................................................... 2
1.4.2 Objectives of the study....................................................................................................................... 2
1.5 RESEARCH METHODOLOGY............................................................................................................................... 3
1.6 LIMITATIONS....................................................................................................................................................... 4
1.7 STRUCTURE OF THE DISSERTATION.................................................................................................................. 4
CHAPTER 2 LITERATURE REVIEW............................................................................................... 7
2.1 INTRODUCTION .................................................................................................................................................. 7

2.2 UNCONVENTIONAL GAS RESOURCES ............................................................................................................... 7
2.2.1 Definition of unconventional gas resources...................................................................................... 7
2.2.2 Formation of unconventional gas ...................................................................................................... 9
2.2.3 Main categories of unconventional gas............................................................................................. 9
2.2.4 Unconventional gas resources ......................................................................................................... 10
2.3 HYDRAULIC FRACTURING ................................................................................................................................ 12
2.3.1 Formation of shales........................................................................................................................... 12
2.3.2 How shale gas is produced ............................................................................................................... 14
2.3.3 Properties of shale gas reservoirs .................................................................................................... 15
2.3.4 Shale gas resources in South Africa ................................................................................................. 16
2.3.5 Shale gas recovery through hydraulic fracturing............................................................................ 18
2.3.5.1 Description of hydraulic fracturing operations ................................................................ 19
2.3.5.1.1 Exploration, site assessment and development phase.................................................................19
2.3.5.1.2 Well drilling and construction........................................................................................................................20
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2.3.5.1.3 Setup and hydraulic fracturing......................................................................................................................22
2.3.5.1.4 Gas production........................................................................................................................................................22
2.3.5.1.5 Site and well closure............................................................................................................................................23
2.3.5.2 Hydraulic fracturing additives ........................................................................................... 23
2.3.5.3 Fate and transport of hydraulic fracturing fluid spills ..................................................... 28
2.3.5.3.1 Flow paths ..................................................................................................................................................................29
2.3.5.4 Physiochemical properties and mobility of chemicals .................................................... 31
2.3.5.5 Drilling fluid/mud chemicals.............................................................................................. 33
2.4 UNDERGROUND COAL GASIFICATION............................................................................................................ 35
2.4.1 Coal formation mechanisms............................................................................................................. 35
2.4.2 Coal gas resources in South Africa ................................................................................................... 36
2.4.3 Coal gas recovery through underground coal gasification............................................................. 37
2.4.3.1 Description of underground coal gasification operations............................................... 38
2.4.3.1.1 Exploration, site assessment and development phase.................................................................39
2.4.3.1.2 Well-drilling, construction and linkage.....................................................................................................40
2.4.3.1.3 Setup and ignition..................................................................................................................................................41
2.4.3.1.4 Cavity growth ...........................................................................................................................................................42
2.4.3.1.5 Gas production........................................................................................................................................................42
2.4.3.1.6 Site and well closure............................................................................................................................................43
2.4.3.2 Underground coal gasification products and by-products.............................................. 44
2.4.3.2.1 Syngas composition.............................................................................................................................................44
2.4.3.2.2 Post-processing effluent....................................................................................................................................45
2.4.3.2.3 Solid underground coal gasification by-products..............................................................................47
2.4.3.3 Fate and transport of underground coal gasification by-products ................................ 48
2.5 GEOLOGY AND GEOHYDROLOGY OF THE KAROO BASIN OF SOUTH AFRICA............................................... 50
2.5.1 Geology of the Karoo Basin .............................................................................................................. 50
2.5.2 General geology and stratigraphy of the Karoo Supergroup ......................................................... 51
2.5.3 Ecca Group......................................................................................................................................... 55
2.5.3.1 Formations of the Ecca Group........................................................................................... 55
2.5.3.2 Shale formations within the Ecca Group .......................................................................... 58
2.5.3.2.1 Lower Ecca Group .................................................................................................................................................58
2.5.3.2.2 Upper Ecca Group .................................................................................................................................................59
2.5.3.3 Coal formations within the Ecca Group............................................................................ 60
2.5.3.3.1 Lower Ecca Group .................................................................................................................................................60
2.5.3.3.2 The Middle Ecca Group......................................................................................................................................60
2.5.3.3.3 The Upper Ecca Group .......................................................................................................................................63
2.5.4 Geohydrology of the Karoo Basin .................................................................................................... 64
2.5.4.1 Karoo aquifer systems ....................................................................................................... 64
2.5.4.2 Groundwater occurrence in the Main Karoo Basin ......................................................... 65
2.5.4.2.1 Groundwater levels in South Africa ...........................................................................................................66
2.5.4.3 Water chemistry of the Karoo aquifers ............................................................................ 66
2.5.4.4 Dissolved gases in the groundwater of the Karoo ........................................................... 71
2.5.4.5 Radioactive isotopes of Karoo rocks ................................................................................. 72
2.5.4.6 Chemistry of shale groundwater....................................................................................... 73
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2.5.4.6.1 Shale formation water........................................................................................................................................73
2.5.4.6.2 Produced water from shales..........................................................................................................................74
2.5.4.6.3 Naturally occurring radioactive material (NORM)............................................................................74
2.5.4.6.4 Organics.......................................................................................................................................................................75
2.5.4.6.5 Composition of shale produced/formation water in the Karoo Supergroup..................77
2.5.4.7 Chemistry of coal groundwater......................................................................................... 78
2.5.4.7.1 Produced water from coal...............................................................................................................................78
2.5.4.7.2 Metals...........................................................................................................................................................................80
2.5.4.7.3 Naturally occurring radioactive material (NORM)............................................................................81
2.5.4.7.4 Organics.......................................................................................................................................................................81
2.5.4.7.5 Composition of coal produced/formation water in the Karoo Supergroup ....................81
2.5.4.8 Description of geological preferential flow paths............................................................ 82
2.5.4.8.1 Dolerite dykes and sills.......................................................................................................................................83
2.5.4.8.2 Breccia pipes.............................................................................................................................................................84
2.5.4.8.3 Hydrothermal vents .............................................................................................................................................85
2.5.4.8.4 Kimberlite Intrusions ...........................................................................................................................................86
2.5.4.8.5 Faults..............................................................................................................................................................................87
2.5.4.8.6 Fractures, joints and mineralised veins....................................................................................................88
2.6 POTENTIAL GROUNDWATER IMPACTS ASSOCIATED WITH HYDRAULIC FRACTURING AND
UNDERGROUND COAL GASIFICATION EXTRACTION TECHNIQUES .............................................................. 89
2.6.1 Potential groundwater impacts due to hydraulic fracturing operations ...................................... 90
2.6.1.1 Water acquisition for hydraulic fracturing operations .................................................... 91
2.6.1.2 Surface handling and transportation ................................................................................ 92
2.6.1.3 Wastewater management and disposal........................................................................... 93
2.6.1.4 Well-related impacts.......................................................................................................... 93
2.6.2 Potential groundwater impacts due to underground coal gasification operations ..................... 94
2.6.2.1 Water acquisition for underground coal gasification operations................................... 95
2.6.2.2 Potential contamination due to issues related to underground coal gasification........ 95
2.6.3 Similar potential groundwater impacts associated with hydraulic fracturing and underground
coal gasification operations.............................................................................................................. 96
2.6.3.1 Geological pathways .......................................................................................................... 96
2.6.4 Hypothetical case study in a Karoo aquifer..................................................................................... 96
2.7 CONCLUSION .................................................................................................................................................... 99
CHAPTER 3 GROUNDWATER BASELINE ESTABLISHMENT METHODOLOGY FOR HYDRAULIC
FRACTURING AND UNDERGROUND COAL GASIFICATION PROJECTS ......................................... 100
3.1 INTRODUCTION ..............................................................................................................................................100

3.2 PURPOSE OF THE BASELINE...........................................................................................................................101
3.3 DESCRIPTION OF THE METHODOLOGY.........................................................................................................103
3.3.1 Overview of the proposed methodology ......................................................................................103
3.3.1.1 Description of the different activities .............................................................................105
3.3.1.1.1 Desk study ...............................................................................................................................................................105
3.3.1.1.2 Defining the preliminary baseline study area size .........................................................................105
3.3.1.1.3 Planning the geological and geohydrological investigation.....................................................105
3.3.1.1.4 Geological investigation..................................................................................................................................107
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3.3.1.1.5 Geohydrological investigation....................................................................................................................107
3.3.1.1.6 Update of preliminary conceptual site model and gap analysis...........................................107
3.3.1.1.7 Drilling new boreholes.....................................................................................................................................107
3.3.1.1.8 Planning for the initial and subsequent sampling events .........................................................108
3.3.1.1.9 Initial and subsequent sampling events...............................................................................................108
3.3.1.1.10 Establishing a groundwater baseline.....................................................................................................108
3.4 DESK STUDY ....................................................................................................................................................108
3.4.1 Geological information and/or data of the study area ................................................................109
3.4.2 Geohydrological and hydrological information of the study area...............................................110
3.4.3 Other information ...........................................................................................................................111
3.5 AREAL EXTENT OF THE PRELIMINARY BASELINE STUDY..............................................................................112
3.5.1 Regional baseline study size...........................................................................................................112
3.5.2 Local baseline study size.................................................................................................................114
3.5.2.1 Hydraulic fracturing .........................................................................................................114
3.5.2.2 Underground coal gasification ........................................................................................115
3.6 GEOLOGICAL AND GEOHYDROLOGICAL INVESTIGATIONS..........................................................................116
3.6.1 The sequence for conducting the geological and geohydrological investigations .....................116
3.6.2 Planning the geological and geohydrological investigations .......................................................119
3.6.2.1 Determining if geological and/or geohydrological investigations are required..........119
3.6.3 Remote sensing...............................................................................................................................120
3.6.4 Conducting the field investigations ...............................................................................................120
3.6.4.1 Surface geophysical survey..............................................................................................120
3.6.4.2 Borehole inspection .........................................................................................................121
3.6.4.3 Borehole logging ..............................................................................................................123
3.6.4.4 Classifying formations as hydrostratigraphic units........................................................125
3.6.4.5 Geohydrological field investigation ................................................................................128
3.6.4.6 Aquifer tests .....................................................................................................................129
3.6.4.7 Borehole aquifer test design ...........................................................................................130
3.6.4.7.1 Selecting boreholes for pumping tests .................................................................................................131
3.6.4.7.2 Selecting observation boreholes for pumping tests.....................................................................132
3.6.4.8 Other tests which may be conducted.............................................................................133
3.6.4.9 Conclusion.........................................................................................................................133
3.7 UPDATING THE PRELIMINARY CONCEPTUAL SITE MODEL AND GAP ANALYSIS........................................133
3.8 DRILLING NEW BOREHOLES...........................................................................................................................134
3.8.1 Purpose of drilling new boreholes .................................................................................................134
3.8.1.1 Borehole construction .....................................................................................................134
3.8.2 Drilling phase...................................................................................................................................135
3.8.3 Borehole geohydrological logging..................................................................................................137
3.9 THE INITIAL AND SUBSEQUENT SAMPLING EVENTS....................................................................................138
3.9.1 The sequence of planning and conducting the initial and subsequent sampling events ..........138
3.9.2 Planning for the initial and subsequent sampling events ............................................................140
3.9.3 Selecting sampling parameters and field measurements ............................................................140
3.9.3.1 Groundwater chemistry of shales...................................................................................141
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3.9.3.2 Groundwater chemistry of coal before and after underground coal gasification
operations.........................................................................................................................143
3.9.3.3 Previous studies on unconventional gas projects..........................................................145
3.9.3.4 Hydraulic fracturing fluid constituents ...........................................................................151
3.9.3.5 Drilling fluid constituents.................................................................................................152
3.9.3.6 Natural background groundwater values of Karoo aquifers.........................................153
3.9.4 Selected parameters to be analysed for during groundwater baseline establishment for
hydraulic fracturing and underground coal gasification projects................................................155
3.9.4.1 Rationale for sampling and analysis of the different parameters ................................160
3.9.4.1.1 Major ions................................................................................................................................................................160
3.9.4.1.2 Trace metals...........................................................................................................................................................162
3.9.4.1.3 Dissolved gases.....................................................................................................................................................163
3.9.4.1.4 Dissolved stable isotopes...............................................................................................................................164
3.9.4.1.5 Radioactive constituents................................................................................................................................166
3.9.4.1.6 Organics....................................................................................................................................................................167
3.9.4.2 Rationale for sampling and analysis of field parameters ..............................................173
3.9.4.2.1 pH..................................................................................................................................................................................174
3.9.4.2.2 Electrical conductivity (EC) ............................................................................................................................174
3.9.4.2.3 Redox potential (Eh) .........................................................................................................................................175
3.9.4.2.4 Temperature (C) ................................................................................................................................................175
3.9.4.2.5 Dissolved oxygen (DO).....................................................................................................................................175
3.9.4.2.6 Alkalinity...................................................................................................................................................................176
3.9.4.3 Rationale for sampling and analysis of physical characteristics in the laboratory ......176
3.9.4.3.1 pH..................................................................................................................................................................................176
3.9.4.3.2 Total dissolved solids (TDS)...........................................................................................................................177
3.9.5 Selecting the sampling devices and sampling methods ...............................................................177
3.9.5.1 Field determination..........................................................................................................179
3.9.5.2 Sampling devices ..............................................................................................................179
3.9.5.2.1 Sampling devices (0 to 300 m)....................................................................................................................179
3.9.5.2.2 Sampling devices (300 to >1 000 m).......................................................................................................181
3.9.5.3 Sampling methods............................................................................................................183
3.9.6 Selecting boreholes for sampling...................................................................................................188
3.9.7 Selecting the sampling frequency ..................................................................................................190
3.9.7.1 Boreholes intersecting shallow (0 to 300 m) aquifers...................................................193
3.9.7.2 Boreholes intersecting deep (300 to >1 000 m) aquifers..............................................194
3.9.7.3 Additional sampling .........................................................................................................194
3.9.7.4 Conclusion.........................................................................................................................195
3.9.8 Establishing quality assurance and quality control measures .....................................................195
3.9.9 Selecting a laboratory(s).................................................................................................................197
3.9.10 Conducting the initial and subsequent sampling events .............................................................197
3.9.10.1 Generalised flow diagram of groundwater sampling steps ..........................................197
3.9.10.1.1 Installation of dedicated pumps and borehole purging.............................................................198
3.9.10.1.2 Borehole purging for sample collection...............................................................................................199
3.9.10.1.3 Preservation of samples .................................................................................................................................204
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3.9.10.1.4 Sample handling and shipment.................................................................................................................204
3.9.10.1.5 Equipment decontamination......................................................................................................................204
3.9.10.1.6 Laboratory validation.......................................................................................................................................205
3.10 ESTABLISHING A GROUNDWATER BASELINE ...............................................................................................205
3.11 CONCLUSION ..................................................................................................................................................206
CHAPTER 4 CASE STUDIES ..................................................................................................... 208
4.1 INTRODUCTION ..............................................................................................................................................208

4.2 CASE STUDY ONE............................................................................................................................................208
4.2.1 Case study description ....................................................................................................................208
4.2.2 Objectives of the project ................................................................................................................209
4.2.3 Investigation sequence...................................................................................................................209
4.2.3.1 Desk study.........................................................................................................................210
4.2.3.2 First-order geochemistry assessment.............................................................................215
4.2.3.2.1 Geochemical sampling....................................................................................................................................215
4.2.3.2.2 Laboratory geochemical analyses............................................................................................................216
4.2.3.3 Hydrocensus and specialised follow-up sampling campaign........................................216
4.2.3.3.1 Hydrocensus ..........................................................................................................................................................216
4.2.3.3.2 Specialised follow-up sampling campaign..........................................................................................217
4.2.3.4 Selected boreholes for sampling.....................................................................................217
4.2.3.4.1 Hydrocensus ..........................................................................................................................................................217
4.2.3.5 Selected parameters for sampling..................................................................................219
4.2.3.5.1 Rationale for sampling and analysing for the selected chemical parameters .............219
4.2.3.5.2 Sampling device(s), procedures and methods.................................................................................219
4.2.3.5.3 Sampling frequency ..........................................................................................................................................221
4.2.3.5.4 Quality assurance and quality control measures ...........................................................................222
4.2.3.5.5 Selected laboratory...........................................................................................................................................222
4.2.3.6 Hydraulic packer testing..................................................................................................222
4.2.3.7 Result interpretation........................................................................................................222
4.2.3.7.1 Hydrocensus and specialised follow-up sampling.........................................................................222
4.2.3.7.2 Hydraulic packer test........................................................................................................................................222
4.2.4 Results ..............................................................................................................................................222
4.2.4.1 First-order geochemical assessments results ................................................................223
4.2.4.2 Hydrocensus .....................................................................................................................223
4.2.4.3 Specialised follow-up sampling campaign......................................................................224
4.2.4.4 Hydraulic packer testing..................................................................................................224
4.2.4.5 Site conceptual model .....................................................................................................224
4.2.5 Case study conclusion.....................................................................................................................225
4.3 SUGGESTIONS FOR CASE STUDY ONE...........................................................................................................225
4.4 CASE STUDY TWO...........................................................................................................................................234
4.4.1 Case study description....................................................................................................................234
4.4.3.1 Hydrocensus .....................................................................................................................235
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4.4.3.2 Specialised follow-up sampling campaign......................................................................235
4.4.3.3 Selected boreholes for sampling.....................................................................................236
4.4.3.3.1 Hydrocensus ..........................................................................................................................................................236
4.4.3.4 Selected parameters for sampling..................................................................................236
4.4.3.4.1 Hydrocensus ..........................................................................................................................................................236
4.4.3.5 Rationale for sampling and analysing for the selected chemical parameters .............236
4.4.3.5.1 Hydrocensus ..........................................................................................................................................................236
4.4.3.5.4 Selected sampling frequency ......................................................................................................................237
4.4.3.5.5 Quality assurance and quality control measures ...........................................................................237
4.4.3.6 Exploration borehole drilling...........................................................................................237
4.4.3.7 Downhole geophysics ......................................................................................................238
4.4.3.8 Hydraulic testing ..............................................................................................................238
4.4.3.9 Conceptual model ............................................................................................................238
4.4.3.10 Numerical model ..............................................................................................................238
4.4.4 Results ..............................................................................................................................................239
4.4.4.1 Hydrocensus .....................................................................................................................239
4.4.4.1.1 Exploration borehole drilling and logging............................................................................................239
4.4.4.1.2 Hydraulic testing..................................................................................................................................................239
4.4.4.1.3 Conceptual model..............................................................................................................................................240
4.4.4.1.4 Numerical model ................................................................................................................................................240
4.5 SUGGESTIONS FOR CASE STUDY TWO..........................................................................................................241
4.6 CASE STUDY THREE ........................................................................................................................................245
4.6.1 Case study description ....................................................................................................................245
4.6.3.1 Groundwater sampling methodology.............................................................................247
4.6.3.1.1 Selecting boreholes and springs for sampling..................................................................................248
4.6.3.1.2 Selecting parameters for sampling..........................................................................................................249
4.6.3.1.3 Rationale for sampling and analysing for the selected chemical parameters .............250
4.6.3.1.5 Selected sampling frequency ......................................................................................................................253
4.6.3.1.6 Selected laboratories........................................................................................................................................254
4.6.4 Results ..............................................................................................................................................254
4.7 SUGGESTIONS FOR CASE STUDY THREE .......................................................................................................256
4.8 DISCUSSION ....................................................................................................................................................259
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4.8.1 Case Study One................................................................................................................................259
4.8.2 Case Study Three.............................................................................................................................260
4.9 CONCLUSION ..................................................................................................................................................262
CHAPTER 5 CONCLUSION AND RECOMMENDATIONS ............................................................... 263
REFERENCES ..................................................................................................................... 266
APPENDIX A SUMMARY OF POTENTIAL CONTAMINA TION .................................................................. 293
APPENDIX B INFORMA TION SHEET (HYDROCENSUS FORM ).................................................................. 315
APPENDIX C HYDRAULIC FRACTURING CHEMICAL PARAMETER FROM STUDIES REVIEWED ............................. 317
APPENDIX D CASE STUDIES ...................................................................................................... 334
APPENDIX E CASE STUDY ONE: C ONC EPTUAL SITE MODEL .................................................................. 340
APPENDIX F M ODIFIED PARAMETERS .......................................................................................... 341
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LIST OF TABLES
Table 2.1: Average remaining global technically recoverable natural gas resources ..................11
Table 2.2: EIA/ARI technically recoverable shale gas resource estimates.................................17
Table 2.3: Proven natural gas reserves of the top 10 countries with technically recoverable shale
gas resources ..................................................................................................17
Table 2.4: Total natural gas consumption of the top 10 countries with technically recoverable
shale gas resources, from 2010 to 2040 ..............................................................18
Table 2.5: Purpose and examples of generally used additives in slickwater gelled and foam
treatments......................................................................................................24
Table 2.6: Thirty-five most used chemicals in hydraulic fracturing fluid, together with the
chemical concentration and the most common uses of the chemical.......................26
Table 2.7: The 10 most mobile known organic chemicals from hydraulic fracturing fluids ..........32
Table 2.8: The 10 least mobile known organic chemicals from hydraulic fracturing fluids ..........33
Table 2.9: Commonly used additives in water based and non-aqueous based drilling fluids .......34
Table 2.10: Compilation of desired coal deposit characteristics for underground coal gasification38
Table 2.11: Inorganic and organic composition of underground coal gasification effluent water ..45
Table 2.12: Concentration of selected trace metals in the underground coal gasification solid
residue by-products and tar ..............................................................................48
Table 2.13: Sorb properties of some chemicals produced by underground coal gasification ........49
Table 2.14: Summary of the southern Ecca Formations..........................................................56
Table 2.15: Summary of the northern Ecca Formations ..........................................................57
Table 2.16: Coal quality of the middle Ecca Springbok Flats ....................................................61
Table 2.17: Compilation of desired coal deposit characteristics for underground coal
classification ...................................................................................................63
Table 2.18: Concentration of selected organic parameters from unconventional shale produced
water, presented as average (minimummaximum) .............................................75
Table 2.19: Organic constituentS detected in the flowback water from two unconventional shale
formations ......................................................................................................76
Table 2.20: Compositional comparison between different shales ............................................77
Table 2.21: Compositional ratio comparison between different shales .....................................78
Table 2.22: baseline groundwater concentrations compared to produced water concentrations at

different underground coal gasification sites .......................................................79
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Table 2.23: Comparison of trace element concentration of South African coals with other global
coals (ppm) .....................................................................................................80
Table 2.24: Summary of the volume of water used per well....................................................92
Table 3.1: Baseline water sampling distance required by different states or companies in the
United States of America ................................................................................ 114
Table 3.2: Suggested hydrostratigraphy of the Stormberg and Beaufort groups ..................... 127
Table 3.3: Suggested spacing of the observation wells ....................................................... 132
Table 3.4: Potential constituents expected to be present in shale groundwater after hydraulic
fracturing operations...................................................................................... 141
Table 3.5: Potential constituents which are expected to be present in coal groundwater after
underground coal gasification operations.......................................................... 144
Table 3.6: List of parameters analysed for during groundwater baseline establishment for
unconventional gas projects ............................................................................ 146
Table 3.7: Constituents found in hydraulic fracturing fluid chemicals ................................... 152
Table 3.8: Constituents found in typical water-based and nonaqueous-based drilling fluid ...... 153
Table 3.9: Natural groundwater quality of the Karoo, with ranges which can be expected during
analysis ........................................................................................................ 154
Table 3.10: Suggested parameters to be analysed for during groundwater baseline establishment
for hydraulic fracturing and underground coal gasification operations ................... 156
Table 3.11: List of suggested cations to be analysed for ....................................................... 161
Table 3.12: List of suggested anions to be analysed for ........................................................ 161
Table 3.13: Trace elements in different mediums and studies ............................................... 163
Table 3.14: List of suggested dissolved gases to be analysed for ............................................ 164
Table 3.15: List of suggested isotopes to be analysed for ..................................................... 165
Table 3.16: List of suggested radionuclides to be analysed for .............................................. 166
Table 3.17: List of suggested VOCs to be analysed for .......................................................... 168
Table 3.18: List of suggested SVOCs to be analysed for ........................................................ 169
Table 3.19: List of suggested PAHs to be analysed for .......................................................... 170
Table 3.20: List of suggested phenols to be analysed for ...................................................... 172
Table 3.21: Range of total petroleum hydrocarbon to be analysed for ................................... 173
Table 3.22: Suggested field measurements ........................................................................ 173
Table 3.23: Suggested physical characteristics to be analysed for .......................................... 176
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Table 3.24: Parameters that need to be tested in the field ................................................... 179
Table 3.25: Suggested sampling methods and procedures for the different chemical groups
suggested to be analysed for groundwater baseline establishment for unconventional
gas projects .................................................................................................. 184
Table 3.26: Sampling frequencies suggested and/or practiced in the literature reviewed.......... 192
Table 3.27: Suggested sampling and analysis frequency for shallow (0 to 300 m) boreholes ...... 193
Table 3.28: Suggested sampling and analysis frequency for deep (300 to >1 000 m) boreholes .. 194
Table 4.1: Summary of activities completed before the geohydrological investigation by

Contractor A ................................................................................................. 211
Table 4.2: List of sampled and analysed isotopes together with the rationale for selecting the
specific isotope(s) .......................................................................................... 251
Table 4.3: List of sampled and analysed dissolved gases together with the rationale for selecting
the gases for analysis ..................................................................................... 251
Table 4.4: Indicators of deep groundwater ....................................................................... 252
Table 4.5: Prioritisation of determinants for identifying deep groundwater........................... 260
Table A 1: Summary of potential contamination, due to surface handling and transportation

issues, related to hydraulic fracturing operations ............................................... 293
Table A 2: Summary of potential contamination due to wastewater management and disposal

issues related to hydraulic fracturing operations ................................................ 297
Table A 3: Summary of potential contamination due to well-related issues relating to hydraulic

fracturing operations...................................................................................... 301
Table A 4: Potential contamination of groundwater resources unique to underground coal

gasification operations ................................................................................... 308
Table A 5: Summary of potential contamination, via geology-related issues associated with

hydraulic fracturing and underground coal gasification operations........................ 310
Table D 1: Case Studies list of chemical constituents analysed ............................................. 334
xiv
LIST OF FIGURES
Figure 1.1: Layout of the study ........................................................................................... 6
Figure 2.1: Permeability, quality, cost, technology, size and exploration effort comparison
between unconventional and conventional gas reservoirs ...................................... 8
Figure 2.2: Diagram showing different types of conventional and unconventional reservoirs ......10
Figure 2.3: Correlation between technically recoverable conventional and unconventional gas
resources........................................................................................................11
Figure 2.4: Illustration of the formation of oil and gas from kerogen due to progressive burial ....13
Figure 2.5: Relative depths of the thermogenic celling and biogenic floor ................................14
Figure 2.6: Generalised version of the activities that take place during the operational phase of
hydraulic fracturing operations ..........................................................................19
Figure 2.7: Typical surface infrastructure at a hydraulic fracturing operation............................20
Figure 2.8 : Different casing types.......................................................................................21
Figure 2.9: Generalised slickwater fracturing fluid ratio of different components ......................24
Figure 2.10: Processes controlling the transport of spilled hydraulic fracturing fluid and the
potential paths they may follow towards surface water and groundwater................30
Figure 2.11: Typical surface infrastructure at an underground coal gasification operation using the
parallel Continuous Retraction Injection Point method..........................................40
Figure 2.12: Schematic view of both reverse (a) and forward (b) combustion linking in underground
coal gasification...............................................................................................41
Figure 2.13: Underground coal gasification cavity growth due to gasification .............................42
Figure 2.14: Distribution of the Main Karoo Basin and the Ellisras Basin ....................................51
Figure 2.15: Karoo Supergroup outcrop distribution of the main lithostratigraphic groups ...........52
Figure 2.16: Stratigraphy of the Karoo Supergroup in the Main Karoo Basin of South Africa .........53
Figure 2.17: Stratigraphic cross section along the profile indicated in Figure 2.15 .......................54
Figure 2.18: Stratigraphic correlation between the distal Main Karoo Basin lithostratigraphy and
the Ellisras Basin lithostratigraphy......................................................................54
Figure 2.19: Stratigraphic column of the Waterberg Coalfield, showing the different formations,
coal sequences and the coal qualities of the 11 coal seams ....................................62
Figure 2.20: Groundwater level distribution in South Africa ....................................................66
Figure 2.21: Major physio-chemical distribution throughout the Main Karoo Basin of South
Africa .............................................................................................................68
xv
Africa .............................................................................................................69
Africa .............................................................................................................70
Figure 2.24: Fluoride distribution expressed as geometric means over the Karoo Basin ...............71
Figure 2.25: Areas of characteristic isotope 13C and D values for methane generated by different
mechanisms....................................................................................................72
Figure 2.26: Distribution of different intrusions in the Karoo Supergroup ..................................83
Figure 2.27: Schematic cross section of a breccia pipe ............................................................85
Figure 2.28: Diagram illustrating an idealised hydrothermal vent complex .................................86
Figure 2.29: Distribution of Cretaceous kimberlite dykes (red lines and dots) in and outside of the
Main Karoo Basin.............................................................................................87
Figure 2.30: Simulated movement of pollutants with an input concentration of 100% at the
Cranemere wellpad, under natural conditions (no active pumping) ........................98
Figure 2.31: Simulated movement of pollutants with an input concentration of 100%, where an
abstraction borehole at the Cranemere farm house is introduced, with an abstraction
rate of 0.5 l/s ..................................................................................................98
Figure 2.32: Simulated movement of pollutants with an input concentration of 100%; where a fault
(green line) crosses the area, the pollutant that reaches the abstraction borehole after
10 years has a concentration of 10%...................................................................99
Figure 3.1: Summary of the proposed groundwater baseline methodology for unconventional gas
projects in South Africa................................................................................... 104
Figure 3.2: Illustrating the different quaternary catchments and drainage-rivers which fall in the
hypothetical study area 45 km south-east of Graaff-Reinet .................................. 113
Figure 3.3: Baseline water sampling distance required by different states and companies........ 115
Figure 3.4: Flow diagram of the sequence of conducting the geological and geohydrological
investigation ................................................................................................. 118
Figure 3.5: Average hydraulic conductivity and permeability of different lithologies ................ 126
Figure 3.6: Dedicated borehole construction ..................................................................... 135
Figure 3.7: Flow diagram of the sequence of conducting the initial and subsequent sampling
events .......................................................................................................... 139
Figure 3.8: Generalised flow diagram of groundwater sampling ........................................... 198
Figure 3.9: Proposed groundwater baseline methodology for unconventional gas projects in
South Africa .................................................................................................. 207
Figure 4.1: Flow diagram of the sequence in which activities took place ................................ 210
xvi
Figure 4.2: Activities that were conducted prior to the geohydrological investigation by
Contractor A ................................................................................................. 214
Figure 5.1: Flow diagram for establishing a groundwater baseline for hydraulic fracturing and
underground coal gasification operations.......................................................... 265
Figure A 1: Potential contamination due to surface handling and transportation issues.

Corresponds to Table A1: 1(A) to 1(D) ............................................................... 295
Figure A 2: Potential contamination due to surface handling and transportation issues.

Corresponds to Table A1: 1(E) to 2(A) ............................................................... 296
Figure A 3: Potential contamination due to wastewater management and disposal issues.

Corresponds to Table A2: 1(A) to 4(A) ............................................................... 299
Figure A 4: Potential contamination due to wastewater management and disposal issues.

Corresponds to Table A 2: 5(A) to 7(A) .............................................................. 300
Figure A 5: Potential contamination due to well-related issues. Corresponds to the pathway

numbers listed in Table A 3 ............................................................................. 305


Figure A 8: Potential contamination of groundwater resources unique to underground coal

gasification operations. Corresponds to Table A 4: 1(A) to 6(A) ............................. 309
Figure A 9: Potential contamination due to geology-related issues. Corresponds to the pathway

Figure A 10: Potential contamination due to geology-related issues. Corresponds to the pathway
xvii
LIST OF ABBREVIATIONS AND ACRONYMS
ABA Acid-base accounting

ANC Acid neutralising content
ARD Acid rock drainage
ARI Advanced Resources International
BTEX Benzene, toluene, ethylbenzene and xylene
CBI Confidential business information
CBM Coal bed methane
CCA Council of Canadian Academies
CFB Cape Fold Belt
COD Chemical oxygen demand
COGCC Colorado Oil & Gas Conservation Commission
CRD Cumulative rainfall departure
CRIP Continuous Retraction Injection Point
CSG Coal seam gas
CV Calorific value
DIC Dissolved inorganic carbon
DO Dissolved oxygen
DOC Dissolved organic carbon
DWAF Department of Water and Forestry
DWS Department of Water and Sanitation
EC Electrical conductivity
EIA Environmental Impact Assessment
EM Electromagnetic
EMP Environmental Management Programme
EPH Extractable petroleum hydrocarbons
FC Fixed carbon
FEFLOW Finite Element subsurface FLOW system
FM Formation
GPS Global Positioning System
ICP-MS Inductively Coupled Plasma Mass Spectrometry
MAG Ground magnetic
MCL Maximum contaminant level
MKB Main Karoo Basin
NAF Non-aqueous drilling fluid
NAG Net acid generation
NGA National Groundwater Archive
NGDB National Groundwater Database
NORM Naturally occurring radioactive material
NPC National Petroleum Council
ORP Oxidation reduction potential
xviii
PAH Polycyclic aromatic hydrocarbon
PDB Passive diffusion bag
PVC Polymerising vinyl chloride
REE Rare earth elements
Ro Vitrinite reflectance
RPD Relative percentage difference
SAL Salinity
SANAS South African National Accreditation System
SAWQG South African Water Quality Guidelines
SPE Society of Petroleum Engineers
SPLP Synthetic precipitation leach procedure
Sst Sandstone
SVF Saturated volume fluctuation
SVOC Semi-volatile organic compound
SWiPS Standard Wireline Packer System
TDS Total dissolved solids
TLC Temperature, Water Level and Conductivity
TOC Total organic carbon
TPH Total petroleum hydrocarbon
TS Total sulphur
TWQR Target water quality range
UCG Underground coal gasification
USA United States of America
USEIA US Energy Information Administration
USEPA United States Environmental Protection Agency
VM Volatile matter
VOC Volatile organic carbon
WBF Water-based fluid
WMS Water management system
xix
LIST OF MEASUREMENT UNITS
Bq/R Becquerel per molar gas constant

bcm Billion cubic metre
m3 /d Cubic metre per day
m3 Cubic metre
ha Hectare
km Kilometre
l Litre
l/s Litre per second
MJ/kg Megajoule per kilogram
m Metre
mbgl Metre below ground level
g/l Microgram per litre
M Micrometre
mD Millidarcy
mg/l Milligram per litre
ml Millilitre
mm millimetre
MT Million tonnes
Ma Million years
mS/m Millisiemens per meter
min Minute
min/m Minute per metre
ppb Point per billion
ppm Point per million
tcf Trillion cubic feet
tcm Trillion cubic metre
xx
GLOSSARY OF TERMS
Term Definition
Aquifer An aquifer is a water saturated geological formation that has sufficient

structures or textures to hold or yield water in usable quantities.
Bailers Bailers are tubes used to collect groundwater samples. A check valve at
the bottom of the bailer allows water to enter but seals under the
weight of a water column when it is lifted out of the borehole. They are
inexpensive and simple to operate as they can be lowered into a
borehole on a wire.
Bladder pump A bladder pump is a positive-displacement pumping device that uses
pulses of gas to push a water sample toward the land surface.
Centrifugal pump A centrifugal pump has an electrically driven rotating impeller that
accelerates water within the pump body, building up pressure and
forcing the water sample up the discharge line.
Dedicated boreholes Dedicated boreholes are boreholes which are installed into specific
geological or geohydrological units to be able to collect water samples
from the specific unit.
Flowback water Flowback water or flowback fluid is a mixture of hydraulic fracturing
fluid and formation water that returns to the surface due to pressure
reduction after hydraulic fracturing.
Holding time Holding time is the maximum allowed time that can transpire from the
moment the sample container is filled to the time the sample is
extracted or analysed by the laboratory, with minimal change in
analyte concentration.
Hydraulic conductivity The hydraulic conductivity is the constant of proportionally in Darcy's
law. It is defined as the volume of water that will move through a
porous medium in a unit time under a unit hydraulic gradient through a
unit area measured at right angles to the direction of flow.
Hydrostratigraphic unit A hydrostratigraphic unit is a combination of lithologies or formations
with similar geohydrological properties.
Kerogen Kerogen is a collective name for organic matter and sediment.
Maximum contaminant MCLs are the maximum permissible level of a contaminant in drinking
level (MCL) water.
Passive diffusion bag A PDB is a low-density polyethylene lay-flat tube which can be used to
(PDB) collect representative samples for specific VOCs.
Piston pump A piston pump is a positive-displacement pumping device, where a

piston is driven up and down by gas pressure controlled from the
surface.
xxi
Term Definition
Preferential flow path A preferential flow path is a structure or feature, such as a fracture,
through which water or gas may migrate more easily compared to the
surrounding structures or features.
Produced water Water that returns to the surface with the gas after the well is placed
in production; production water return occurs during the life of a well.
Proppant Granular material, such as silica sand, ceramic media, or bauxite, that
keeps fractures open so that gas can flow to the wellbore.
Purging Purging is the action of removing old stagnant water from a borehole
or well.
Pyrolysis Pyrolysis occurs as coal heats up in the absence of oxygen during

gasification.
Quality control (QC) Quality controls are procedures used to ensure that the laboratory
analytical results accurately express the actual concentrations of
chemicals in groundwater.
Reserve Reserves are a subset of discovered resources which have a specific

probability of being produced.
Resource Volume or amount of the resource contained within a rock formation,
irrespective of the ability to produce it.
Stray gas Gas contained in the geologic formation outside the wellbore that is
accidentally mobilized by drilling and/or hydraulic fracturing.
Synthetic gas Synthetic gas or syngas is produced during UCG operations due to
combustion/gasification of the coal.
Syringe sampler A syringe sampler is a grab sampling device which is used to collect
groundwater samples at specific depths. It can also be used as the
sample container.
Target water quality The TWQR for the South African Water Quality Guidelines for Domestic
range (TWQR) Use is defined as the range of concentrations or levels at which the
presence of the constituent(s) would have no known adverse or
anticipated effects on the fitness of the water assuming long-term
continuous use, and for safeguarding the health of the domestic users.
Technically recoverable Technically recoverable gas resources are the volume of gas that is
gas resource recoverable with the available technology, regardless of oil and natural
gas prices and production costs and is determined by multiplying the
risked gas in place by a recovery factor.
Total organic carbon TOC is a present day measure of organic richness.
(TOC)
xxii
ABSTRACT
A standard methodology for establishing a groundwater baseline for unconventional gas projects in
South Africa did not exist at the time the study was undertaken; therefore, the study was aimed at
filling this gap and establish a groundwater baseline methodology which may be used for
unconventional gas projects in South Africa, specifically for on hydraulic fracturing and underground
coal gasification operations. The study also attempted to answer questions which have not been fully
addressed in available literature on establishing groundwater baselines, such as which chemical
parameters should be analysed for when attempting to establish a groundwater baseline for
unconventional gas projects and whether the drilling of dedicated boreholes are required to collect
representative groundwater samples.
An extensive literature review was conducted in order to establish the baseline methodology. The
latest literature on hydraulic fracturing and underground coal gasification was reviewed to determine
which activities may potentially impact or contaminate the groundwater environment , as well as
which pathways contaminants would follow that might potentially contaminate the groundwater
environment which are unique to South Africa, such as fractures along dolerite intrusions. After
determining these activities and pathways, literature on groundwater baseline establishment were
reviewed to answer questions such as what size the study area should be, what geological and
hydrogeological investigations need to be conducted before embarking on the sampling events, what
chemical parameters need to be analysed for and why, and also how to collect representative samples
for these different chemical parameters.
After these questions were answered and the groundwater baseline methodology established, the
methodology was tested against three case studies on groundwater baseline establishment for
unconventional gas projects in South Africa, to determine how the findings/results of the studies could
have been improved and also to refine/modify the established methodology based on the findings
and results of the case studies.
The improved baseline methodology was then presented in the form of a flow chart to be used to
guide future groundwater baseline establishment projects in South Africa.
It is believed that the methodology utilised reproducible, simple, cost-effective and accurate
techniques to acquire high quality data to establish a groundwater baseline for unconventional gas
projects in South Africa.
Keywords: Unconventional gas; Underground coal gasification; Hydraulic fracturing; Hydraulic

fracturing fluid; Groundwater; Main Karoo Basin; South Africa; Groundwater baseline; Chemical
parameters; Groundwater sampling; Hydrostratigraphic unit; Dedicated boreholes.
xxiii
OPSOMMING
Geen standaard metodologie vir die skepping van 'n grondwaterbasislyn vir onkonvensionele
gasprojekte in Suid-Afrika het ten tye van die huidige studie bestaan nie. Die studie was derhalwe
daarop gemik om hierdie gaping te vul deur 'n grondwaterbasislynmetode daar te stel wat gebruik
kan word vir onkonvensionele gasprojekte in Suid-Afrika, met spesifieke fokus op hidrouliese breking
en ondergrondse steenkoolvergassingsondernemings. Die studie het ook probeer om vrae te
beantwoord wat nog nie ten volle in die beskikbare literatuur aangespreek is oor die vestiging van 'n
grondwaterbasislyn nie, soos die keuse van chemiese parameters vir ontleding wanneer gepoog word
om 'n grondwaterbasislyn vir onkonvensionele gasprojekte vas te stel en of die boor van toegewyde
boorgate nodig sal wees om verteenwoordigende grondwatermonsters te verkry.
'n Uitgebreide literatuurstudie is gedoen om die metodologie daar te stel. Die nuutste literatuur oor
hidrouliese breking en ondergrondse steenkoolvergassing is gebruik om te bepaal watter aktiwiteite
potensieel 'n invloed op besoedeling van die grondwateromgewing sal h, asook watter roetes
besoedeling sou volg wat dalk die grondwateromgewing wat uniek is aan Suid-Afrika, soos frakture
langs doleriet-intrusies, potensieel kan besoedel. Na die bepaling van watter aktiwiteite potensieel 'n
invloed die grondwateromgewing sal h en die paaie wat die besoedeling moontlik sou volg, is
literatuur oor die daarstel van 'n grondwaterbasislyn bestudeer om vrae te beantwoord soos watter
grootte die studie-area moet wees, watter geologiese en hidrogeologiese ondersoeke gedoen moet
word voor die monsterneming gedoen word, watter chemiese parameters getoets moet word en
waarom, en ook hoe om verteenwoordigende monsters in te samel vir die verskillende chemiese
parameters.
Na hierdie vrae beantwoord is en die grondwaterbasislynmetodologie ontwikkel is, is die metode

getoets met behulp van drie gevallestudies op grondwaterbasislynsamestelling vir onkonvensionele
gasprojekte in Suid-Afrika, om vas te stel hoe die bevindinge en resultate van die gevallestudies
verbeter kon word en ook om die gevestigde metode te verfyn of aan te pas deur dit te baseer op die
bevindinge en resultate van die gevallestudies.
Die aangepaste basislynmetodologie is dan in die vorm van 'n vloeidiagram voorgestel om gebruik te
word om toekomstige grondwaterbasislynvestigingsprojekte in Suid-Afrika te lei.
Daar word aanvaar dat die metode reproduseerbare, eenvoudige, koste-effektiewe en akkurate
tegnieke gebruik het om data van 'n ho gehalte te bekom om 'n grondwaterbasislyn vir
onkonvensionele gasprojekte in Suid-Afrika vas te stel.
Sleutelwoorde: Onkonvensionele gas; Ondergrondse steenkoolvergassing; Hidrouliese breking;

Hidrouliese brekingvloeistof; Grondwater; Hoof Karoo-kom; Suid-Afrika; Grondwaterbasislyn;
Chemiese parameters; grondwatermonsterneming; Hidrostratigrafiese eenheid; Toegewyde
boorgate.
xxiv
Chapter 1
INTRODUCTION
1.1 GENERAL
Unconventional natural gas resources have been one of the main exploration targets in recent years
due to the quest for lower carbon emitting gas resources, the fact that conventional natural gas
resources are steadily being depleted locally and internationally, and the prospects of increased gas
production by utilising advanced technology such as hydraulic fracturing and underground coal
gasification (UCG) (Wang and Lin, 2014; Weijermars et al., 2011).
The growing interest in unconventional gas was encouraged by the United States of America (USA)
when the production of shale gas increased tenfold between 2006 and 2010, which led to an
oversupply of liquefied natural gas in the world market and stimulated business and policy interest
around the world (Birol et al., 2012).
The development of unconventional resources around the world has a number of claimed benefits,
such as reducing global energy cost, job creation and supplying energy security to countries that
import their gas supply (Weijermars et al., 2011). It is believed that if South Africa were to develop its
11.0 tcm technically recoverable shale gas resources, and only 0.2 tcm of the total natural gas is
consumed up until 2040 by South Africa, the country would change from being an importer of natural
gas to a prominent exporter of natural gas. Also, it is believed that South Africa would benefit the most
from shale gas development compared to other countries (Melikoglu, 2014). Furthermore, Van der
Riet (2008) stated that almost three quarters of South African coal resources are regarded as
unmineable when considering conventional coal mining techniques and that these resources may
potentially be extracted by utilising UCG.
1.2 BACKGROUND
Although unconventional gas development has had many proponents, hydraulic fracturing and UCG
has had many obstacles hindering their development, such as social, environmental, economic, and
investment concerns (Weijermars et al., 2011). One of the biggest public concerns is the risk of these
unconventional gas resource technologies potentially polluting the potable groundwater in the area
of development (Burton et al., 2006; De Wit, 2011; Steyl et al., 2012).
Cases of alleged groundwater contamination in the USA, due to oil and gas activities, could usually not
be proven because changes in groundwater quality could not be linked to oil and gas activities as a
1
groundwater quality baseline did not exist before oil and gas development started. In the USA, some
states such as Colorado and Ohio require that a groundwater baseline should be established in certain
cases before shale gas development could begin (United States Government Accountability Office [US
GAO], 2012). Esterhuyse et al. (2013) and OBrien et al. (2013) believed that a groundwater baseline
needs to be established in South Africa before undertaking in unconventional natural gas development
to proactively protect South Africas water resources. Furthermore, by establishing a groundwater
baseline prior to unconventional gas activities would have a number of advantages such as (a) to help
resolve disputes regarding the causes of groundwater contamination; (b) to document the existing
groundwater conditions of the site; and (c) the data could lead to more informed policy and regulatory
decision-making.
1.3 PROBLEM STATEMENT

Previously, no methodology had been constructed for establishing a groundwater baseline for
unconventional gas extraction projects in South Africa. The research in this dissertation was aimed at
filling this gap by constructing a standard methodology to be used as a guideline for establishing
groundwater baselines prior to unconventional gas development projects in South Africa, specifically
focussing on hydraulic fracturing and UCG operations.
1.4 AIMS AND OBJECTIVES OF THE STUDY
1.4.1 Overall aim of the study

To establish a groundwater baseline methodology for unconventional gas projects in South Africa,
specifically focussing on hydraulic fracturing and underground coal gasification operations.
1.4.2 Objectives of the study

The following objectives were set to be building blocks to achieve the overall aim of the study:
To determine how unconventional gas is recovered through hydraulic fracturing and UCG
operations and which activities of these operations may potentially impact the groundwater
environment; and the pathways which the contaminants may follow due to the unconventional
gas operations.
To determine where in South Africa the unconventional gas operations might take place and the
geology and geohydrology of these areas which control fluid and gas migrations as well as the
chemical composition of the groundwater in these areas.
To do an extensive literature review on groundwater baseline establishment to determine which
geological and geohydrological investigations need to be conducted before embarking on the
2
initial sampling event, to establish what chemical parameters need to be analysed for, and how to
collect representative groundwater samples for the different chemical parameters.
The study also attempted to provide answers to questions that have not been fully answered in the
existing literature on establishing a groundwater baseline for unconventional gas projects, namely: (a)
during which phase of the unconventional gas project should the baseline be established; (b) what
information should be collected before conducting a sampling event; (c) what size should the study
area be; (d) how should potential groundwater sampling locations be selected; (e) how frequently
should groundwater samples be collected; (f) is drilling of dedicated monitoring boreholes required to
collect representative groundwater samples; (g) what chemical parameters should be analysed; (h)
how to collect representative samples for these different chemical parameters; (i) and what water
quality standards are required for interpreting different chemical constituents that have been
analysed.
1.5 RESEARCH METHODOLOGY

An extensive literature review was conducted to establish the groundwater baseline methodology and
provide answers to questions that have not been fully answered in the existing literature. The latest
publicly available literature on hydraulic fracturing and UCG was reviewed to determine which
activities may potentially impact or contaminate the groundwater environment; and also to determine
which contaminants are found in hydraulic fracturing treatment fluids; and contaminants that are
found in by-products of UCG operations. The geology and geohydrology of the areas in South Africa
where unconventional gas operations might take place were then reviewed.
The potential pathways created due to hydraulic fracturing and UCG operations and also pathways
unique to South Africa were reviewed to determine how contaminants may migrate to groundwater
resources.
After determining which activities may potentially impact the groundwater environment and the
pathways which the contaminants may follow, literature on groundwater baseline establishment were
reviewed to answer questions such as what size the study area should be, what geological and
geohydrological investigations need to be conducted before embarking on the sampling events, what
chemical parameters need to be analysed for, and also how to collect representative groundwater
samples for the different chemical parameters.
After these questions were answered and the groundwater baseline methodology was established,
the methodology was tested against the investigation design, the practices, the results and findings of
three case studies. Two of the case studies were based on establishing groundwater baselines for
unconventional gas projects in South Africa. The aim of the third case study was to determine whether
3
sub-thermal spring water (>25 C) would be a suitable sampling alternative for deep Karoo
groundwater during groundwater hydrochemical baseline studies for shale gas development projects
(hydraulic fracturing). The established methodology was compared to the three case studies to
determine how the practices, results and findings of these studies could have been improved.
The practices as well as the results and findings of these case studies were also used to determine if
the established baseline methodology could be improved or refined.
The refined baseline methodology was presented in the form of a flow diagram which may be used to
guide future hydraulic fracturing and UCG groundwater baseline establishment projects in South
Africa.
1.6 LIMITATIONS
The key limitation of this study was that the established methodology was based on the findings,
results, practices and recommendations made in publicly available reports, manuals, journal articles
and books which covered one or more of the topics which were used to establish the methodology.
None of the recommended activities and steps for establishing a groundwater baseline were
quantitatively tested to determine the validity of the recommended activities, steps and/or
techniques. Therefore, the established methodology is entirely qualitative and is subject to scrutiny.
The unconventional gas resource extraction techniques included for review consideration in this study
were shale gas extraction through hydraulic fracturing and coalbed methane (CBM) (also known as
coal seam gas) extraction through UCG. CBM extraction through CBM extraction techniques, which
are similar to hydraulic fracturing of shale, were not discussed in this study due to time constraints
and the large scope of the work. Tight gas extraction was also not discussed as it was not considered
to be economically recoverable in South Africa at the time of writing this dissertation, with no mention
of it becoming an economically recoverable resource in the near future.
1.7 STRUCTURE OF THE DISSERTATION

The dissertation is structured as follows:
Chapter 1 served as an introduction, contextualising the study by discussing the background and
problem statement of the study and also the research objectives and research methodology upon
which the study is based.
Chapter 2 constitutes the literature study and background to put the findings and established
methodology in context. The chapter discusses the difference between conventional and
unconventional gas, and the techniques that are typically used to extract the different unconventional
4
gas resources. The chapter also discusses the contaminants that are typically associated with these
techniques.
The geology and geohydrology of the Karoo Basin and sub-basin of South Africa are then covered,
focussing on the Karoo Supergroups Ecca Group formations. This is followed by the geological
preferential flow paths that may serve as pathways for contaminant migration in South Africa. The
chapter ends by reporting on the different potential impacts that hydraulic fracturing and UCG
operations may have on groundwater resources.
In Chapter 3 the established groundwater baseline methodology for hydraulic fracturing and UCG
operations in South Africa will be discussed, covering the different activities of establishing a
groundwater baseline, from the desktop study through to finally establishing groundwater quantity
ranges for each hydrostratigraphic unit in the study area.
In Chapter 4 the established groundwater baseline methodology is tested against three case studies
on groundwater baseline establishment for unconventional gas projects in South Africa. After
reviewing the case studies, suggestions are made on how the studies could have been improved.
Lastly, the practices and the results/findings of the case studies are used to determine if the
established methodology could have been improved and refined.
Chapter 5 presents the major findings of the research and also the recommendations for future
research. Also, the refined groundwater baseline methodology is presented in the form of a flow
diagram at the end of the chapter.
Figure 1.1 presents the general layout of the study.
5
Figure 1.1: Layout of the study
6
Chapter 2
LITERATURE REVIEW
2.1 INTRODUCTION
As the primary objective of this research was to establish a groundwater baseline methodology for
unconventional gas projects in South Africa, specifically for hydraulic fracturing and UCG projects, it is
prudent to first review and discuss what makes a natural gas resource unconventional, how the
natural gas is formed, what are the different types of natural gas resources, and how much of these
resources are available globally.
The chapter also focusses on the hydraulic fracturing and UCG extraction techniques which may be
used in South Africa to extract these unconventional gas resources, and also what contaminants may
be associated with these extraction techniques.
As unconventional gas development is most likely to take place in the Karoo Basin, the geology and
geohydrology of the basin will be discussed as the geology and geohydrology control contamination
migration and the groundwater quality. This is followed by a review of the known and speculated
groundwater impacts associated with the hydraulic fracturing and UCG extraction techniques. The
potential groundwater impacts will be discussed as it is essential to be aware of the different potential
impacts, sources of contamination and migration pathways which the contaminants may use to
migrate towards potable groundwater resources as the pathways control the borehole selection
process for aquifer test and groundwater sampling as will be seen in Chapter 3.
2.2 UNCONVENTIONAL GAS RESOURCES
2.2.1 Definition of unconventional gas resources

Unconventional and conventional gas are both natural gas, but what differentiates them from each
other are the geological characteristics of their reservoir rock (because of different host rock
permeabilities), the technology required to produce the gas at economically viable rates, the size of
the resource and how the gas has accumulated (Andrews, 2009) (see Figure 2.1).
A gas reservoir is considered unconventional when the source rock has a permeability of less than
0.1 mD (millidarcy) (Perry and Lee, 2007). The Society of Petroleum Engineers [SPE] (2007) described
unconventional gas as accumulations of petroleum that are found throughout a large area and are
not significantly affected by pressure exerted by water (hydrodynamic influences), whereas
conventional oil and gas accumulations are found in porous and permeable rock such as sandstone
7
under hydrodynamic influences. The hydrocarbons migrate upward from organic sources through
strata until they reach an impermeable cap rock and become trapped in the permeable sandstone
reservoir. According to Perry and Lee (2007) unconventional gas can be defined as natural gas that
cannot be produced at economic flow rates nor in economic volumes of natural gas unless the well is
stimulated by a large hydraulic fracture treatment, a horizontal wellbore, or by using multilateral
wellbores or some other technique to expose more of the reservoir to the wellbore .
Therefore, the separation of unconventional gas from conventional gas generally relies on the
temporally variable measurements of economics and technology required to extract the gas from the
source rock (McGlade et al., 2013).
Figure 2.1: Permeability, quality, cost, technology, size and exploration effort comparison
between unconventional and conventional gas reservoirs
Figure 2.1 indicates that as the permeability of the reservoir decreases from the top of the resource
triangle towards the bottom, so does the quality of the reservoir. The lower permeability reservoirs
are, however, usually much larger than the higher quality reservoirs.
These low-quality natural gas (unconventional gas) deposits require advanced technology and
adequate gas prices before they can be economically produced. The concept of the resource triangle
applies to every hydrocarbon-producing basin in the world (Naik, 2003; Perry and Lee, 2007).
8
2.2.2 Formation of unconventional gas
Unconventional natural gas may be created by two mechanisms:
Biogenic gas is gas that is that is mostly methane which is created by methanogens as a metabolic
by-product in anoxic conditions and are produced near the surface in association with fine-grained
sediments at temperatures lower than 50 C (Booth et al., 1996; Stolper et al., 2014).
Approximately 20% of the worlds natural gas resources are produced by microorganisms
(microbes).
Thermogenic gas is gas that is created under high pressures at depths greater than biogenic g as
and temperatures between 157 C and 221 C from kerogens, which are derived from organic
matter over time within deposits of oil, coal and shale (Cokar et al. 2013).
2.2.3 Main categories of unconventional gas

Unconventional natural gas consists mainly of shale gas, CBM and tight gas (Birol et al., 2012):
Shale gas is a natural gas contained within a fine-grained sedimentary rock called shale which has
a characteristic lower permeability with a limited ability for gas to flow through the rock than in
the case of a conventional reservoir. These shale formations are often rich in organic matter and
act as the original source rock of the gas; the gas remains either trapped in or close to the source
rock and requires techniques such as hydraulic fracturing to increase the permeability of the rock
to allow gas to flow (Pearson et al., 2012; Birol et al., 2012).
Coalbed methane, also known as coal seam gas in Australia, is a natural gas that is adsorbed in
the solid matrix of the coal seams/coal beds, which means the host rock is both the source rock
and the reservoir for the gas. Extraction of CBM through UCG (see Section 2.4) and CBM extraction
technique were initially performed to make mines safer, but is now typically undertaken to
produce methane from un-mineable coal seams (Birol et al., 2012; Pearson et al., 2012).
Tight gas is a natural gas that is found in low permeability formations such as limestone or
sandstone that cannot produce economic amounts of gas without the use of techniques to
stimulate flow of gas towards the well (Birol et al., 2012; Pearson et al., 2012).
Figure 2.2 illustrates the difference between conventional and unconventional gas reservoir types.
9
Figure 2.2: Diagram showing different types of conventional and unconventional reservoirs
2.2.4 Unconventional gas resources

The purpose of this section is to provide global technically recoverable gas resource estimates of
unconventional gas and compare it to conventional gas resource estimates. These estimates are not
accurate because the potential amount and extent of unconventional gas resources are still relatively
unknown. (Shale gas and coal resources will be discussed in more detail in Section 2.3 and 2.4,
respectively).
Table 2.1 indicates the remaining technically recoverable natural gas resources1 according to the
region and type of resource, in trillion cubic meters, from studies conducted by Birol et al. (2012) and
McGlade et al. (2013). According to these authors, unconventional gas resource estimates are difficult
to predict and are ever-changing as further exploration and research are conducted to estimate the
resources.
1
Technically recoverable resources: Volume of gas that is recoverable with the available technology, regardless of oil and
natural gas prices and production costs and is determined by multiplying the risked gas in place by a recovery factor
(McGlade et al., 2013).
10
TABLE 2.1: AVERAGE REMAINING GLOBAL TECHNICALLY RECOVERABLE NATURAL GAS RESOURCES
Total (tcm) Unconventional (tcm)
Region Coalbed
Conventional Unconventional Shale gas Tight Gas
methane
Africa
37.0 37.0 30.0 7.0 0.0
Birol et al. (2012)
Africa
30.9 32.5 29.3 2.3 0.9
McGlade et al. (2013)
Global
421.0 331.0 208.0 76.0 47.0
Birol et al. (2012)
Global
432.5 286.6 193.2 54.2 39.2
McGlade et al. (2013)
Africa average 33.95 34.75 29.65 4.65 0.45
Global average 426.75 308.8 200.6 65.1 43.1
Global percentage
Shale gas 64.96%
Tight gas 21.10%
Coalbed methane 13.95%
Compared to other regions which have technically recoverable natural gas resources, Africa has the
fifth most technically recoverable resources with approximately 37 tcm unconventional natural gas
resources, and Asia/Pacific having the most resources with approximately 93 tcm unconventional
natural gas resources (Birol et al., 2012). It is believed that if Africas unconventional gas resources are
developed effectively, it would lead to substantial investment, economic growth, infrastructure
development, decrease in unemployment and improved social well-being.
Figure 2.3 indicates the volume correlation between conventional and unconventional technically
recoverable gas resources, where conventional gas comprises 58.02%, shale gas 27.27%, tight gas
8.85% and CBM comprises only 5.86%.
Figure 2.3: Correlation between technically recoverable conventional and unconventional gas resources
11
2.3 HYDRAULIC FRACTURING
As stated in Section 2.2.3, shale gas is extracted unconventionally through a process known as
hydraulic fracturing. The purpose of this section is to discuss shale formation mechanisms; how shale
gas is produced; shale gas reservoir properties required for hydraulic fracturing; South African shale
gas resources; and lastly, shale gas recovery through hydraulic fracturing, while focussing on the
different hydraulic fracturing treatment chemicals which may be used, the fate and transport of these
chemicals if spilled on the surface, and also the physiochemical properties which control the mobility
of the chemicals.
It is necessary to be aware of the different chemicals which may be used during hydraulic fracturing
treatment as the chemicals may potentially migrate from the treatment z one into potable
groundwater resources. Furthermore, it is necessary to be aware of the flow pathways which the
chemicals can use to migrate from the wellpad, as this knowledge would help in selecting and installing
new boreholes for groundwater sampling and aquifer tests purposes.
2.3.1 Formation of shales

Shales are typically derived from fine-grained sedimentary rocks that form from compaction of clay
silt-size mineral particles (60.9% clay minerals [illite, kaolinite], 30.8% quartz, 4.5% feldspar, 3.6%
carbonate, 2% other materials such as sulphide minerals and heavy mineral grains, 1% organic matter,
<0.5% iron oxides) (Shaw and Weaver, 1965).
It is generally believed that shales are the product of deposited sediments (mud/clay-sized particles)
and organic matter, in anoxic environments, in quiet water environments as hemipelagic rain. Due
to the growing popularity of organic rich shales and mud rocks as a future long -term energy source,
the prospect of shale gas as long-term energy source led to significant interest in interpreting their
environment of deposition (Abouelresh and Slatt, 2011).
According to Abouelresh and Slatt (2011) the following transport, depositional and reworking
processes for mudstones exist: hemipelagic rain; hyperpycnal flows; turbidity current flows; and
tempestite (shelf storm deposits).
Hemipelagic sediments are sediments which are deposited slowly on continental shelves and rises
(O'Brien and Slatt, 1990). The Prince Albert, Whitehill and Collingham formations of the Karoo
Supergroup are believed to be deposited as pelagic sediments through suspension settling (rain) in
deep marine environments (Kingsley, 1977; Visser, 1991; Visser, 1992).
Gas deposits develop mainly from the accumulation of phytoplankton in marine settings such as the
Whitehill shale of the Ecca group. When, for example, phytoplankton dies, it breaks down to simple
12
molecular constituents such as carbon dioxide (CO2 ) and water (H2 O) through bacterial decay. This
process does not lead to the formation of fossil fuels (coal and petroleum [crude oil and natural gas])
because complex organic hydrocarbon material is not preserved; therefore, suitable source rocks from
which fossil fuels can accumulate must be deposited in reducing environments with suitable
sedimentation rates (not too fast and not too slow).
Petroleum and coal are formed through syndeposition of organic matter and sediments and then
altered through different pressure and temperature stages (see Figure 2.4). When a significant
amount of marine organic matter (12% phytoplankton and zooplankton [Robb, 2013]) is
progressively buried, liberation of CO2 and H2 O occurs and the formation of kerogen (in this case type
II) occurs. Kerogen is a collective name for organic matter and sediment (Bjorlykke, 1989). At around
34 km depth and 100140 C liquid hydrocarbon develops in the interval that is known as the oil
window, and with further burial and cracking of molecular bonds, gas develops (mainly methane
[CH4 ]) (Robb, 2013).
According to Geel et al. (2013), the Whitehill and Collingham formations contain type II kerogen. This
kerogen type is from organic matter such as zooplankton and phytoplankton, and has a sulphur
content of generally between 8 and 14 weight percentage (Tissot et al., 1974).
Figure 2.4: Illustration of the formation of oil and gas from kerogen due to progressive burial
13
2.3.2 How shale gas is produced
Shale gas (predominantly methane) is produced from shale formations through biogenic reactions and
by thermogenic mechanisms, or a combination of biogenic-thermogenic reactions (Curtis, 2002). Dry
gas (methane) is generally formed during the final stage of hydrocarbon maturation at a burial depth
of between 5 km and 6 km (Hunt, 1996).
The biogenic methane gas is generated from either mature or immature organic matter during
diagenesis from anaerobic bacteria (CO2 reduction and fermentation) in areas of fresh water recharge,
whereas the thermogenic methane gas is generated from the thermal cracking of mature complex
organic matter (kerogens) at high temperatures (between 70 C and 250 C) and pressures, and
forming simple hydrocarbons (Cokar et al., 2013; Hunt, 1996; Rokosh, 2009; Stolper et al., 2014).
The produced natural gas is trapped in the shale reservoir due to its low permeability (Golding et al.,
2013). To distinguish between thermogenic and biogenic gas isotopes can be used. Thermogenic gas
generally has a higher 13 C/12 C ratio than that of biogenic gas (Vidic et al., 2013) and also has a higher
13 C CH4 / D CH4 value than biogenic gas (Kaplan et al., 1997).
Natural gas systems are normally placed into three categories (see Figure 2.5):
1. The shallowest system is a favourable environment for microbes to generate methane. The
bottom of this area is the biogenic floor which is at an average depth of 550 m.
2. In the deepest system, the thermogenic kitchen, gas is produced by thermogenesis. This area is
capped off by a thermogenic ceiling. The depth of the ceiling varies with temperature and
geothermal gradient.
Figure 2.5: Relative depths of the thermogenic celling and biogenic floor
14
3. The third system is found between the thermogenic and biogenic systems, and contains displaced
gas from the thermogenic system and some biogenic gas.
2.3.3 Properties of shale gas reservoirs

It is important to note that the term shale is used loosely and does not describe the lithology of the
reservoir. Furthermore, it is necessary to note that not all shales are reservoir rocks and can have the
potential to be a cap or seal rock. American shale gas reservoirs have lithological variations which
indicate that the natural gas is retained in a wide range of lithologies and that the gas is not merely
held in shale but also in mudstone, siltstone, sandstone or any formation which might be of siliceous
or carbonate composition which imbeds the shale laminations/beds (Cramer, 2008; Rokosh, 2009).
The presence of multiple rock formations implies that there are multiple gas storage mechanisms, as
gas may be adsorbed onto organic material and stored as free gas in fractures and pores. These
laminations serve a dual purpose as they both store free gas and transmit desorbed gas to the wellbore
during production (Rokosh, 2009).
It is essential to determine the permeability and porosity of the laminations, and to link these
laminations to the wellbore via hydraulic fracturing for efficient development. For resource and
reserve evaluation of the shale gas reservoir, it is vital to determine the percentage free gas versus
desorbed gas because it is a significant issue in reserve calculation and gas production, as free gas
diffuses at a higher pressure than desorbed gas (Bustin, 2006).
Because of the variety of rock types observed in organic rich shales it implies the presence of a variety
of shale gas reservoirs, where each of these reservoirs may have their own geological and geochemical
characteristics and require their own unique methods of resource and reserve evaluation, drilling,
production and completion (Cramer, 2008).
The four main characteristics in each shale gas reservoir are:
Maturity of the organic matter: Generally, more mature organic matter = higher gas-in-place
resources compared to less mature organic matter, if all other factors are equal. An effective
source rock, which can generate gas, is where the organic maturity, expressed in terms of vitrinite
reflectance (% Ro), has a value above approximately 1.01.1% Ro.
Type of gas generated and stored in the reservoir: Biogenic or thermogenic.
Total organic carbon (TOC) content of the strata: TOC is a present-day measure of organic
richness.
Permeability of the reservoir: Permeability is the most critical factor influencing sustainable shale
gas production (Bennett et al., 1991; Bustin et al., 2008; Rokosh, 2009).
15
Other factors that need to be considered when attempting to locate and produce shale: thickness of
the organic shale; gas generative capacity; kerogen type; percentage of heavy hydrocarbon
components; textural variations; mineralogy; micro-porosity; presence of natural fractures; fresh
water recharge; and brittleness (Rokosh, 2009).
Of all these properties/factors, the TOC content, thickness of organic shale and organic maturity are
the key attributes in determining the economic viability of a shale gas reservoir. There is no unique
combination of these three factors that determines the economic viability of the shale gas reservoir,
but at the lower end of these factors very little gas is generated, and on the other side of the scale
more gas is generated and stored in the shale and this shale can be targeted for exploration and
possible production (Speight, 2013).
The characteristics of a shale formation has major control over the flow rate of gas to the well. For
example, if a shale formation is well-fractured, contains an abundance of mature organic matter and
is under high pressure (deep), the formation will have a high initial flow rate of a few million cubic
metres per day after induced fracturing. However, this rate rapidly declines after the first year by
approximately 5060% (Hayden and Pursell, 2005) after which the gas flow rate will be a function of
the rate of diffusion from the matrix to the induced fractures (Bustin et al., 2008). The average flow
rate per horizontal well after 35 years, with no additional fracturing of the formation, is
approximately 5 66311 326 cubic metre per day with an average decline of 10% per year (Rokosh,
2009).
2.3.4 Shale gas resources in South Africa

The average remaining technically recoverable shale gas in the world is 209.3 tcm, of which South
Africa has 11.0 tcm (Kuuskra et al., 2013).
The top 10 countries with technically recoverable shale gas resources according to the US EIA/ARI
world shale gas and shale oil resource assessment (Kuuskra et al., 2013) are shown in Table 2.2.
Because shale gas is an unconventional gas the technically recoverable resources cannot be used to
make a sound judgement about the role of shale gas in the South African energy market of tomorrow
without taking into account the proven natural gas reserves and the consumption projections
(Melikoglu, 2014).
Therefore, the proven natural gas reserves and consumption projections until 2040 for the top 10
countries listed in Table 2.2 are reported in Table 2.3 and Table 2.4, respectively.
16
TABLE 2.2: EIA/ARI TECHNICALLY RECOVERABLE SHALE GAS RESOURCE ESTIMATES
Trillion cubic feet (tcf) Trillion cubic meter (tcm) Billion cubic meter (bcm)
Rank Country
EIA ARI EIA ARI EIA ARI
1 China 1 115.00 31.60 31 573.20
2 Argentina 802.00 22.70 22 710.10

3 Algeria 707.00 20.00 20 020.00
4 USA 665.00 1 161.00 18.80 32.90 18 830.70 32 875.80

5 Canada 573.00 16.20 16 225.50
6 Mexico 545.00 15.40 15 432.60

7 Australia 437.00 12.40 12 374.40
8 South Africa 390.00 11.00 11 043.50

9 Russia 285.00 8.100 8 070.30
10 Brazil 245.00 6.900 6 937.60
World total 7 299.00 7 795.00 206.70 220.70 206 684.10 220 729.20
Notes:
: No data available
EIA: U.S. Energy Information Administration
ARI: Advanced Resources International
Source: Adapted from Kuuskraa et al. (2013)
The role of shale gas development will only be discussed for South Africa. The other countries are only
included to provide perspective. The data presented in Table 2.3 are from 2012 to 2015.
TABLE 2.3: P ROVEN NATURAL GAS RESERVES OF THE TOP 10 COUNTRIES WITH TECHNICALLY
RECOVERABLE SHALE GAS RESOURCES
Country Natural gas reserves (tcm)
China 4.6
Argentina 0.3
Algeria 4.5
USA 9.6
Canada 2.0
Mexico 0.5
Australia 0.9
South Africa 0.016
Russia 47.8
Brazil 0.5
World total 197.4
Source: Adapted from US EIA (2012)
Table 2.4 is adapted from Melikoglu (2014), who analysed the role of shale gas in the global energy
market using data from the U.S. Department of Energy, Energy Information Agency (US EIA). Melikoglu
calculated the total natural gas consumption of the top 10 countries with technically recoverable shale
gas resources by carrying out a regression analysis using the average annual percentage change in
natural gas consumption data between 2010 and 2040. The data is provided in column 4 of Table 2.4.
17
TABLE 2.4: TO TAL NATURAL GAS CONSUMPTION OF THE TOP 10 COUNTRIES WITH TECHNICALLY
RECOVERABLE SHALE GAS RESOURCES, FROM 2010 TO 2040
Average annual percentage
Total natural gas Total natural gas
Country change in natural gas
consumption in 2010 (tcm) consumption until 2040 (tcm)
consumption, 20102040
China 0.107 5.3 7.9
Argentina 0.043 2.0 1.8
Algeria 0.029 3.1 1.5
USA 0.682 0.7 23.6
Canada 0.082 1.7 3.3
Mexico 0.065 3.6 3.6
Australia 0.033 1.7 1.4
South Africa 0.004 3.1 0.2
Russia 0.424 0.9 15.0
Brazil 0.025 3.9 1.5
World total 3.209 1.7 128.7
Source: Adapted from Melikoglu (2014)
From Table 2.2 it can be seen that South Africa has an estimated 11.0 tcm technically recoverable
shale gas resources, which is 690 times the proven natural gas reserves of 0.016 tcm (US EIA, 2012),
which makes South Africa a good candidate country for shale gas development. Table 2.4 is adapted
from Melikoglu (2014), who analysed the role of shale gas in the global energy market using data from
the U.S. Department of Energy, Energy Information Agency (US EIA). Melikoglu calculated the total
natural gas consumption of the top 10 countries with technically recoverable shale gas resources by
carrying out a regression analysis using the average annual percentage change in natural gas
consumption data between 2010 and 2040. The data is provided in column 4 of Table 2.4.
Table 2.4 shows that in 2010, South Africas natural gas consumption was 0.004 tcm, and it is
estimated that up until 2040 the total amount of natural gas consumption will be 0.2 tcm.
If 100% of the 11.0 tcm technically recoverable shale gas resources are developed and 0.2 tcm of the
total natural gas is consumed by South Africa up until 2040, the country would change from being an
importer to a prominent exporter of natural gas (Melikoglu, 2014).
2.3.5 Shale gas recovery through hydraulic fracturing

There are several different types of hydraulic fracturing techniques; the technique used depends on
the type of reservoir (Fink, 2013). The conventional method used for hydraulic fracturing of shale
reservoirs is using water-based slickwater as fracture treatment, which will possibly also be utilised in
South Africa (Republic of South Africa. Department of Mineral Resources [RSA DMR], 2012).
18
Hydraulic fracturing is the process of injecting fluids under high pressure into the low permeability
shale reservoir (less than 0.1 mD) to fracture the rock and release gas. It is a short-term process by
itself, it only takes about 10 days, whereas the entire operation of hydraulic fracturing, from
exploration and site assessment to site and well closure, can last 560 years (see Figure 2.6). The time
it takes depends on the rate of gas depletion, production cost and gas price (United States
Environmental Protection Agency [USEPA], 2015b).
Figure 2.6: Generalised version of the activities that take place during the operational phase
of hydraulic fracturing operations
Shales gas has long been produced from natural fractures. It has, however, become possible to create
artificial fractures around well bores; the process is known as hydraulic fracking (Sumi, 2008).
The first use of shale gas in the USA was in 1821 when a shallow well was drilled into the Devonian
Dunkirk shale in New York, and the first use of hydraulic fracturing was in 1947 by the Pan American
Petroleum Corporation in the Hugoton gas field in Grant County, Kansas (Curtis, 2002).
2.3.5.1 Description of hydraulic fracturing operations
In this section the activities that take place from the initial site development through to production
and closure will be covered. It should be noted that the details of a specific well preparation and
operation differ from company to company and area to area, therefore, a generalised version is
presented here.
2.3.5.1.1 Exploration, site assessment and development phase
Before hydraulic fracturing can commence, exploration, site assessment and well/site development
activities have to be completed. Examples of exploration and site assessment practices include:
Geophysical surveys to delineate subsurface features.
19
Drilling for rock core samples, which provide information on the underlying geological formations,
such as thickness, extent, porosity, permeability, and also the quality and quantity of the shale
(USEPA, 2015b).
Some of the factors that are taken into account when choosing a site for hydraulic fracturing
operations are: topography, sensitivity of the environment, proximity to cities (Arthur et al., 2009).
After an area has been chosen and the oil and gas company has granted a drilling permit, the site has
to be developed. During site development, the site must be prepared for equipment to reach the well
area; this includes building of access roads for vehicles, levelling the area and removing vegetation.
The operator should then excavate storage pits for flowback and produced water and drilling mud
(the fluids may also be kept in storage tanks), holes must then be dug for pipes which transport fluids
to and from the wellhead (Arthur et al., 2009).
After site preparation and development, drill rigs, drilling platforms, drilling mud components, storage
tanks, blowout preventers, different drill pipes and casings and pumps can be moved on and off the
wellpad during the life of the operation until site closure. See Figure 2.7 for the generalised surface
infrastructure at a typical hydraulic fracturing operation.
Figure 2.7: Typical surface infrastructure at a hydraulic fracturing operation
2.3.5.1.2 Well drilling and construction
The construction of the production well involves different drilling stages together with the installation
and cementation of different casings which mainly serve to support the wellbore and to prevent the
unwanted release of hydrocarbons into the environment (USEPA, 2015b).
20
The wells are drilled vertically and are progressively deviated to the horizontal, from the kick-off
point into the target shale formation. Therefore, the horizontal part which is termed lateral, is in
contact with the producing shale over significantly longer distances (50100 m compared to tens of
metres in the vertical) which optimises the natural gas recovery (Ground Water Protection Council,
2009; Wang et al., 2014).
As drilling proceeds deeper and deeper with repeated addition of drilling rods, different casing
diameters are installed and cemented into the drilled holes which become successively smaller in
diametre with increased depth (USEPA, 2015b). The specific casing is installed and cemented into
place before deeper drilling continues (Council of Canadian Academies [CCA], 2014). (See Figure 2.8
for the different casing types).
The general purpose of the casings is to isolate hydrocarbons from aquifers, and transport
hydrocarbons to the surface (Hyne, 2012). The conductor casing string forms the outer barrier closest
to the surface and keeps the upper portion of the well from collapsing. The surface casing protects
surface water and shallow aquifers from contamination. The intermediate casing is used to keep the
borehole stable, it is also serves to isolate any non-economically recoverable gas it may intersect. The
production casing is used to transport the hydrocarbons to the surface (CCA, 2014).
Once well construction is completed for all the wells that will be hydraulically fractures, the drill rig is
removed, and a wellhead installed with attachments such as a blowout preventer and prepared for
well stimulation by hydraulic fracturing and finally gas production (USEPA, 2015b).
Figure 2.8 : Different casing types
21
2.3.5.1.3 Setup and hydraulic fracturing
Hydraulic fracturing is a short, intense, repetitive process which requires machinery and equipment
which are brought to the site and remain there during use.
After the surface equipment and machinery have been installed, the required hydraulic fracturing
chemicals/additives are mixed together with water and proppant in a truck-mounted blender; the
hydraulic fracturing fluid is then transferred to the pump truck by pipes and hoses from where the
fluid is pumped under high pressure down the wellhead. The fracture fluid generally consists of
approximately 98% water and sand (as proppant), and the rest are chemical additives which improve
the effectiveness of the fracturing (Gandossi, 2013; Ground Water Protection Council, 2009).
The entire length of the production zone is not fractured all at once. The length of the well is divided
in 10 to 15 segments, with lengths between 5 m and 15 m (Lowe et al., 2013), with the distance
between the segments ranging from 100 m to 300 m (Rivard et al., 2012). A segment is then
perforated and fractured by hydraulic fracturing fluid and sealed off from the next segment with a
packer. Each well consumes on average 17 000 cubic metres of water (Rivard et al., 2012).
Fracturing usually takes place from the furthest point in the production zone, known as the toe, and
continues towards the heel of the production zone. It is vital to integrate the produced fracture system
to the natural fracture system in the shale gas reservoir because the natural fracture system can
enlarge the transport channels and increase the specific surface of the shale (Ding et al., 2013).
After hydraulic fracturing, the packers which isolate the segments from one another, are drilled out,
the pressure is reduced and some of the hydraulic fracturing fluid, together with naturally occurring
fluids and gas from the production zone, return to the surface (Mair et al., 2012). This fluid is known
as flowback fluid or flowback water. After a few weeks, the water that returns to the surface is
predominantly water from the fractured rock formation and is known as produced fluid or produced
water. In general, 3040% of the injected fluid will be recovered, but can, however, be much less (King,
2012; Rivard et al., 2012).
The wastewater (flowback water and produced water) is kept on-site in lined ponds or storage tanks
(see Figure 2.7). The water is generally moved off-site by trucks or pipes and disposed by injection in
Class II disposal wells or treated to acceptable levels at a water treatment plant (CCA, 2014).
2.3.5.1.4 Gas production
After hydraulic fracturing, when no more well-drilling is planned, the site equipment is removed,
storage pits are filled and the wellpad size is reduced to 0.4 ha. The produced gas flows from the well
22
to a separator through flowlines, from where the gas is separated from other liquids, the gas is then
sent to a compressor station where the gas is compressed and from there sent to a pipeline for sale.
In the Karoo, the predicted production duration from a well may be as long as 4060 years because of
the low permeability of the shales due to depth (Ross and King, 2007; Rowsell and De Swardt, 1976).
2.3.5.1.5 Site and well closure
Once a well no longer produces gas at economical rates it is plugged, the well site is shut down and
the surface area undergoes reclamation to the extent possible. The wells are usually plugged with
cement across fresh water formations or formations that contain gas (National Petroleum Council
[NPC], 2011).
2.3.5.2 Hydraulic fracturing additives
Different types of hydraulic fracturing fluids can be used to hydraulically fracture shales. Each type of
base fluid used has its own characteristics, advantages and disadvantages and must meet a number
of requirements, while being able to create conductive paths for gas migration from the formation to
the wellbore and carry proppant material into fractures to keep the fractures open (Fink, 2013).
The predominant and most basic fluid currently being used for fracture treatment is water-based
slickwater. It has a low viscosity (due to the majority of additives which are used to reduce the
viscosity) and generates complex fractures with lengths exceeding the widths, which increases the
reservoir to wellbore connectivity. Because of the low viscosity of the fluid, higher pumping rates are
required to overcome the proppants tendency to settle out before being evenly distributed
throughout the fracture network, resulting in poor connectivity and productivity. Linear and
crosslinked fluids (see Table 2.5) containing gel have, therefore, been used to reduce this concern as
the high viscosity gel (for example guar) carries the proppant more efficiently towards the open
fractures (Fink, 2013; Gandossi, 2013). The general composition of slickwater is presented in Figure
2.9.
23
Figure 2.9: Generalised slickwater fracturing fluid ratio of different components
From Figure 2.9 it can be seen that water and sand make up the majority of the fluids with 99.55%,
and the remaining 0.44% consisting of a variety of chemicals which serve different purposes. The
purpose(s) of these additives are listed in Table 2.5. The colours of the additive types in Table 2.5
match the colours used in Figure 2.9 for the same additive types.
TABLE 2.5: P URPOSE AND EXAMPLES OF GENERALLY USED ADDITIVES IN SLICKWATER GELLED AND FOAM
TREATMENTS
Additive type Purpose and description Common additives
Water Fresh water (>500 parts per million TDS)
Keeps fractures open to allow gas migration Sand (quartz), clay or alumina ceramics,
Proppant
towards the wellbore sintered bauxite, magnesium silicate
Acid Prevents iron build-up, adjust pH, clean the well Hydrochloric acid
Reduces friction pressure (drag-on tubing) which

Friction Non-acid form of polyacrylamide, hydrotreated
subsequently reduces the required pumping
reducer light petroleum distillate, mineral oil
energy required to fracture the rock
Disinfectant Prevents the growth of bacteria which causes Glutaraldehyde

(Biocide) decay in gelled fluid 2,2-dibromo-3-nitrilopropionamide
Aids in fluid recovery by modifying tension at the

Napthalene, methanol, isopropanol,
Surfactant surface and interfaces, and prevents emulsions of
ethoxylated, alcohol
gases
24
Additive type Purpose and description Common additives
Can be used in linear and cross-linked gels with

Borate salts, potassium hydroxide,
Crosslinker the advantage of increased vis cosity that does
ethylene glycol
not break down quickly
Prevents formation plugging by deposited and Polymer phosphate esters phosphonates,

Scale inhibitor
crystalising minerals ethylene glycol, ammonium chloride
Corrosion N,N-dimethylformamide, methanol,

Prevents rusting of pipes and connectors
inhibitor ammonium bisulphate, isopropanol
Used to reduce the viscosity of gels, which causes

the release of proppants into fractures, and
Breaker Peroxydisulphates, sodium, chloride
subsequently allows liquefied gels to return to
the surface
Clay Prevents the blocking of fractures by preventing Potassium, chloride, salts (e.g., tetramethyl
stabilisation the swelling and migration of clay minerals ammonium chloride)
Prevents iron oxide precipitation (iron Citric acid, glucono-lactone,

Iron control
precipitation may decrease permeability) ethylenediaminetetraacetic acid
Guar gum, cellulose polymers (hydroxyethyl

Increase the viscosity of the fluid which enables it
Gelling agent cellulose), hydrotreated light petroleum
to carry more proppant into fractures
distillates
pH adjusting Enhances the effectiveness (stability) of other Sodium or potassium carbonate, acetic acid,
agent additives by controlling the pH of the fluid carbonic acid, potassium hydroxide
Other additives that are not generally used in slickwater
2-Butoxyethanol,
Help disperse one immiscible fluid into another
Emulsifier polyoxyethylene(10)nonylphenyl ether;
by reducing the surface tension
methanol, nonyl phenol ethoxylate
Non- Separates problematic emulsions in the Methanol, nonyl phenol ethoxylate,

emulsifiers formation isopropanol
Foaming
Stabilises foam fracturing fluids Nitrogen, isopropanol, methanol, ethanol
agent
Source: Adapted from CCA (2014), Fink (2013) and USEPA (2015c)
This general order according to which the additives are used is not followed by most competing
companies, who prefer to use their own sequence and chemical mixtures which might offer them an
advantage over other companies. Because of this specific reason companies are reluctant to disclose
the composition of their fracking fluid, which makes it difficult to determine which chemicals to
analyse and sample for during groundwater baseline establishment. The operators may also decide to
change the composition of the fluid over time to meet certain requirements (for example, pumping
rates, enhance stability of additives) (Arthur et al., 2008; CCA, 2014; King, 2012).
The general order and the type of additives to use depends on the site conditions, the local geology
and the companys experience tasked with conducting the hydraulic fracturing. Generally, the fluids
25
that are injected first are friction reducers, clay stabilisers and flow facilitators to create the fractures
in the shale. After the fractures have been created, granular material such as sand is added to prop
open the fractures, and gelling agents such as gaur are added to increase the viscosity of the fluid to
increase the carrying capability of the fluid into the fractures. The breakers in the gelling agents are
activated after the proppants (sand) have been emplaced, which causes the gel to liquefy. This
promotes flowback and recovery of the fracturing fluid and also allows gas to flow through the induced
and natural fracture system towards the surface through the production casing (CCA, 2014).
Table 2.6 provides a list of the 35 most used additives in the hydraulic fracturing treatment fluid. This
list is compiled from 10% of the disclosures made to FracFocus2 (a US national hydraulic fracturing
chemical registry) between 2011/01/01 and 2013/02/28 (USEPA, 2015a; USEPA, 2015b).
From the table, it is clear that the five most used additives are hydrochloric acid, methanol,
hydrotreated light petroleum distillates, isopropanol and water. Of these five additives water had the
highest median maximum concentration in the hydraulic fracturing fluid with a concentration of 63%.
Furthermore, it can be seen that although peroxydisulphuric acid; 2,2-dibromo-3-nitrilopropionamide;
choline chloride; carbonic acid; formic acid; and polyethylene glycol are only present in 27.2%, 21.6%,
14.6%, 12.7%, 12.5% and 10% of disclosures, respectively, they have median maximum concentrations
of more 50% in the hydraulic fracturing fluids in which they have been used.
TABLE 2.6: THIRTY-FIVE MOST USED CHEMICALS IN HYDRAULIC FRACTURING FLUID, TOGETHER WITH THE
CHEMICAL CONCENTRATION AND THE MOST COMMON USES OF THE CHEMICAL
Median maximum
concentration in Common uses of these chemical
Number of Percentage of
Chemical name hydraulic additives, according to the
disclosures disclosures
fracturing fluids FracFocus database 3
(% by mass)
Acids, solvents, scale control,
Hydrochloric acid 12 351 72.8% 15%
clean perforations
Corrosion inhibitors, surfactants,

Methanol 12 269 72.3% 30%
non-emulsifiers, scale control
Friction reducers, gelling agents
Hydrotreated light
11 897 70.1% 30% and gel stabilizers, crosslinkers and
petroleum distillates
related additives, viscosifiers
Corrosion inhibitors, non-

Isopropanol 8 008 47.2% 30%
emulsifiers, surfactants, biocides
Acids, biocides, clay control, scale

Water 7 998 47.1% 63%
control
2
There are many different types of chemicals that can be used during hydraulic fracturing treatment, therefore it would not
be practical to list all the chemicals that can, and have been used, and therefore the reader is referred to the FracFocus
database (https://fracfocus.org/data-download-form) for a full list of known chemicals used in hydraulic fracturing.
3
https://fracfocus.org/data-download-form
26
Median maximum
(% by mass)
Surfactants, biocides, corrosion
Ethanol 6 325 37.3% 5% inhibitors, fluid foaming agents
and energisers
Corrosion inhibitors, inhibitors,
Propargyl alcohol 5 811 34.2% 10%
acid inhibitors, base fluids
Biocides, surfactants, crosslinkers

Glutaraldehyde 5 635 33.2% 30%
and related additives, sealers
Crosslinkers and related additives,
Ethylene glycol 5 493 32.4% 35% scale control, corrosion inhibitors,
friction reducers
Iron control agents, scale control,
Citric acid 4 832 28.5% 60% gelling agents and gel stabilisers,
pH control

Sodium hydroxide 4 656 27.4% 5%
biocides, pH control, scale control
Breakers and breaker catalysts,
Peroxydisulphuric acid,
4 618 27.2% 100% oxidisers, stabilisers, clean
diammonium salt
perforations
Breakers and breaker catalysts,
gelling agents and gel stabilisers,
Quartz 3 758 22.1% 10%
scale control, crosslinkers and
related additives
Biocides, clean perforations,
2,2-Dibromo-3-
3 668 21.6% 100% breakers and breaker catalysts,
nitrilopropionamide
non-emulsifiers
Breakers/breaker catalysts,
Sodium chloride 3 608 21.3% 30% friction reducers, scale control,
clay control
Gelling agents and gel stabilisers,
Guar gum 3 586 21.1% 60% viscosifiers, clean perforations,
breakers and breaker catalysts
pH control, iron control agents,
Acetic acid 3 563 21.0% 50%
acids, gelling agents and stabilisers
Surfactants, corrosion inhibitors,

2-Butoxyethanol 3 325 19.6% 10% non-emulsifiers, fluid foaming
agents and energisers
Surfactants, non-emulsifiers,
Naphthalene 3 294 19.4% 5%
corrosion inhibitors, inhibitors
Solvent naphtha, Surfactants, non-emulsifiers,

3 287 19.4% 30%
petroleum inhibitors, corrosion inhibitors
Quaternary ammonium
compounds, benzyl- Biocides, non-emulsifiers,
3 259 19.2% 7%
C12-16-alkyldimethyl, corrosion inhibitors, scale control
chlorides
27
Median maximum
(% by mass)
Potassium hydroxide 2 843 16.8% 15% pH control, friction reducers,
gelling agents and gel stabilisers
Friction reducers, crosslinkers and
Ammonium chloride 2 483 14.6% 10% related additives, scale control,
clay control
Clay control, clean perforations,
Choline chloride 2 477 14.6% 75%
base fluids, biocides
Poly(oxy-1,2-
ethanediyl)- Surfactants, friction reducers,
2 455 14.5% 5%
nonylphenyl-hydroxy non-emulsifiers, inhibitors
(mixture)
Breakers/breaker catalysts,
Sodium chlorite 2 372 14.0% 10%
biocides, oxidisers, proppants
1,2,4-Trimethyl- Surfactants, non-emulsifiers,

2 229 13.1% 1%
benzene corrosion inhibitors, inhibitors
Carbonic acid, pH control, proppants, acids,

2 154 12.7% 60%
dipotassium salt surfactants
Proppants, crosslinkers and

Methenamine 2 134 12.6% 1% related additives, biocides, base
fluid
Corrosion inhibitors, acids,

Formic acid 2 118 12.5% 60%
inhibitors, pH control
Didecyl dimethyl
2 063 12.2% 10% Biocide, non-emulsifier
ammonium chloride
Corrosion inhibitors, acid
N,N-Dimethyl-
1 892 11.2% 13% inhibitors, clean perforations,
formamide
biocides
Proppants, biocides, clean
Phenolic resin 1 852 10.9% 5%
perforations, base fluid
Corrosion inhibitors, acid

Thiourea polymer 1 702 10.0% 30% inhibitors, clean perforations,
biocides
Biocides, non-emulsifiers,
Polyethylene glycol 1 696 10.0% 60%
surfactants, clay control
Source: Adapted from USEPA (2015b)
2.3.5.3 Fate and transport of hydraulic fracturing fluid spills
Spills of hydraulic fracturing fluid on the surface can follow different paths towards groundwater and
surface water resources (see Figure 2.10).
28
During migration, these chemicals may undergo different processes:
Chemicals may transform due to different reactions (for example, biodegradation and oxidation).
The chemicals may volatise and migrate to the atmosphere.
The chemicals may leach into the soil and reach the groundwater or partition in the soil and form
ponds.
The chemicals may reach surface water resources through surface runoff.
Whatever path the spilled chemicals may take, the impact depends on the specific environment al
conditions; the volume and concentration of the spill; the climate and weather during the spill; and,
most importantly, the chemical properties and the point of chemical mixing that was taking place
during the spill. For instance, if the chemicals are not mixed with the base fluid (for example, water)
the chemicals are in their most concentrated form, whereas if the chemicals were mixed with the base
fluid, the chemicals will be diluted. If the chemicals have already been mixed, interactions between
the chemicals may have taken place, changing the chemical characteristics of the chemicals present
(USEPA, 2015b).
The general properties which control the fate and transport of inorganic chemicals are pH, organic
matter, cation exchange capacity, major ion chemistry and oxidation state of chemicals present.
Furthermore, the factors controlling the transport of these inorganic chemicals into groundwater are
the nature of groundwater flow and flow through the unsaturated zone. Non-reactive inorganic
chemicals move with their carrier liquid and are driven by physical flow processes such as advection
and dispersion. Which of these physical flow processes will be the dominant transport mechanism
depends on the environment and the chemical (USEPA, 2015b; USEPA, 1996).
Being aware and taking into account the fate and transport, as well as the physiochemical properties
of specific chemicals when establishing a methodology for establishing a groundwater baseline for
hydraulic fracturing operations (and also UCG operations) is essential, as it would aid in determining
the distance and depth from the wellpad to sample for specific chemicals.
2.3.5.3.1 Flow paths
When released on surface, the chemical additives in hydraulic fracturing fluid may travel along
different paths as shown in Figure 2.10. The spilled fluid may (A) infiltrate/leach into the underlying
unsaturated zone/soil from where it may precipitate or reach the groundwater; and it may also
(B) travel laterally in the unsaturated zone and reach the surface water. The fluid may (C) flow
overland and potentially reach surface water, and the fluids may (D) move between surface water and
groundwater, depending on whether the stream is a losing or gaining stream.
29
Figure 2.10: Processes controlling the transport of spilled hydraulic fracturing fluid and the potential paths they may
follow towards surface water and groundwater
P a t h s A , B a n d D M o v e m e n t t h r o u gh t h e s u b s u r f ac e
When a spill occurs on the surface, the movement of the spills through the unsaturated zone is
controlled by the depth of ponding (which is a factor of the volume of the spill); capillary forces in the
subsurface (cohesion and adhesion); gravity driven flow; infiltration mechanisms (for example,
fractures); and interflow (Fetter and Willard, 2001; USEPA, 2015b). Some of the chemicals may be
sorbed to the soil, while other reach the groundwater or surface water. The sorbed chemicals may be
mobilised in the future due to precipitation events, or because they sorbed to chemicals which
increased their solubility (for example, dissolved organic carbon). When the fluids reach the
groundwater, they generally move in the direction of groundwater flow, except, for example, dense
non-aqueous phase liquids (DNAPLs) such as coal tar (Pretorius, 2007). Fluids are generally
transported furthest in systems of high groundwater flow rates and recharge (USEPA, 2015b).
P a t h C M o v e m e n t a c r o s s t h e l a n d s u r f ac e
Overland flow generally occurs if the soils have low permeability. During overland flow the liquids may
sorb onto soil particles and leach into the unsaturated zone and reach the groundwater through
infiltration or surface water bodies through lateral flow, while the remaining liquid may reach surface
water bodies. The spill type affects the pollution spread on surface; when a blowout or tank failure
occurs greater overland flow will occur and less soil infiltration, whereas a slow leak from a pipe can
cause the liquid to pond and the spreading will be slow (USEPA, 2015b).
30
2.3.5.4 Physiochemical properties and mobility of chemicals
It is necessary to consider the physiochemical properties and mobility of elements when establishing
a groundwater baseline for hydraulic fracturing operations as it would aid in determining where new
boreholes should be installed and which boreholes should be selected to sample for specific chemicals
at a specific distance from the wellpad.
The physiochemical properties that are used to describe the movement of chemicals are:
Kow (octanol water partitioning coefficient): Used to determine whether a chemical will sorb to
organic matter hydrophobic (log Kow >0), or stay in water hydrophilic (log Kow <0).
Aqueous solubility: Quantity of a pure chemical that will dissolve in water.
Henrys law constant: Used to determine whether a chemical will volatise or remain in the water.
It is a ratio between concentrations of a chemical in air : concentration in water.
USEPA (2015) estimated and measured physiochemical properties of 453 chemicals of 1 076 listed as
used in hydraulic fracturing; although some of these chemicals are deemed as confidential business
information (CBI). The results of this study indicated that the physiochemical properties of the known
and CBI chemicals are similar; they cover similar ranges which suggest that although the CBI chemicals
are not publicly known, they have the same physiochemical properties (they move in the same
manner) as the known chemicals, which suggest that the fate and transport of the known and
unknown chemicals are generally the same (USEPA, 2015b).
Table 2.7 indicates the 10 most mobile chemicals known to be used in hydraulic fracturing fluids from
453 chemicals. They are ranked according to their log Kow values. Other physiochemical properties are
included as well as the frequency of use based on FracFocus disclosures from 2011 to 2013 (USEPA,
2015a).
From the table, it can be seen that the most mobile chemicals have the lowest log K ow values and are
fully miscible [1.00 106 (mg/l @ 25 C)] which means that they can move with water through the
environment at high concentrations, which may lead to greater severity impacts. They also have
negative log Henrys law constants and will therefore not volatilise but remain in the water.
After spillage and heavy precipitation, these chemicals will dissolve in water and follow the paths
mentioned in 2.3.5.3.1. Due to this combination of properties, these chemicals have a greater
potential to reach groundwater and surface water resources (USEPA, 2015b).
31
TABLE 2.7: THE 10 MOST MOBILE KNOWN ORGANIC CHEMICALS FROM HYDRAULIC FRACTURING FLUIDS
Estimated
Estimated
Percent Henry's law
Estimated water
of wells constant
Rank Chemical name log Kow solubility
(USEPA, (atm
(unitless) (mg/l @
2015a) m3/mole
25C)
@ 25 C)
1,2-Ethanediaminium, N,N'-bis[2- [bis(2-
1 hydroxyethyl)methylammo nio]ethyl]-N,N'-bis(2- 2.0% 23.19 1.00 10 6 2.33 10 35
hydroxyeth yl)-N,N'-dimethyl-, tetrachloride
Phosphonic acid, [[(phosphonomethyl)imino]bis
2 0.2% 9.72 1.00 10 6
[2,1-ethanediylnitrilobis (methylene)]]tetrakis-
3 [2,1-ethanediylnitrilobis (methylene)]]tetrakis-, 0.07% 9.72 1.00 10 6
sodium salt
4 [2,1-ethanediylnitrilobis (methylene)]]tetrakis-, 9.72 1.00 10 6
ammonium salt (1:x)
Phosphonic acid, (((2-[(2-
hydroxyethyl)(phosphonomethyl)
5 6.73 1.00 10 6 5.29 10 42
amino)ethyl)imino]bis(methylene
))bis-, compd. with 2-aminoethanol
2-Hydroxy-N,N-bis(2- hydroxyethyl)-N-
6 6.70 1.00 10 6 4.78 10 19
methylethanaminium chloride
7 N-(3-Chloroallyl) hexaminium chloride 0.02% 5.92 1.00 10 6 1.76 10 8
3,5,7-Triazatricyclodecane, 1-(3- chloro-2-
8 5.92 1.00 10 6 1.76 10 8
propenyl)-, chloride, (Z)
(2,3-dihydroxypropyl) trimethylammonium
9 5.80 1.00 10 6 9.84 10 18
chloride
10 0.01% 5.79 1.00 10 6
[6,1-hexanediylnitrilobis (methylene)]]tetrakis
Note:
: No values available
Table 2.8 indicates the 10 least mobile chemicals known to be used in hydraulic fracturing fluids from
453 chemicals. They are ranked according to their log Kow values. Other physiochemical properties are
included, as well as the frequency of use based on FracFocus disclosures from 2011 to 2013 (USEPA,
2015a). The aqueous solubilities of some of the chemicals are extremely low, and will therefore have
low dissolved concentrations in water. The Henrys law constants are variable for the low mobility
chemicals; chemicals with high log Kow values (larger than 0) and high Henrys law constants will
strongly sorb to solid and organic phases and potentially volatilise, whereas chemicals with low
Henrys law constants will readily sorb to solids and organic phases. Because these chemicals are less
mobile, they will remain in soils for extended periods and cause long-term impacts on drinking water
resources.
32
TABLE 2.8: THE 10 LEAST MOBILE KNOWN ORGANIC CHEMICALS FROM HYDRAULIC FRACTURING FLUIDS
Estimated
Percent Estimated
Estimated Henry's law
of wells water
Rank Chemical name log Kow constant
(USEPA, solubility
(unitless) (atm m3/mole
2015a) (mg/l @ 25 C)
@ 25 C)
1 Sorbitan, tri-(9Z)-9 octadecenoate 0.05% 22.56 1.12 10 19 4.02 10 11
2 Dimer Acid 14.60 2.31 10 10 4.12 10 08
3 Sorbitan sesquioleate 0.02% 14.32 2.31 10 11 7.55 10 12
4 Tri-n-butyltetradecyl-phosphonium chloride 6.00% 11.22 7.90 10 7 2.61 10 1
sodium 1,2-bis (tridecyloxycarbonyl)

5 11.15 7.46 10 9 8.51 10 11
ethanesulphonate
6 1-Eicosene 10.03 1.26 10 5 1.89 10 1
7 Phloxine B 9.62 1.64 10 8 6.37 10 21
8 Solvent Red 26 9.27 5.68 10 5 5.48 10 13
9 1-Octadecene 9.04 1.256 10 4 1.07 10 1
10 Alkenes, C>10 - 8.00% 8.55 3.941 10 4 8.09 10 0
Note:
From the table above, it can be see that the least mobile chemicals have the highest log K ow values and
are fully miscible [1.00 106 (mg/l @ 25 C)] which means that they can move with water through the
environment at high concentrations, which may lead to greater severity impacts. They also have
negative log Henrys law constants and will therefore not volatilise but remain in the water.
Information similar to those presented in Table 2.7 and Table 2.8 is crucial when selecting parameters
to analyse for at specific distances from the wellpad during groundwater baseline establishment for
hydraulic fracturing operations if it is known which chemicals will be used during hydraulic fracturing
treatment.
2.3.5.5 Drilling fluid/mud chemicals
Drilling fluid is used during drilling boreholes for both hydraulic fracturing and UCG operations, as well
as when drilling deep exploration boreholes and monitoring boreholes. Drilling fluid is used during
drilling of boreholes to:
carry drill cuttings to the surface;

form a filter cake which seals pores and openings in the country rock penetrated by the drill bit;
33
clean and cool the bit;
reduce friction;
stabilise the borehole; and
prevent unwanted inflow of fluids from penetrated formations (Caenn et al., 2011).
According to Haris et al. (2013) the chances of groundwater resources becoming contaminated with
drilling fluid (drilling mud) during borehole drilling is high. Invasion of the drilling fluid into the
groundwater is unavoidable due to a number of reasons. Generally, during drilling, the borehole
pressure is kept greater than the formation pressure to prevent formation fluid from entering the
borehole. This pressure forces the mud into porous and permeable formations (Gatlin, 1960). In
addition, mud seepage from surface pits could also be problematic (Haris et al., 2013).
Drilling mud/fluid is characterised according to the base fluid. There are two broad categories for
drilling fluid: water-based fluid (WBF) and non-aqueous drilling fluid (NAF) which consist of oil or
synthetic based base fluid. It is common practice to use both WBF and NAF when drilling different
sections of a well. The WBF is generally used in the shallow upper well section, and NAFs are used in
the more technically demanding sections of the well. Each drilling mud type has its advantages and
disadvantages which need to be considered before drilling of a well.
Table 2.9 presents a list of additives which may be used during drilling. This is not an exhaustive list of
the additives used as there are more than a 1 000 trade name and generic additives that may be used.
TABLE 2.9: COMMONLY USED ADDITIVES IN WATER BASED AND NON-AQUEOUS BASED DRILLING FLUIDS
Additives Additives
Fresh water Glycols (polyglycols)

Sea water Gypsum (CaSO42H2O)
Brine Polyacrylamides
Saturated sodium chlorite (NaCl) Polycyclic aromatic compounds (PAC)
Sodium hydroxide/potassium hydroxide
Calcium chloride (CaCl 2)
vvvv(NaOH/KOH)
Potassium chloride (KCl) Calcium hydroxide (Ca(OH)2)
Zinc bromide/Calcium Bromide (ZnBr/CaBr) Citric acid (C6H8O7)
Barite (BaSO4) Sodium bicarbonate (NaHCO3)
Calcium carbonate (CaCO3) Bactericides
Iron carbonate (FeCO3) Polymer stabilisers
Corrosion control (oxygen scavengers, filming vvvv
Hematite (Fe 2O3)
ssss.agents)
Ilmenite (FeTiO3) Salts (KCl)
Bentonite Lignosulphonates
Organophillic clay Tannins
Source: Adapted from IPIECA/OGP (2009)
34
2.4 UNDERGROUND COAL GASIFICATION
As stated in Section 2.2.3, coal gas may be extracted unconventionally through a process known as
UCG. The purpose of this section is to discuss coal formation mechanisms; coal gas resources in South
Africa; coal gas recovery through UCG, while focussing on UCG operations; the composition of
different UCG products and by-products such as syngas, post-processing effluent, solid UCG by-
products; and the fate and transport of UCG by-products.
It is essential to be aware of the different chemicals which may potentially migrate from the
combustion zone into potable groundwater resources. Furthermore, it is also necessary to be aware
of the fate and transport of different UCG by-products as it would help select and install new boreholes
for groundwater sampling and aquifer tests.
2.4.1 Coal formation mechanisms

Coal is an organic sedimentary rock which is composed of amorphous, degraded plant remains which
have been metamorphosed to various degrees and is intermixed with minute mineral grains (major
species are quartz, clays, carbonates and pyrite). The character and composition of the coals depend
on the original organic and inorganic matter accumulation and the degree of diagenesis it has
undergone.
After the organic and inorganic matter have been deposited through different specialised geological
processes, the accumulated material, mostly plant biopolymers, undergo synsedimentary and
postsedimentary processes, namely biological (biodegradation), geochemical and geological
(temperature and pressure changes) which lead to the transformation of the organic material to peat
(peatification) and ultimately to coal (coalification). These processes determine the coal rank and also
the degree of structural complexity of the coal (Orem and Finkelman, 2003; Thomas, 2002).
According to Thomas (2002) the following general depositional models exists for the formation of coal:
coastal barrier and back barrier deposits; alluvial fan; lower delta plain deposits; upper delta and
alluvial plain deposits; and lacustrine deposits. The Waterberg coalfield which contains 40% of the
remaining recoverable coal in South Africa was deposited in a fluviodeltaic environment (Vryheid
formation) (Hobday, 1973) and in deep to shallow basinal marine environments (Volksrust)
(Catuneanu et al., 2005).
For coal to form, organic matter needs to accumulate in areas where organic matter is preserved.
After plant material has been buried/accumulated, the plant biopolymers undergo fungal and
bacterial degradation during diagenesis to form peat (petrification). Peat is formed in areas where the
organic matter accumulation exceeds the microbial degradation of the organic matter. These are areas
35
such as shallow aquatic environments, for example, swamps and marshes, where waterlogged
conditions limit biodegradation and anaerobic microbial processes dominate (Orem and Finkelman,
2003).
Peat is transformed to coal under anoxic (or low-oxygen) conditions by anaerobic metabolic processes
(such as bacterial biodegradation) generally in subsiding basins under a range of conditions of which
the most important are temperature and time. As peat is transformed into coal (coalification) there is
a loss of oxygen and hydrogen and an increase in the organic carbon content. The early stage
coalification products are known as lignite and brown coal and the later stage coalification products
subbituminous coal, bituminous coal and anthracite are the results of deeper burial (increased
pressure and temperature) of the organic matter over time.
South African coal is contained within the Karoo Basin and are generally classified as shallow, almost
horizontal, high volatile bituminous coal, with variable sulphur and high ash content (Orem and
Finkelman, 2003).
2.4.2 Coal gas resources in South Africa

In 2013 the World Energy Council estimated that there were 869 billion tonnes of coal reserves in the
world and around 6 000 billion tonnes of coal resources. This figure suggests that only 15% of these
resources are accessible through conventional coal mining methods.
The Department of Energy (Republic of South Africa, 2016), mentioned the report by Bredell (1987)
wherein it was estimated that South Africa had 55 billion tonnes of coal reserves and an estimated
115 billion tonnes of coal resources. Even though a number of previous surveys have attempted to
determine the quantity of coal resources and reserves in South Africa, no consensus has yet been
reached on the exact quantities (World Energy Council, 2013). Therefore, an estimate for the quantity
of coal appropriate for UCG operations would also not be accurate.
According to Van der Riet (2008), Eskom Resources and Strategy have estimated that South Africa
have an estimated 45 billion tons of coal suitable for UCG which was previously unmineable, excluding
the coalfields in KwaZulu-Natal, Ermelo and Witbank. Van der Riet (2008) further estimated that
almost three quarters of South African coal resources (of which 70% is found in the northern Karoo
Basin of South Africa and 40% found in the Ellisras basin) are regarded as unmineable when
considering conventional coal mining techniques; these resources may, however, potentially be
extracted by UCG. It is estimated that the UCG process is able to produce 350 gigawatt of electricity
within South Africa (Van der Riet, 2008). Currently, the Majuba UCG project has been producing syngas
since January 2007 by using UCG technology, and is the longest running UCG trial in the western
world (Bhutto et al., 2013).
36
2.4.3 Coal gas recovery through underground coal gasification
The two most widely used UCG techniques in establishing a connection between the injection wells
and production wells are the Continuous Retraction Injection Point (CRIP) process and the UCG4
process.
UCG is the process of gasifying coal in situ within the coal seam underground by using a matrix of wells
drilled into the coal bed. The coal is mined by igniting the coal underground in a cavity and injecting
oxygen and water (steam) into the injection well to sustain the burning process. This is done to
produce combustible synthetic gas (syngas) which is captured by the production well. Essentially,
syngas compromises predominantly of moisture, CO, CO2 , H, CH4 and other hydrocarbons which are
the product of pyrolysis (Creedy et al., 2001). The syngas produced at El Tremedal in Spain consisted
of 40% CO2 , 12% CO, 25% H2 , 13% CH4 and 8% H2 S (Creedy et al., 2001). CO2 and moisture are essential
to liberate heat which drives the gasification process (Van der Riet, 2008).
UCG is intended to mine coal resources which cannot be conventionally mined through open-pit
mining or longwall mining due to the following reasons:
The coal is too deep to be economically mined at a certain point in time.

The thickness, slope, fracturing and displacement of the coal make it uneconomical or unsafe to
mine conventionally (Van der Riet, 2008).
To determine if a coal can be used for UCG operations, the coal quality needs to be determined. To
classify the coal the following needs to be determined:
Ash content (%) is the inorganic residue that remains after coal combustion and losing volatile
components such as CO2 and H2 O.
Calorific value (CV) is the amount of heat that is produced per unit mass of coal when combusted.
It can be expressed in two ways: gross calorific value and lower heating value.
Volatile matter% (VM) is the component of the coal that is derived/liberated from the organic
fraction of the coal at high temperatures and does not include moisture or volatile matter derived
from mineral matter.
Fixed carbon% (FC) is the carbon content that remains after the volatile matter has been liberated
from the coal.
Total sulphur (TS) is the combination of the different forms of sulphur that can be present in coal,
for example, organic sulphur, pyritic sulphur and sulphate minerals (Thomas, 2002).
4
UCG (or Energy UCG) is a proprietary process with little published information on its workings (Burton et al.,
2006).
37
Other analyses that may be required are determining the carbon and nitrogen content; nitrogen
content; and oxygen content. Of these properties/factors, the most essential for UCG operations are
ash content. Table 2.10 is a compilation of the required coal characteristics for UCG operations
according to different references.
TABLE 2.10: COMPILATION OF DESIRED COAL DEPOSIT CHARACTERISTICS FOR UNDERGROUND COAL
GASIFICATION
Burton et al.
Characteristic Reddy (2013) PWC (2008) Exergy (2010) Average
(2006)
Depth 100 600 m 100 600 m >150 m 30 800 m 315 m
Thickness >5 m >5 m >1.5 m 0.5 30 m 7m
Lignite through to Bituminous and

CV/rank bituminous lower rank 830 MJ/kg 23 MJ/kg
(1733 MJ/kg) (1733 MJ/kg)
Ash <60% <60% <60%
Must be below
Absence of any water table;
Should be isolated
Water good-quality Not a potable
from aquifers
aquifers water source
(TDS >1 000 ppm)
Coal must have
Minimal seam Strong overlying
Geology minimal Dip 0 70
discontinuities strata preferable
discontinuities
Access for drilling
Other
and monitoring
Note:
The first suggestion to gasify coal underground is credited to Sir William Siemens from Germany.
However, the first suggestion for drilling underground injection and production wells is credited to
Dmitriy Mendeleyev from Russia, both in the late 1800s. The first UCG operations were started by
Joseph Stalin in 1928, which continued at high levels for over 50 years (Burton et al., 2006).
Some of the well-documented UCG sites are those in Chinchilla (Australia); and Hanna and Centralia
(USA) (Burton et al., 2006).
2.4.3.1 Description of underground coal gasification operations
In this section the activities that take place from the initial site development through to production
and closure will be discussed. The details of each UCG operation differ from company to company and
area to area, therefore only a generalised version is presented here.
38
2.4.3.1.1 Exploration, site assessment and development phase
Before UCG can be conducted, a site has to be selected. Site selection includes exploration and site
assessment. After the site has been selected, the site has to be developed. Exploration activities
include:
Geophysical surveys to delineate subsurface features and to reduce geological and environmental
risk.
Drilling exploration boreholes to determine the depth, orientation, thickness, extent and quality
of the coal seam(s) and to reduce geological and environmental risk.
Geohydrological studies to determine the potential influx of water into the cavity during
gasification (Burton et al., 2006; Creedy et al., 2001; Pana, 2009).
Some of the factors that are taken into account when choosing a site for UCG operations are coal seam
thickness; depth; orientation; volatile matter; coal rank, the strength of the overlying strata; the depth
of the water table and the accessibility of the site (Burton et al., 2006; Creedy et al., 2001; Hancox and
Gtz, 2014; Van der Riet, 2008; Younger, 2011). After the site has been selected, surface facility
planning needs to be done. The facilities chosen should be engineered to handle swing in production
characteristics, which may occur if, for example, groundwater influx increases, gas product is lost, and
because of faulty increase in operational pressure (Burton et al., 2006).
During site development, the site needs to be prepared for equipment to reach the UCG development
area; this includes building of access roads for vehicles, levelling the area and removing vegetation.
The operator may then excavate the drilling mud from storage pits (the fluids may also be kept in
storage tanks), holes may then be dug for pipes which transport fluids to and from the wellhead
(Arthur et al., 2009).
After site preparation and development drill rigs, drilling platforms, drilling mud components, storage
tanks, different drill pipes and casings, pumps, oxygen supply generators, boiler and steam generators,
and gas collectors can be moved to the UCG site. Figure 2.11 illustrates the generalised surface
infrastructure at a typical UCG operation using the parallel CRIP method.
39
Figure 2.11: Typical surface infrastructure at an underground coal gasification operation using the
parallel Continuous Retraction Injection Point method
2.4.3.1.2 Well-drilling, construction and linkage
During drilling the injection well and production well are drilled near vertically and then deviated to
the horizontal to intercept the target coal seam at depth. The purpose of the injection well is to
introduce gasification agents, such as water and air or pure O 2 , to the coal seam and to introduce the
ignition device at the coal seam. The ignition device burns through the well and ignites the coal to
initiate the gasification process (Creedy et al., 2001).
With the deviated drilling technology, the ends of the two wells (injection and production wells) can
be positioned within one metre from each other in the coal seam at depth. The wellheads at the
surface can be as far as 400 m or even further apart (Creedy et al., 2001).
The injection well is cemented into place above the reaction zone to prevent gases from escaping
through the stainless steel well into the overlying formations and also to facilitate controlled
introduction of air into the reaction zone (Burton et al., 2006).
The injection well (which constitutes the underground reactor or gasifier) and the production well
needs to be linked within the coal seam in order to collect the produced syngas. This can be done by
(a) reverse combustion which works by injecting oxidants into one well, and ignition of coal in the
other well, therefore the combustion would propagate towards the oxidant, or (b) forward
combustion which works on precisely the opposite principle as reverse combustion (Bahl et al., 2014;
40
Bhutto et al., 2013; Blinderman et al., 2008; Creedy et al., 2001). The two methods are presented in
Figure 2.12.
Figure 2.12: Schematic view of both reverse (a) and forward (b) combustion linking in underground coal gasification
2.4.3.1.3 Setup and ignition
After the wells have been constructed, the coal seam needs to be dried near the injection well; this
can be done by blowing air through the injection well. When the location near the ignition site is
sufficiently dry, the coal seam can be ignited.
Different methods can be used to ignite the coal seam, but the most successful method is CRIP which
was developed in the USA. CRIP involves the use of a burner attached to a coiled tubing. The device is
ideal for burning through the well casing to ignite the coal (Bahl et al., 2014; Creedy et al., 2001). By
using the CRIP process, the injection point is retracted in the coal seam to control the location of the
combustion front, so that different portions of the coal even further from the production well may be
gasified (Younger, 2011).
After the coal has been ignited, oxidants (air or pure oxygen) and steam are injected into the injection
well (at a pressure equal to or greater than the surrounding hydrostatic pressure, to prevent
uncontrollable ingress of water into the chamber) to maintain the combustion of the coal, and
produce syngas. The produced CO2 and moisture (which is produced together with the syngas) drives
the gasification process in the pyrolysis zone (Van der Riet, 2008). The pyrolysis zone is where the coal
is exposed to high temperatures due to radiant heat (Bahl et al., 2014; Burton et al., 2006).
41
2.4.3.1.4 Cavity growth
Figure 2.13 depicts the UCG cavity growth process in the coal seam due to gasification. As the cavity
grows, due to continued burning of the coal (combustion/gasification), new coal fronts are heated.
This causes the coal to lose moisture through the pore structures (drying), and then undergoes
pyrolysis at temperatures above 400 C. Pyrolysis of organic matter produces hydrogen-rich volatile
matter, together with phenols, hydrocarbon gases, liquid products (oils) and tars. The material which
is left after pyrolysis is solid residue, rich in carbon content and is known as char. As gasification
continues, a cavity is formed, consisting of of voids, coal, ash, char and rubble.
Figure 2.13: Underground coal gasification cavity growth due to gasification
2.4.3.1.5 Gas production
As gasification continues, in the coal seam, a cavity develops. The cavity grows towards the point of
least resistance. The lateral extent of the cavity is controlled by the influx of groundwater from the
surrounding formations and from the injection well 5 (Chappell and Mostade, 1998). Groundwater
influx into the cavity under optimal pressure confines the chemical processes to the gasification zone,
thus preventing contamination in the area (i.e. positive hydraulic gradient towards the gasifier)
(Burton et al., 2006). Furthermore, the rate of gasification is controlled by the rate of flow of oxygen
5
The water flows from the injection well and the influx from the surrounding formations should be controlled and
monitored to prevent cooling which will reduce the efficiency of the gasification. The influx can be controlled by increasing
the reactor back-pressure (Creedy et al., 2001).
42
to the reactor, and the proportion of useful products in the product gas is controlled by the
oxygen:water ratio. The rate of flow and the ratios are controlled at the surface (Sury et al., 2004).
The cavity will extend until the roof collapses, which is vital as it aids the lateral growth of the gasifier
(Creedy et al., 2001).
The produced syngas6 from gasification then flows from the gasification area through the horizontal
linkage channel(s) to the production well, which then transports the syngas to the surface where it
undergoes treatment to convert CO, CH 4 and hydrocarbons to H. Furthermore, the gas undergoes
treatment to remove CO2 , NH3 , H2 S and traces of other gases and particulate matter which may be
entrained in the gas flow. After being treated, the gas is piped to the end-user which will most likely
be a gas turbine (Burton et al., 2006; Creedy et al., 2001).
The CO2 portion of the syngas (generally 15% by molar mass) which is removed at the surface facility
may be transported to enhanced oil recovery schemes (through a carbon capture system) (Moorhouse
et al., 2010).
It is suggested that in order to prevent groundwater contamination the pressure in the gasifier should
be kept lower than the pressure in the surrounding strata and in the coal seam. Therefore, it is
suggested that there should be no drive for groundwater flow, gas products or contaminants from the
gasification zone into the surrounding formations (Burton et al., 2006).
2.4.3.1.6 Site and well closure
After all the planned coal gas has been extracted, or when the quality of the gas product declines, the
gasification process is brought to a halt by ceasing to pump air and water to the reactor (Creedy et al.,
2001). The gasification module is then depressurised by releasing the gas from the system (Sury et al.,
2004).
The remaining coal and char are then cooled down by flooding the cavity with water to permanently
extinguish the cavity. The purpose of the flooding process is to prevent the formation of any
contaminants in the remaining coal via pyrolysis (Bahl et al., 2014). To prevent any further reactions,
the gasifier should be purged with nitrogen via the injection well (Creedy et al., 2001).
Once the coal within the underground gasifier has been exhausted, new wells are drilled alongside the
exhausted gasifier and the process is restarted (Creedy et al., 2001).
6
The pressurised gas in the gasification area and in the linkage channel(s) are kept in place by the pressure of the overlying
formation (Van der Riet, 2008).
43
2.4.3.2 Underground coal gasification products and by-products
The UCG process leads to the formation of both gaseous products and by-products (liquid and solid).
These products and by-products may come in contact with groundwater resources through many
different pathways (Lutynski and Suponik, 2014). For more information on the migration pathways,
see Section 2.6.
During the UCG gasification process the following products and by-products are formed:
Products:
Synthetic gas, also known as syngas, which is formed due to combustion/gasification of the coal.
By-products:
Effluent water, which is formed through condensation of moisture in the produced gas.
Solid residue such as ash, coal residue (char) and tar (liquid), which are left in the cavity after
gasification of the coal (Kapusta et al., 2013).
The distribution of produced gases and contaminant by-products varies as a function of the amount
of steam, whether air or oxygen is used, the temperature, and pressure during the gasification
process. Also, the contaminants of the by-products and the syngas composition depend on the type
of coal, the chemical composition of the coal, the mineralogy of the coal and the surrounding rock,
and the gasification conditions (Kapusta et al., 2013; Wobus and Ritter, 2010). Therefore, it is evident
that the composition of the products and by-products that will be formed/released during UCG
operations will vary from site to site; consequently, the chemical composition of the different products
and by-products presented in Sections 2.4.3.2.1, 2.4.3.2.2 and 2.4.3.2.3 are generalisations from the
available literature and do not necessarily represent the products and by-products that might be
produced from the coals of the Karoo Basin during UCG.
2.4.3.2.1 Syngas composition
The gas that is produced through UCG mainly comprises of H2 0, CO, H2 , CO2 , N2 , H2 S, CS2 and small
quantities of CH 4 , C2 H6 , C4 H10 (Holloway et al., 2005; Islam et al., 2015). This gas is a synthetic gas and
is known as syngas. The gas composition depends on many different factors such as (a) type of oxidant
used, air or pure oxygen; (b) water ingress into the area of gasification; (c) the quality of the coal; and
(d) the reaction type (i.e. coal combustion or coal gasification) (Bahl et al., 2014; Creedy et al., 2001;
Kapusta and Staczyk, 2011).
Syngas contains several potential contaminants, such as phenols, polycyclic aromatic hydrocarbons
(PAHs), nitrogen, ammonia, chlorine, hydrogen cyanide, sulphur compounds, carbon disulphide, and
44
trace and heavy metals (such as arsenic, selenium and mercury which are volatile metals) from the
combustion process (Burton et al., 2006; Kapusta et al., 2013; Liu et al., 2006; Sury et al., 2004).
Aromatics such as PAHs are not produced during efficient, high temperature, gasification. However, if
the temperature in the gasification chamber is too low, which may be caused due to excessive influx
of groundwater, aromatics may be produced in the wastewater (Sury et al., 2004).
2.4.3.2.2 Post-processing effluent
One of the main potential sources of groundwater and surface contamination, due to UCG, are from
the post-processing effluent which is produced as condensates during the production phase. This
effluent is collected in the different modules of the surface gas processing system and, if not treated
appropriately, can pose serious environmental risks (Kapusta et al., 2013).
The compounds and average concentrations for the production phase are presented in Table 2.11.
TABLE 2.11: INORGANIC AND ORGANIC COMPOSITION OF UNDERGROUND COAL GASIFICATION EFFLUENT
WATER
Parameter/compound Unit Production phase Cooling phase
Inorganics
Ammoniacal nitrogen (NH3-N) mg/l N 1 950 1 425
Total nitrogen mg/l N 2 003 1 465
Nitrite (NO2) mg/l <0.02 <0.02
Chloride (Cl ) mg/l 1 660 643
Cyanide (Cn) mg/l 1.26 1.03
Sulphate (SO42) mg/l 3 220 6 305
Antimony (Sb) mg/l <0.05 <0.05
Arsenic (As) mg/l 2.93 2.61
Boron (B) mg/l 6.48 6.05
Chromium (Cr) mg/l 0.51 0.16
Zinc (Zn) mg/l 3.53 5.00
Aluminium (Al) mg/l 17.7 35.0
Cadmium (Cd) mg/l <0.02 0.026
Chromium (Cr) mg/l 0.031 0.077
Manganese (Mn) mg/l 4.91 9.90
Copper (Cu) mg/l <0.01 <0.01
Molybdenum (Mo) mg/l 0.133 <0.01
Nickel (Ni) mg/l 0.243 0.140
Lead (Pb) mg/l 0.044 <0.05
Mercury (Hg) mg/l <0.005 <0.005
45
Parameter/compound Unit Production phase Cooling phase
Selenium (Se) mg/l 0.14 <0.01
Titanium (Ti) mg/l 0.52 0.34
Iron (Fe) mg/l 650 1 110
Organics
Total organic carbon (TOC) mg/l 616 1 490
Phenolics mg/l 484 610
Total BTEX g/l 55.8 15.3
Benzene g/l 51.10 14.8
Toluene g/l 3.73 1.09
Ethylbenzene g/l 0.70 <0.01
Xylene g/l 1.82 <0.01
Total PAHs g/l 1 912 378
Naphthalene g/l 1 641 220
Acenaphthene g/l 17.0 4.0
Fluorene g/l 118.4 59.1
Phenanthrene g/l 116.3 81.6
Anthracene g/l 4.10 2.85
Fluoranthene g/l 12.25 6.84
Pyrene g/l 7.25 3.87
Benzo(a)anthracene g/l 0.10 0.10
Chrysene g/l 0.14 0.19
Benzo(b)uoranthene g/l <0.01 0.02
Benzo(k)fluoranthene g/l <0.01 <0.01
Benzo(a)pyrene g/l 0.11 0.04
Dibenzo(a,h)anthracene g/l <0.01 <0.01
Benzo(g,h,i)perylene g/l <0.01 <0.01
Indeno(1,2,3-cd)pyrene g/l <0.01 <0.01
Total N-heterocyclic compounds mg/l 6.47 11.69
Pyridine mg/l 3.42 0.67
Quinoline mg/l 1.62 6.66
Isoquinoline mg/l 2.05 2.19
Indole mg/l 1.59 0.69
Acridine mg/l 1.20 1.83
Carbazole mg/l 1.03 <0.1

Source: Adapted from Kapusta et al. (2013)
As can be seen from Table 2.11, the most abundant organic compound found in the UCG effluent
water is phenolic compounds, which relate to the results from studies by Liu et al. (2007) and Sury
46
et al. (2004). The reason for this abundance is the high water affinity of the phenolic compounds
(Kapusta et al., 2013). Of the BTEX compounds, benzene had the highest concentration, and is a
characteristic organic UCG pollutant (Kapusta and Staczyk, 2011).
From the table, it can also be seen that of the 15 PAHs analysed, only 11 were above the lower
detection limit of >0.01 g/l. The dominant compound was naphthalene which contributed
approximately 86% of the total PAHs during the production phase. Other dominant compounds
among the PAHs were fluorene and phenanthrene, which also correspond to the results from previous
studies (Kapusta et al., 2013).
N-heterocyclic compounds also had relatively high concentrations in the post-processing effluent; this
is also due to their high affinity to water solutions (Kapusta et al., 2013). PAHs and heterocyclic
compounds are, however, of minor concern (LIU et al., 2007).
Ammonia, cyanides, boron, sulphates and heavy metals are usually identified as the main inorganic
compounds and are usually identified in UCG-effluent water (Creedy et al., 2001; Kapusta and
Staczyk, 2011). Furthermore, the following inorganic element concentrations of the effluent water
were below the lower detection limits: nitrites, antimony, copper and mercury.
2.4.3.2.3 Solid underground coal gasification by-products
After the gasification process, residual by-product material such as ash, char (coal residues) and tars
remain underground in the created cavity. These by-products become sources of contaminants which
may be leached out with the ingress of water into the cavity and migrate into the groundwater
resources through different pathways (Kapusta et al., 2013).
In a study by Kapusta et al. (2013) samples for ash, char and tars were collected to assess the possible
environmental risks related to leaching of contaminants from these by-products of coal gasification.
The concentration results for different trace metals are presented in Table 2.12.
From the table it can be seen that arsenic, manganese, iron and titanium had relatively high
concentrations in all of the by-products, whereas antimony, mercury and cobalt had relatively low
concentrations throughout (Kapusta et al., 2013).
According to a study conducted by Liu et al. (2007), calcium, sodium sulphate and bicarbonate are the
major inorganic constituents leached from ash. Other minor inorganics include aluminium, arsenic,
boron, iron, zinc and uranium (Ahern and Frazier, 1982). PAHs and phenolics are also potential
contaminants (Sury et al., 2004).
47
TABLE 2.12: CONCENTRATION OF SELECTED TRACE METALS IN THE UNDERGROUND COAL GASIFICATION SOLID
RESIDUE BY-PRODUCTS AND TAR
Parameter/compound Char (mg/kg) Ash (mg/kg) Tar (mg/kg)
Antimony (Sb) <2 <2 <2
Arsenic (As) 11 13 17
Boron (B) 55 74 <5
Chromium (Cr) <1 85 5
Zinc (Zn) 21 33 861
Aluminium (Al) 8 500 142 254
Cadmium (Cd) <1 <1 21
Cobalt (Co) 10 68 <2
Manganese (Mn) 385 126 4
Copper (Cu) 15 54 19
Molybdenum (Mo) 2 5 6
Nickel (Ni) 30 117 2
Lead (Pb) 9 2 47
Mercury (Hg) 0.02 0.02 9
Selenium (Se) <2 <2 33
Thallium (Ti) 400 6 100 26
Iron (Fe) 6 200 58 958
Source: Adapted from Kapusta et al. (2013)
2.4.3.3 Fate and transport of underground coal gasification by-products
The underground strata and groundwater may be polluted by the diffusion and penetration of
contaminants formed by the UCG process, and by the potential leaching of contaminants from
underground residue by natural groundwater influx after the gasification process.
The extent and concentration of the groundwater pollution plume depends primarily on the
groundwater flow velocity. Other factors which control the extent and concentration of groundwater
pollution are the mobility of the contaminant; the degree of adsorption, dispersion and reactions
between the different contaminants with one another; and the surrounding environment. The more
volatile the constituent, the further it will be transported before condensing or dissolving into the
groundwater.
48
According to (Ahern and Frazier, 1982) the two mechanisms which control the migration and
distribution of produced UCG chemicals after UCG are:
Convection mixing which distributes chemicals around the burn cavity.

Regional groundwater flow which controls the plume migration of the altered water downgrading
from the UCG site.
Furthermore, the migration of aqueous phase contaminants is controlled by the permeability of the
host rocks and the geological setting in which gasification occurs (LIU et al., 2007).
In a study conducted by Kapusta et al. (2013), it was found that pollutant concentrations tend to
decrease with both time and distance from the burn cavity, which is similar to the findings at the
former Soviet Union UCG field site (LIU et al., 2007). This indicates a self-restoration process of the
water-quality with time (approximately two years) (Kapusta et al., 2013).
This self-restoration process is attributed to the following processes: adsorption and ion exchange
properties of the surrounding strata; precipitation reactions; dilution and dispersion by natural
groundwater flow; and biological conversion reactions (Kapusta et al., 2013).
The compounds with medium to high affinity for solid surfaces will travel slowly in the groundwater
and will show significant concentration decreases with time, whereas compounds with low affinity for
solid surfaces will travel at the rate of groundwater flow and will show a low decrease in concentration
with time (LIU et al., 2007). Table 2.13 presents chemical species which sorb strongly and species
which do not sorb.
TABLE 2.13: SORB PROPERTIES OF SOME CHEMICALS PRODUCED BY UNDERGROUND COAL GASIFICATION
Chemicals which sorb strongly Chemicals which do not sorb
Ammonium (NH 4+) Calcium (Ca +)
Cadmium (Cd) Bromide (Br )
Iron (Fe) Chloride (Cl )

Lead (Pb) Selenium (Se)
Manganese (Mn) Sulphate (SO42-)
Zinc (Zn)
Phenols
Naphthol
Polynuclear aromatic hydrocarbons

Source: Adapted from Ahern and Frazier (1982)
49
2.5 GEOLOGY AND GEOHYDROLOGY OF THE KAROO BASIN OF SOUTH
AFRICA
South Africa has one thick sedimentary basin that contains potentially economical amounts of organic-
rich shales in the southern portion of the basin, and economical amounts of coal in different parts
throughout the basin and sub-basins; this basin is known as the Karoo Basin. The prospective hydraulic
fracturing and UCG operations will take place in either the Main Karoo Basin (MKB) or one of the Karoo
sub-basins (RSA DMR, 2012; Van der Riet, 2008; Van Tonder, 2012; Van Tonder et al., 2013).
The geology and geohydrology of the Karoo Basin and Karoo sub-basins are reviewed in this section
as it is necessary to have a good understanding of the geology and geohydrology of the study area in
which the unconventional gas project will be taking place when establishing a groundwater baseline
for unconventional gas projects as the geology and geohydrology of the study area control the
potential fluid and gas migration from the production zone towards potential receptors.
Also, the geology and geohydrology control the chemical composition of the groundwater, and also
to some degree the chemical composition of the fluids and gas contaminants.
This section will focus on the different geological formations that are found in the Karoo Basin,
focusing mainly on depositional history and formations of the Ecca Groups as it is the Ecca Group that
is mainly targeted for its unconventional gas resources.
2.5.1 Geology of the Karoo Basin

The Karoo Basin of South Africa can be divided into the MKB, which is significant for shale gas
development through hydraulic fracturing, and the Karoo sub-basins (northern Karoo Basins), which
are more significant for UCG operations.
The basins that will be covered for this discussion are the MKB and the Ellisras Basin. The Ellisras Basin
is one of the MKB equivalent aged northern Karoo basins and contains the coal which is considered
for UCG operations (Van der Riet, 2008). The Waterberg coalfield is located in the Ellisras Basin and
contains 4050% of South Africas remaining coal resources, and is also considered as the countrys
last major coal resource (Hancox and Gtz, 2014). Figure 2.14 presents the geographical distribution
of the basins.
50
Figure 2.14: Distribution of the Main Karoo Basin and the Ellisras Basin
The MKB is the thickest and stratigraphically most complete mega-sequence deposit in the south-
western Gondwana out of several other Permo-Carboniferous to Jurassic age depositories (Catuneanu
et al., 1998).
Even though there is not yet consensus on the evolution and tectonic setting of the basins, it is
believed by most researchers that the MKB is a Late CarboniferousMiddle Jurassic retroarc foreland
ll, which developed in front of the Cape Fold Belt (CFB) in relation to the Late PalaeozoicEarly
Mesozoic subduction of the palaeo-Pacic plate underneath the Gondwana plate (Catuneanu et al.,
1998; Cole and McLachlan, 1991; Johnson et al., 2006).
Whatever the tectonic mechanism of formation, the Karoo-aged depositories in South Africa were
formed as part of two linked tectonic settings. The MKB is related to compression and the northern
Karoo Basins (Ellisras Basin) is linked to extension or transtension (Rust, 1975).
Even though the lithologies of the northern Karoo Basins show differences to their correlative
counterparts in the MKB, these lithologies show similarities at group level to the geological groups of
the MKB (Hancox and Gtz, 2014). Therefore, the general geological overview that is discussed in the
following section is pertinent to both the MKB and the northern Karoo Basins (including the Ellisras
Basin) of South Africa.
2.5.2 General geology and stratigraphy of the Karoo Supergroup

The Karoo Supergroup can be divided into five geological groups, namely: the Dwyka, Ecca, Beaufort,
Stormberg and Drakensberg Groups. The distribution of these groups in the MKB is illustrated in Figure
2.15, and the age relationship between these groups is illustrated in Figure 2.16. The stratigraphic
correlation between the distal MKB lithostratigraphy and the Ellisras Basin is presented in Figure 2.18.
51
The Karoo groups were deposited through sedimentary processes of weathering, erosion, deposition
and lithification, apart from the igneous rocks of the Drakensberg Group, and is referred to as the
Karoo sedimentary sequence.
The sedimentary succession of the Karoo Supergroup reflects changes in depositional conditions from
glacial (Dwyka Group) to shallow, deep marine and deltaic (Ecca Group), fluvial and aeolian (Beaufort
and Stormberg groups) (Smith et al., 1993). The accumulation of these sedimentary deposits was
controlled by tectonism and climate. The tectonic regimes in the MKB were dominantly flexural, in
relation to processes of subduction and mountain building (orogeny) along the palaeo-Pacic margin
of Gondwana (Duncan et al., 1997).
The Ecca Group, which contains the shale and coal formations and is of economic importance for
potential hydraulic fracturing or UCG operations, will be discussed in more detail in the sections
following the figures.
Note: The cross section AB, indicated in Figure 2.17 connects the proximal (south [A]) to the distal (north-east [B])
facies.
Figure 2.15: Karoo Supergroup outcrop distribution of the main lithost ratigraphic groups
52
Figure 2.16: Stratigraphy of the Karoo Supergroup in the Main Karoo Basin of South Africa
53
Note: FM = formation
Figure 2.17: Stratigraphic cross section along the profile indicated in Figure 2.15
Note: FM = formation; GP = group; Sst = sandstones
Figure 2.18: Stratigraphic correlation between the distal Main Karoo Basin lithostratigraphy and the Ellisras Basin
lithostratigraphy
54
2.5.3 Ecca Group
After the Dwyka glacial episode, thick mudrock successions (Prince Albert, Whitehill and Collingham
formations) were deposited in the southern Ecca Group, which represent suspension settling in deep
water. This was followed by deep water submarine fan deposits (Ripon formation) and deepshallow
deltaic deposits (Fort Brown and Waterford formations) (Johnson et al., 1996). In the MKB the Ecca
Group is of Late Carboniferous to early Late Permian age and is approximately 3 000 m thick in the
foredeep basin (Catuneanu et al., 2005).
The southern Ecca Group includes the Prince Albert, Whitehill, Ripon, Collingham, Fort Brown and
Waterford formations, which partially correlate with the Pietermaritzburg, Vryheid and
Volksrust/Grootegeluk formations in the north-east of the MKB, and partially correlate with the
Wellington, Swartrant and Grootegeluk formations of the Ellisras Basin, respectively (see Figure 2.17
and Figure 2.18). It should be noted that some authors refer to the Wellington, Swartrant and
Grootegeluk formations as the Pietermaritzburg, Vryheid and Volksrust/Grootegeluk formations,
respectively.
The Ecca Group sedimentary sequence is, in certain places, essentially a clastic sequence of siltstones,
mudstones, sandstones, minor conglomerate and coal (Johnson et al., 1996; Johnson et al., 1997). In-
between the siliclastic deposits of the Ecca and Beaufort Groups are interbeds of tuffaceous horizons,
with rhyodacitic and rhyolitic tuff beds, particularly abundant in the Prince Albert, Whitehill and
Collingham formations. These tuffs are derived from the magmatic arc along the Gondwana
continental margin (Van der Werff and Johnson, 2003).
The base and top of the Ecca groups are diachronous, as it is younger in the distal sector and older in
the proximal sector (Cole, 1992), which makes the non-marine facies of the Koonap and Middleton
formations correlative to the upper distal marine Volksrust facies (Rubidge, 1995).
2.5.3.1 Formations of the Ecca Group
The Ecca formation can be divided into the southern and northern formations. The southern
formations occur in the MKB and the northern formations occur in the northern Ka roo Basins
(Ellisras/Waterberg Basin).
Table 2.14 presents a summary of the southern lower and upper Ecca formations and Table 2.15
presents a summary of the northern age equivalent Ecca formations. The southern Ecca formations
are of more importance for hydraulic fracturing operations, whereas the northern formations are of
more importance for UCG operations.
55
TABLE 2.14: SUMMARY OF THE SOUTHERN ECCA FORMATIONS
Group Location Formation Lithology Deposition mechanism/environment Comment
Deposited in a regressive shallow marine

Argillaceous siltstone, sandstone and
Waterford environment (Rubidge et al., 2000) in a delta None
mudstone.
front depositional setting (Johnson, 1976).
Greenish-grey shale with minor sandstone at
Deposited in an overall regressive deep The mudrocks (shales) and rhythmites of the
Southern the base, which becomes more prominent
Fort Brown marine environment (Kingsley, 1977; Fort Brown are marine shelf shales and pro-
Upper Ecca upwards (Catuneanu et al., 1998; Cole, 1998;
Rubidge et al., 2000). delta deposits (Kingsley, 1977).
Formations Visser and Loock, 1978).
The formation is arranged into a Bouma
Deposited as turbidites in deep water
sequence and consists of greywacke,
Ripon submarine fan complexes at the foot of None
siltstones and shales (Visser and Loock,
advancing delta slopes (Johnson et al., 1996).
1978).
Mudstone sheet of, chert, phosphorite,
siltstone, dark carbonaceous claystone
Deposited in a deep water environment at
interbedded with siliclastic turbidites, pyrite The main mineral components of the
the base of submarine fan complexes
(Geel et al., 2013), calcareous lenses and Collingham Formation are quartz and illite,
Collingham (Kingsley, 1977) through suspension and
wind-blown rhyodacitic ash (illite rich- with pyrite close to the contact with the
Ecca turbidite flow deposition (Johnson et al.,
mudstone (K-bentonites)) from arc Whitehill Formation (Geel et al., 2013).
2006; Viljoen, 1994).
volcanoes (Elliot and Watts, 1974; Viljoen,
1994; Weaver, 1953).
Carbonaceous pyritic shale which weathers
white, due to subaerial oxidation and Deposited in a deep water (maybe on marine
Southern
reaction of the sulphuric acid with shelves (Demaison and Moore, 1980),
Lower Ecca Laterally time correlative to the distal
carbonates resulting in the formation of pelagic environment under anoxic conditions
Formations Whitehill Vryheid Formation (Cole and McLachlan,
gypsum, tuffaceous shale. Contains chert (which would favour the preservation of
1991; Visser, 1992).
bands and lenses and dolomite lenses organic material) through suspension
(Catuneanu et al., 1998; Faure and Cole, settling (Johnson et al., 1997; Visser, 1992).
1999; Johnson et al., 1996).
Represented by pelagic sediments and
upward coarsening successions (Kingsley, Deposited in a deep water environment by Age correlative to the Pietermaritzburg
1981) of greenish-dark grey shales/ syn- to post-glacial suspension fall-out, with formation of the distal MKB and to the
Prince Albert
mudstones (Catuneanu et al., 1998). These periodic input by turbidites and mudflows Wellington and Swartrant formations of the
mudstones contain phosphatic chert nodules (Tankard et al., 1982; Visser, 1991). Ellisras Basin (Johnson et al., 1996).
and concretions (Visser, 1991).
56
TABLE 2.15: SUMMARY OF THE NORTHERN ECCA FORMATIONS
Group Location Formation Lithology Deposition mechanism/environment Comment
Consists of dark shales (or siltstones and

mudstones) with phosphatic/carbonate Deposited in a deep to shallow basinal
The Volksrust formation grades laterally into
concretions and intercalations of fine- marine environment
Volksrust the southern Tierberg formation (Catuneanu
grained sandstone and coal (Catuneanu et al., 2005; Van Vuuren and
et al., 2005).
(Catuneanu et al., 2005; Van Vuuren and Cole, 1979).
Cole, 1979).
Correlates with the Whitehill Formation in
Sandstone, shales and subordinate coal
the proximal southern part of the basin
Northern beds. The formation starts with a fine
(Visser, 1992). In a study by Ruckwied et al.
Ecca Ecca grained marine facies, which grade upwards
Deposited in a fluviodeltaic environment (2014) it was determined that the coals of
Formations Vryheid into coarser deltaic cycles from delta fronts
(Whateley, 1980). the Vryheid formation correlate to the
and delta plainfluvial facies
organic-rich shales of the uppermost
(Cadle, 1982; Hobday, 1973; Johnson et al.,
Prince Albert and Whitehill formations in the
1996).
Main Karoo Basin.
Consists mainly of shales (or dark grey Correlates with the proximal southern Prince
Deposited in a moderatedeep marine
Pietermaritzburg siltstones and mudstones) with subordinate Albert formation
environment (Du Toit, 1954).
sandstone (Du Toit, 1954). (Johnson et al., 2006).
57
2.5.3.2 Shale formations within the Ecca Group
This section will cover the shale properties of the Upper and Lower Ecca Group within the Karoo Basin,
covering information on the carbon content, maturity and gas resources of the individual shale units.
The formation of most interest for shale gas development is the Permian-age Whitehill Formation of
the lower Ecca Group which contains an organic-rich, thermally mature black shale unit (Kuuskraa
et al., 2013). The reason this formation is considered the most likely for shale gas development is
because the Whitehill Formation is regionally persistent in thickness and composition, and can be
traced throughout the MKB (Branch et al., 2007).
2.5.3.2.1 Lower Ecca Group
The lower Ecca Group has approximately 11.0 tcm risked technically recoverable shale gas resources
(Kuuskraa et al., 2013), with the Whitehill Formation as the most promising formation for shale gas
development with a risked technical recoverable value of 5.98 tcm, with the Prince Albert Formation
and Collingham Formation both with values of less than 3 tcm.
The lower Ecca Group includes the Prince Albert Formation at the base, and overlain by the Whitehill
and Collingham Formations.
Pr in c e Alb e r t S ha le
The main mineral components of the Prince Albert Formation are quartz, muscovite and illite (Geel
et al., 2013). The net pay zone of the organic-rich shale has a total organic carbon content (TOC) of
1.54.5%, averaging 2.5%. TOC values of higher than 5% have been recorded (Svensen et al., 2007).
The average TOC of the Prince Albert formation is 0.7% (Geel et al., 2013).
The thermal maturity of the Prince Albert shale is estimated to be between 2% and 4% R o, which places
the shale in the dry gas window (Geel et al., 2013; Kuuskraa et al., 2013; Svensen et al., 2007).
Within the dry gas prospective area of 155 865 km2 , the shale has a resource concentration of about
3 131 tcm/m2 , and risked shale gas in place of about 24 tcm. Based on the TOC and favourable
mineralogy, and taking into account the complex geology and dolerite intrusions, Kuuskraa et al.
(2013) estimated a risked technically recoverable shale gas resource of 2.73 tcm for the Prince Albert
shale formation.
58
W h i t e h i l l S h al e
The organic-rich shale layer of the Lower Permian Whitehill Formation is one of the main targets for
shale gas development in the Karoo Basin. The main mineral components of the Whitehill Formation
are quartz, chlorite illite, muscovite, albite and pyrite, with dolomite/calcite boudins occurring at the
base of the formation (Faure and Cole, 1999).
The organic-rich shale has a TOC of 28%. TOC values as high as 15% have been recorded (Branch et
al., 2007; Faure and Cole, 1999) where extensive dolerite intrusions have occurred (Cole and
McLachlan, 1994). The average TOC of the Whitehill Formation is 4.5%, which fulfils the basic
prerequisites of a good gas-bearing shale, and makes it the key target for potential shale gas extraction
(Geel et al., 2013).
The thermal maturity of the Whitehill shale is estimated to be between 2% and 4% Ro, which places
the shale in the dry gas window (Geel et al., 2013; Kuuskraa et al., 2013; Svensen et al., 2007).
4 289 tcm/m2 , and risked shale gas in place of about 11 tcm. Based on the TOC and favourable
(2013) estimated a risked technically recoverable shale gas resource of 5.98 tcm for the Whitehill shale
formation.
C o l l i n g h am S h a l e
The main mineral components of the Collingham Formation are quartz and illite, with pyrite close to
the contact with the Whitehill Formation (Geel et al., 2013).
The average TOC of the Collingham Formation is 0.7% (Geel et al., 2013).The thermal maturity of the
Collingham shale is estimated to be between 2% and 4% R o, which places the shale in the dry gas
window (Geel et al., 2013; Kuuskraa et al., 2013; Svensen et al., 2007).
2 662 tcm/m2 , and risked shale gas in place of about 9.29 tcm. Based on the TOC and favourable
(2013) estimated a risked technically recoverable shale gas resource of 2.32 tcm for the Collingham
shale formation.
2.5.3.2.2 Upper Ecca Group
The Upper Ecca Group includes the Ripon, Fort Brown and Waterford Formations, each having their
own shale sequences. The organic content and thermal maturity of the Upper Ecca formation shales
are less than the Lower Ecca formation shales. The TOC ranges between 1% and 2%, and with the
59
thermal maturity ranging from 0.9% to 1.1% R o, the shales are believed to be in the oil to wet gas
window. Because the average TOCs of these formations are below 2% they will not be discussed
further as they are not considered prospective areas for shale gas development at this time (Kuuskraa
et al., 2013).
2.5.3.3 Coal formations within the Ecca Group
This section will cover the coal properties of the Ecca Group within the northern Karoo Basin, covering
information such as ash content and coal resources of each formation.
South Africa has a total of 19 coalfields which were either deposited as part of the Ecca, Beaufort or
Molteno Group sedimentary successions. Four of these coalfields may contain as much as 70% of
South Africas remaining coal resources. These are also the coalfields which have been the recent focus
due to their UCG and CBM potential (Hancox and Gtz, 2014).
The four coalfields are the Limpopo (Tuli) Coaleld, Soutpansberg Coaleld (Mopane, Tshipise and
Pafuri sub-basins), Waterberg Coaleld (Ellisras Basin) and the Springbok Flats Coaleld. These
coalfields are located north of the MKB (distal depocentres) in the Limpopo (Tuli) Basin, the
Soutpansberg (Tshipise) Basin, Waterberg (Ellisras) Basin and Springbok Flats Basin, respectively.
These basins all form part of the Karoo Basin, and the coalfields were deposited as part of the Ecca or
Beaufort Groups (Hancox and Gtz, 2014). These coalfields are preserved in isolated extensional
intracratonic and intercratonic grabens and are collectively referred to as the northern Karoo Basins.
Only the Waterberg coalfield will be discussed as it contains between 40% and 50% of South Africas
remaining coal resources and is considered, according to Hancox and Gtz (2014), as the last major
coal resource in the country. Furthermore, it has been considered for UCG development.
2.5.3.3.1 Lower Ecca Group
The Lower Ecca Group of the northern Karoo Basins includes the Pietermaritzburg Formation which
has no coal seams (Hancox and Gtz, 2014).
2.5.3.3.2 The Middle Ecca Group
In the Waterberg coalfield the Middle Ecca Group has approximately 101.3 million tonnes proven coal
reserves and 628.6 million tonnes inferred coal reserves (Dreyer, 2014).
60
V r y h e i d F o r m at i o n
The Vryheid Formation in the Ellisras/Waterberg Basin is approximately >300 m deep, 55 m thick and
has approximately 12 coal seams with thicknesses that range between 1 m and 6 m. Most authors
have accepted the following numbering system for the dull coal seams: 1, 2, 3, 4A and 4 (Hancox and
Gtz, 2014).
Zones 1 to 4 consist of dull coal with brighter coal at the base of each seam. The thicknesses of the
different coals are indicated in Figure 2.19. The lower coal parts of each coal zone have better lower
ash coal which have some coking properties, but in general, the coal zones have little coking potential.
Furthermore, from Figure 2.19 it can be seen that the ash content increases upward from 21% to 43%.
The Zone 1 and Zone 2 coal from the Grootegeluk Mine are used as steam coal at the Matimba Power
Station and can be used as metallurgical coal, depending on the phosphorus content (Hancox and
Gtz, 2014).
The raw coal analyses of the upper Vryheid and lower Vryheid coal seams in the Tuinplaas (Springbok
Flats Basin) area are illustrated in Table 2.16.
TABLE 2.16: CO AL QUALITY OF THE MIDDLE ECCA SPRINGBOK FLATS
Inherent
Calorific Value Volatile Matter Total Sulphur (TS)
Seam Ash (%) Moisture
(CV) (MJ/kg) (VM) (%) (%)
(IM) (%)
Upper Vryheid seam 23.5 27.8 30.2 2.1 2.9
Lower Vryheid seam 20.6 34.6 26.8 2.5 2.4
Source: Adapted from Linning et al. (1983)
According to the desired coal characteristics required for UCG (see Table 2.17), the Vryheid formation
in the Waterberg/Ellisras basin might be considered for UCG, as the coal is deeper than 300 m, the
coal seams have a thickness between 1 m and 6 m, with the no. 3 coal seam with a thickness of 5.5 m.
The no. 3 coal seam of the upper Vryheid seams, might have a calorific value of 23.5 MJ/kg and have
an ash percentage of less than 60%, when considering the ash values from the Springbok Flats Vryheid
Formation. Furthermore, the coal of the Vryheid Formation may be considered because the entire
formation displays a remarkable lateral continuity in the distal region of the Karoo Basin (Cadle, 1982).
Problems that may be encountered are geological features which may serve as pathways for
contamination to migrate towards potable groundwater resources.
61
Figure 2.19: Stratigraphic column of the Waterberg Coalfield, showing the different formations,
coal sequences and the coal qualities of the 11 coal seams
62
TABLE 2.17: COMPILATION OF DESIRED COAL DEPOSIT CHARACTERISTICS FOR UNDERGROUND COAL
CLASSIFICATION
Pricewaterhouse
Characteristic Reddy (2013) Coopers (PWC) Burton et al. (2006) Exergy (2010) Average
(2008)
Depth 100 600 m 100 600 m >150 m 30 800 m 315 m
Thickness >5 m >5 m >1.5 m 0.5 30 m 7m
Lignite through to Bituminous and
CV/rank bituminous lower rank 8-30 MJ/Kg 23 MJ/Kg
(1733 MJ/kg) (1733 MJ/kg)
Ash <60% <60% <60%
Must be below
Absence of any water table;
Should be isolated
Water good-quality Not a potable water
from aquifers
aquifers source
(TDS >1 000 ppm)
Coal must have
Minimal seam Strong overlying
Geology minimal Dip 0 70
discontinuities strata preferable
discontinuities
Access for drilling
Other
and monitoring
Note:
2.5.3.3.3 The Upper Ecca Group
In the Waterberg coalfield, the Upper Ecca Group has approximately 45 005 million tonnes proven
coal reserves and 2 127.40 million tonnes inferred coal reserves (Dreyer, 2014).
V o l k s r u s t/ Gr o o te gel u k F o r m a t i o n
The Upper Ecca Group of the northern Karoo Basins includes the Volksrust/Grootegeluk Formation
which is approximately 250 m deep, 7090 m thick and consists of mudstones interbedded with coals
(Cadle, 1982; Faure et al., 1996). The Volksrust Formation has approximately seven coal zones which
are named Zones 511, as they are found on top of the four Vryheid Formations, of which the thickest
coal seam is approximately 1 m thick (Hancox and Gtz, 2014) (see Figure 2.19).
The seven coal zones of the Volksrust Formation are all similar with 10.3% ash after being beneficiated
(washed), except for Zone 6 which, due to its higher phosphorus content, can only be used for the
production of thermal coal. After the secondary wash the ash content can be as high as 35% which is
suitable for power generation (Hancox and Gtz, 2014). The mean vitrinite reflectance of the
Grootegeluk Formation is 0.72%.
Little information is published on the overall coal qualities of the Volksrust Formation, although it is
known that the coal rank increased steadily from west to east and that most of the coal is classified as
63
dull coal with thin bright laminae and has semi-soft coking ability (Hancox and Gtz, 2014), therefore
it can be assumed that the coal CV percentage would be in the range of 526 MJ/kg.
Based on the depth of the coal seams, the ash percentage and the probable calorific value of the coal
seams, the Volksrust coal might have UCG potential, except that the coal seams are less than the
required coal seam thickness of 5 m, of which the thickest coal seam in the Volksrust Formation of the
Waterberg Basin is approximately 1 m.
2.5.4 Geohydrology of the Karoo Basin
The danger facing the Karoo groundwater through hydraulic fracturing and UCG, stems from the fact
that the groundwater at different depths may be interconnected with one another. If a deep aquifer
is polluted, the pollution may reach shallow freshwater aquifers through springs, faults, dykes and
other possible pathways.
This section will focus on the different aspects of the MKB aquifer system, starting with a brief
description of the Karoo aquifer system, followed by the groundwater occurrence depths, the macro-
chemical constituents of the Karoo aquifers, the dissolved gases in the groundwater of the Karoo, the
radioactive isotopes of Karoo rocks, the chemistry of shale and coal groundwater one would expect at
hydraulic fracturing and UCG operations, respectively, and lastly, a description of the different
geological preferential flow paths which fluid and gas contaminants may use to migrate towards fresh
potable groundwater sources.
As mentioned in the geology section above, even though the formations of the northern Karoo basins
show differences to their correlative counterparts in the MKB, these formations show similarities at
group level to the geological groups of the MKB (Hancox and Gtz, 2014). Therefore, the geohydrology
of the MKB is believed to be similar to the geohydrology of the northern Karoo Basins and will be
collectively referred to as the Karoo.
2.5.4.1 Karoo aquifer systems
More than 80% of South African aquifers occur in hard rock formations. These hard rock formations
can be divided into two aquifer classes: the first class is fractured aquifers, which occur in igneous and
metamorphic rock sequences; and the second class, which occurs mainly in layered sedimentary rocks,
such as the rocks of the Karoo Supergroup sedimentary succession and is known as multi-porous
fractured aquifers. These sedimentary rocks/formations display the geometry of a porous medium,
but have large porosity variations and are often intersected by bedding plane fractures (Botha, 1998;
Van Tonder et al., 2001). One of the major characteristics of Karoo Supergroup aquifers is that they
64
have low permeabilities, which means that the majority of the boreholes drilled into these aquifers
have very low yields (less than 1 l/s).
Groundwater contained in fractured and weathered rock aquifers is one of the most important
resources for local communities who use the water for livestock, irrigation and domestic purposes
(Karoo Groundwater Expert Group [KGEG], 2013).
There are a known knowledge gaps concerning the geohydrology of the Karoo Group, namely:
Hydraulic and hydrochemical characteristics of deep formations (> 300 m).

Presence of deep aquifers (>1 000 m).
Hydrostatic pressures in the Ecca Group.
Water compartments created by dolerite intrusions.
Hydraulic interconnectivity between the deep groundwater and shallow aquifers.
Upward migration of deep groundwater (Rosewarne et al., 2013).
2.5.4.2 Groundwater occurrence in the Main Karoo Basin

Groundwater can occur in three potential aquifers systems within the Karoo Basin, these are:
Shallow aquifers (0 to 300 m): It was postulated by Van Tonder (2012) that the shallow aquifer
system is less than 300 m below surface, possibly between 10 m and 30 m deep, with a thickness
between 150 m and 170 m (with a top weathered zone with a thickness of possibly 30 m, the
groundwater level lies within this zone, and a fractured zone with a thickness of 130 m) (KGEG,
2013). The shallow aquifers may be separated by the deep groundwater by impermeable rocks
(1001 000 m thick).
Deep aquifers (300 to 1 000 m): Little is known about deeper formations (>300 m below surface)
and their groundwater status and the possible interconnection to shallow aquifers, but it is
unlikely (although the possibility does exist) that a continuous aquifer zone deeper than 300 m
would occur; the water deeper than 300 m would be defined at thermal (>25 C) brackish to saline
water that occurs under pressure (Rosewarne et al., 2013).
Ultra-deep aquifers (>1 000 m): It is not yet known whether an aquifer deeper than 1 000 m below
surface exists. The possibility of such an aquifer will be resolved by deep exploration drilling, and
the possibility of deep groundwater moving upward into shallow aquifers is being investigated
(Rosewarne et al., 2013).
65
2.5.4.2.1 Groundwater levels in South Africa
The depth of groundwater in South Africa was determined by Musekiwa and Majola (2013) by
interpolating the average water levels of approximately 244 733 boreholes on the National
Groundwater Archive (NGA) to exploit the correlation between water level and topography (see Figure
2.20). From the figure, it can be seen that the average water level in South Africa is in the range of 5
30 m below ground level.
Figure 2.20: Groundwater level distribution in South Africa
2.5.4.3 Water chemistry of the Karoo aquifers
On a regional scale the water quality in the Karoo Formations are highly variable throughout Southern
Africa, where climatic patterns are the major control on mineralisation and water types. On a local
scale, due to the nature of groundwater flow, anomalies to the regional scale generalisation are
widespread, and on a micro-scale, quality variations occur due to the nature of the groundwater flow
in the Karoo rocks, which are controlled by the residence time differences within the matrix and
fracture components of the groundwater flux (Woodford and Chevallier, 2002).
M a j o r c o n s ti t u en t s
In this section the distribution of major hydrochemical constituents of the groundwater in the MKB
are discussed. Emphasis is placed on macro-scale trends and not on small-scale variations. Woodford
and Chevallier (2002) used the available data from the National Water Quality Database (QUALDB
database) during their analysis to construct the distribution figures of major hydrochemical
66
constituents of the groundwater in the MKB. The major constituent distribution for the rest of South
Africa (which includes the northern Karoo Basins) was unfortunately not available, and only the major
constituents of the groundwater in the MKB will therefore be presented. However, as the lithologies
in the northern Karoo basins are similar to those found in the MKB, one would expect similar
concentration ranges.
T o t a l d i s s o l v e d s o l i d s , p H , c a l c i u m a n d m a g n e s i u m d i s t r i b u ti o n
Figure 2.21. Insert A indicates the TDS distribution expressed as geometric means over the Karoo
Basin. Insert B indicates the mean pH distribution over the Karoo Basin. The pH values ranged from
low in high-lying territories, such as near the Drakensburg area to higher in flat-lying areas such as the
Free State (Woodford and Chevallier, 2002). Insert C indicates the calcium distribution expressed as
geometric means over the Karoo Basin. Calcium, together with bicarbonate, are usually the dominant
constituents in recharge water (Woodford and Chevallier, 2002). Insert D indicates the magnesium
distribution expressed as geometric means over the Karoo Basin. Magnesium had a similar distribution
pattern to calcium, but not at the same concentration levels.
S o d i u m , t o t a l h a r d n es s a n d e l e c t r ic al c o n d u c ti v it y d i s t r ib u ti o n
Figure 2.22: Insert A indicates the sodium distribution expressed as geometric means over the Karoo
Basin (Woodford and Chevallier, 2002). Insert B Indicates the total hardness distribution over the
Karoo Basin. Insert C Indicates the electrical conductivity (EC) distribution over the Karoo Basin
(Murray et al., 2012; Van Tonder, 2012).
T o t a l a l k a l i n it y , c h l o r id e , s u l p h a te a n d n i t r a te d i s t r i b u ti o n
Figure 2.23: Insert A indicates the total alkalinity distribution expressed as geometric means over the
Karoo Basin. Bicarbonate and carbonate represent total alkalinity, and are formed by (1) introduction
of CO2 with rainfall and biological soil activities, and (2) dissolution of carbonates in the aquifer
(Woodford and Chevallier, 2002). Insert B indicates the chloride distribution expressed as geometric
means over the Karoo Basin. Insert C indicates the sulphate distribution expressed as geometric means
over the Karoo Basin. Insert D indicates the nitrate distribution expressed as geometric means over
the Karoo Basin. Nitrate does not pose a regional health-risk problem but does occur locally in
excessive concentrations usually due to point source contamination of the groundwater from the
surface (Woodford and Chevallier, 2002).
F l u o r i d e d i s t r i b u t io n
Figure 2.24 indicates the fluoride distribution expressed as geometric means over the Karoo Basin.
High fluoride concentrations are found in acid igneous rocks, which are not found in the Karoo Basin
(Woodford and Chevallier, 2002).
67
Figure 2.21: Major physio-chemical distribution throughout the Main Karoo Basin of South Africa
68
69
70
Figure 2.24: Fluoride distribution throughout the Main Karoo Basin of South Africa
2.5.4.4 Dissolved gases in the groundwater of the Karoo
According to Kent (1949), the main gases that might be present in the groundwater of the Karoo are
H2 , N2 , Ar, He, NO2 , CO2 and CH4 -C4 H10 .
The methane throughout the Karoo Basin, and dissolved in groundwater, can be classified as being
biogenic (sub-surface sources) or thermogenic (deep sources) (Molofsky et al., 2013; Talma and
Esterhuyse, 2013). There are three different processes which can produce methane (see Figure 2.25).
The shaded area represents methane that can be produced through any of the mechanisms. The blue
area box indicates the general area values for thermogenically produced gas and the red area box
indicates the general area values for biogenically produced gas (Schoell, 1980).
BIO-F refers to biological fermentation, which is said to produce the most biogas and usually occurs at
landfills and organic-rich freshwater environments; BIO-R refers to biological CO2 reduction. This is a
process of CO2 reduction by H2 , and is the most significant in marine environments. THERMO refers to
thermogenic processes, which produces methane through burial and thermal decomposition of
71
organic matter due to the earth geothermal gradient, at temperatures greater than 70 C and isotope
ratios closer to that of the source material (Kaplan et al., 1997; Schoell, 1980).
Figure 2.25 can be used to determine the source of the methane in the groundwater. If it was, for
instance, determined during the groundwater baseline establishment phase that the methane from
shallow groundwater resources was biogenically produced, and during monitoring it was found that
the methane was thermogenically produced (or a mixture of thermogenic and biogenic gas), it might
be an indication that a pathway towards the shallow groundwater resources has been
created/induced due to unconventional gas activities.
Figure 2.25: Areas of characteristic isotope 13C and D values for methane generated by different mechanisms
2.5.4.5 Radioactive isotopes of Karoo rocks
Publicly available reports on the occurrence and distribution of different radioactive material in the
Karoo Basin are scarce, with few reports discussing the concentration of radioactive constituents in
the groundwater. In a recent study by Baiyegunhi et al. (2014) on the Aliwal North hot springs it was
concluded that the hot springs contain uranium, potassium and thorium at concentrations acceptable
for consumption. In the report by Steyl et al. (2012) it was proposed that before drilling for shale gas,
a baseline should be established which should measure for stable isotopes as well as radioactive
isotopes. When flowback and produced water from unconventional gas operations return to the
surface, the water is generally saline, and contains a variety of dissolved minerals, some of these
dissolved minerals may contain naturally occurring radioactive materials (NORMs) (RSA DMR, 2012).
72
This water (or drill cuttings) containing radioactive materials may be stored on the surface (Resnikoff
et al., 2010). If this radioactive material is spilled on the surface, it may leach into the soil and reach
the groundwater resources. The hazard of contamination depends on the mobility of the radioactive
material, the type of radioactive material, the volume and concentration of the leak (CCA, 2014). In
other words, the physical, biological and chemical properties of the contaminant and also local
(geohydrological) conditions (Fetter and Willard, 2001).
The radionuclides that may be present in Karoo groundwater are uranium ( 238 U, 235 U, 234 U), radon
(222 Rn), radium (228 Ra, 226Ra), and lower concentrations of polonium (210 Po), lead (210 Pb stable isotope)
and thorium (232 Th) (Focazio et al., 2001; Xu et al., 2012).
Other radionuclides such as thorium are insoluble in water and therefore not of concern. Radium is
mobile in acidic water but less mobile in alkaline water, and may be of concern. Radon is an inert gas
which is very mobile and therefore very important (Young, 2013).
2.5.4.6 Chemistry of shale groundwater
To establish a groundwater baseline for unconventional gas projects, it is necessary to determine

which chemical parameters to analyse for. Therefore, the results obtained from previous studies on
the chemical composition of shale formation water should be taken into account as similar chemicals
may be encountered at a specific site at which a groundwater baseline should be established for a
hydraulic fracturing operation.
The following sections cover the chemical composition of shale formation water, produced water from
shales, the general water quality of shales and the composition of shale produced water in the Karoo.
2.5.4.6.1 Shale formation water
Shales are one of the most abundant rock formations on earth and are considered as host of various
wastes. A test conducted by Von Damm (1989) suggested that groundwater in shales have a wide
range compositions and are primarily a Na-Cl-HCO3 or Na-HCO3 -Cl type.
During the study by Von Damm (1989), it was determined that the most abundant anions in shale
groundwater are Cl, HCO3 and SO4 (which is likely due to the oxidation of pyrite). Furthermore, it was
determined that Ca, K and Na are the major cations. Shales that have a high clay content (for example,
illite, smectite, montmorillonite) and tend to be associated with groundwater with higher K
concentration.
73
2.5.4.6.2 Produced water from shales
The chemistry of unconventionally produced water (water co-produced with oil and gas) from shale
and coal varies from well to well and lithology to lithology, but it is dominated by the same chemistry
as conventionally produced water from coals and shales (USEPA, 2015b).
Produced water from shale is generally enriched in the following constituents:
Major anions: chloride, bicarbonate, sulphate.

Major cations: sodium, calcium, magnesium.
Metals: barium, strontium, bromide (Chapman et al., 2012).
NORMs: radium-226, radium-228 (Rowan et al., 2011).
Organics: hydrocarbons (such as BTEX and oil and grease) (USEPA, 2015b).
Unconventional produced water may also contain low levels of some metals such as chromium,
aluminium, copper, arsenic, boron, lead, cadmium, mercury, zinc, vanadium, cobalt and nickel (Hayes,
2009; Orem et al., 2014).
Alley et al. (2011) compiled geochemical parameter data of shale produced water from original
analyses, peer-reviewed reports, as well as confidential industry sources; a total of 541 shale gas
records were analysed. From the data, it was concluded that the major ions in produced water are
calcium, magnesium, zinc, chloride, potassium and sodium. Furthermore, the produced water tends
to be acidic and enriched in strontium, barium and bromide.
From a study conducted by USEPA (2011) on four different shale gas plays it was concluded that
produced water from shales are generally characterised as Na-Cl-Ca water type, with elevated levels
of bromide, sulphate, potassium, and bicarbonate and seldom elevated chloride, fluoride, nitrate as
N, nitrite as N, strontium and barium levels.
2.5.4.6.3 Naturally occurring radioactive material (NORM)
Shales commonly contain uranium (normally Uranium235 and Uranium238 ), thorium (normally as Th232)
and radium, together with their decay products. These radioactive materials are present in most
unconventionally produced water. Other radionuclides which may be present in shale produced water
are 222 Rn and 40 K (Orem et al., 2014).
Depending on the depositional conditions, marine black shales (such as the Ecca shales of the Karoo
Supergroup) are estimated to contain an average of 5250 ppm uranium and 9.515.1 ppm thorium,
depending on the depositional conditions (Bloxam, 1964; Fertl and Chilingar, 1988; Polaski and
Lange, 1965).
74
2.5.4.6.4 Organics
Produced water from conventional an unconventional coal and shale gas sources contain various
organic contents in different wells and lithologies, and can contain any of the following:
Volatile organic compounds (VOCs), such as benzene toluene, ethylbenzene and xylenes (BTEX).
Semi-volatile organic compounds (SVOCs), such as phenols (primarily C0-C5).
Polycyclic aromatic hydrocarbons (PAHs).
Saturated hydrocarbons.
Macromolecular natural organic matter (Benko and Drewes, 2008; Orem et al., 2014).
Table 2.18 presents concentration ranges of selected organic parameters in produced water from two
shale gas plays in the USA.
TABLE 2.18: CONCENTRATION OF SELECTED ORGANIC PARAMETERS FROM UNCONVENTIONAL SHALE

P RODUCED WATER, PRESENTED AS AVERAGE (MINIMUMMAXIMUM)
Barnett shale Marcellus shale

Parameter Unit Pennsylvania,
Texas Pennsylvania
West Virginia
163.5 74 16.9
Oil and grease mg/L
(88.21 430) (5802) (4.7802)
680 220
Benzene g/L
(495 300) (5.82 000)
760 540
Toluene g/L
(798 100) (5.16 200)
29 42
Ethylbenzene g/L
(2.2670) (7.6650)
360 300
Xylenes g/L
(431 400) (156 500)
Average total BTEX g/L 1.829 2.910 1.102
Notes:
Bold italic numbers indicate median values
VOCs and SVOCs have been detected in produced water from shale and coal. The produced water
from shale may contain naphthalene, alkylated toluene, and methylated aromatics in the form of
several benzene and phenol compounds (see Table 2.19). It should be noted that the data presented
in Table 2.19 was collected from 190 days of flowback after hydraulic fracturing was ended, therefore
the results are a mixture between produced water and flowback water (Spellman, 2012).
75
TABLE 2.19: O RGANIC CONSTITUENTS DETECTED IN THE FLOWBACK WATER FROM TWO UNCONVENTIONAL
SHALE FORMATIONS
Barnett Marcellus
Parameters (g/l) Pennsylvania, Maryland, New York,
Texas
Ohio, Virginia, Wyoming
Acetone 145 (27540) 83 (145 800)
1,2,4-Trimethylbenzene 173 (6.91 200) 66.5 (7.74 000)
1,2-Diphenylhydrazine 4.2 (0.57.8) ND
1,3,5-Trimethylbenzene 59 (6.4300) 33 (5.21 900)
1,4-Dioxane 6.5 (3.112) ND
2,4-Dichlorophenol (ND15) ND
2,4-Dimethylphenol 14.5 (8.321) 12
2-Methylnaphthalene 1 362 (5.420 000) 3.4 (2120)
2-Methylphenol 28.3 (5.876) 13 (1115)
3-Methylphenol and 4-Methylphenol 41 (7.8100) 11.5 (0.35-16)
Acetophenone (ND4.6) 13 (1022)
Benzidine (ND35) ND
Benzo(a)anthracene (ND17.0) ND
Benzo(a)pyrene (ND130.0) 6.7
Benzo(b)fluoranthene 42.2 (0.584.0) 10
Benzo(g,h,i)perylene 42.3 (0.784.0) 6.9
Benzo(k)fluoranthene 32.8 (0.665.0) 5.9
Benzyl alcohol 81.5 (14.0200) 41 (17750)
Bis(2-Ethylhexyl) phthalate 210 (4.8490) 20 (9.6870)
Butyl benzyl phthalate 34.3 (1.9110) ND
Carbon disulfide ND 400 (197 300)
Chloroform ND 28
Chrysene 120 (0.57240) ND
Dibenz(a,h)anthracene 77 (3.2150) 3.2 (2.311)
Di-n-butyl phthalate 41 (1.5120) 14 (11130)
Di-n-octyl phthalate (ND270) 15
Diphenylamine 5.3 (0.610.0) ND
Fluoranthene (ND0.18) 6.1
Fluorene 0.8 (0.461.3) 8.4
Indeno(1,2,3-cd)pyrene 71 (2.9140) 3.1 (2.49.5)
Isopropylbenzene 35 (0.869) 120 (86160)
Naphthalene 238 (4.83 100) 195 (141 400)
N-Nitrosodiphenylamine 8.9 (7.810) 2.7
N-Nitrosomethylethylamine (ND410) ND
Phenanthrene 107 (0.521 400) 9.75 (322)
Phenol 63 (1793) 10 (2.421)
Phenolic compounds 119.65 (9.3230) ND
Pyrene 0.2 (ND0.18) 13
Pyridine 413 (100670) 250 (102 600)
Notes:
ND: No data available
Bold italic numbers indicate median values
76
Organics such as acetone, 2-butanone, carbon disulphide, and pyridine can potentially be used as
friction reducers or industrial solvents in hydraulic fracturing treatment; these organics have been
detected in shale produced water (Hayes, 2009).
BTEXs are associated with petroleum and have been found in produced water from several basins.
The average total BTEX concentration in unconventional produced water ranges from 20 to 3 000 g/l
(USEPA, 2015b).
PAHs have been found in shale produced water but high levels are associated with coal produced
water (Sirivedhin and Dallbauman, 2004). The major PAHs that were identified in a study by Orem
et al. (2014) in produced and formation water from shale were naphthalene and alkyl naphthalenes,
phenanthrene and alkyl phenanthrenes, anthracene and alkyl anthracenes, acenaphthene and alkyl
acenapthenes, pyrene, and chrysene and alkyl chrysenes.
2.5.4.6.5 Composition of shale produced/formation water in the Karoo Supergroup
There are not many publicly available sources on the composition of formation water in shales of the
Karoo. Work done by Kent (1949) suggests that formation water in the Ecca series is enriched in
sodium chloride (NaCl) and that the total dissolved solids (TDS) exceed 2 000 mg/l.
Chemical concentration values for the Ecca Whitehill Formation were determined through a leaching
test by Steyl and Van Tonder (2013) and compared to different shales to see if a comparison exists.
From Table 2.20 it can be seen that the concentrations of the constituents are very different from one
another. This might be due to the different analysis methodologies used. Therefore, to compare the
values, ratios of the major elements were used to determine if a correlation exists (see Table 2.21).
TABLE 2.20: COMPOSITIONAL COMPARISON BETWEEN DIFFERENT SHALES
Element (mg/l)
Source
Ba Ca Fe Li Sr Mg K Na
250 22 500 38 800 46 290 16 400 24 900 4 850 Hem (1985)
1 552 8 451 64 70 1 650 728 237 24 043 Hayes (2009)
2.7 2 400 770 1 3.2 308 50 50 Karoo
Source: Alley et al. (2011); Hayes (2009); Hem (1985); Steyl and Van Tonder (2013)
From Table 2.21 it can be seen that a good correlation exists between the Hem (1985) and Karoo data.
The Hayes data differs notably in the Ba/Ca, Ba/Li and Ba/Mg ratios when compared to the Karoo data.
This difference might be due to two possibilities: the first being that produced water from the Hayes
data might have been changed due to the mixing of the water with hydraulic fracturing fluid, and
secondly, there might be a significant difference between the geology of the two data sets.
77
TABLE 2.21: COMPOSITIONAL RATIO COMPARISON BETWEEN DIFFERENT SHALES
Element (mg/l)
Source
Ba/Ca Ba/Sr Ba/Li Ba/Mg Ba/Na Ca/Mg Sr/Na
0.01 0.86 5.43 0.02 0.05 1.37 0.06 Hem (1985)
0.18 0.94 22.17 2.13 0.06 11.61 0.07 Hayes (2009)
0.01 0.84 2.7 0.01 0.05 7.79 0.06 Karoo
Source: Alley et al. (2011); Hayes (2009); Hem (1985); Steyl and Van Tonder (2013)
2.5.4.7 Chemistry of coal groundwater
To establish a groundwater baseline for unconventional gas projects, it is necessary to determine

which chemical parameters to analyse for. Therefore, the results obtained from previous studies on
the chemical composition of coal formation water should be taken into account as similar chemicals
may be encountered at a specific site at which a groundwater baseline should be established for a
UCG operation.
The following sections summarise the chemical composition of produced water from coal, the general
water quality of coal and the composition of coal produced water in the Karoo.
2.5.4.7.1 Produced water from coal
See also Post-Processing Effluent (Section 2.4.3.2.2).
Table 2.22 presents the baseline groundwater concentrations for constituents generally associated
with UCG operations compared to the maximum concentration values for those constituents in the
produced water collected after UCG has occurred. As can be seen from the table, all the UCG produced
water constituent concentrations increased when compared to the baseline concentrations. From the
table, it is also apparent that the maximum concentration values vary significantly from site to site.
This can be explained by considering the distance of the sampled well from the cavity, where higher
concentrations are found in water samples collected from wells closer to the cavity. The time of
sampling is also vital, as the lower concentrations are related to increased time since gasification
occurred. According to Ahern and Frazier (1982), the coal aquifer water type from groundwater
baseline studies is typically the Na-HCO3 type, with TDS values in the range of 5001 500 mg/l.
Work done by Von Damm (1989) on six coal basins in the USA indicated that there is a large variability
in coal formation water chemistry. The results from the study indicated that at least six major inorganic
constituents could be found in all the coal formation water from the different basins, namely: calcium,
magnesium, sodium, bicarbonate, chloride, and sulphate. Furthermore, it is conceivable that sulphuric
acid would be a major concern in UCG projects as air and water may be introduced to pyrite enriched
coal seams during the UCG operation (Pinetown and Boer, 2006).
78
TABLE 2.22: BASELINE GROUNDWATER CONCENTRATIONS COMPARED TO PRODUCED WATER
CONCENTRATIONS AT DIFFERENT UNDERGROUND COAL GASIFICATION SITES
Location
Constituent Hoe Creek 1 Hanna 1 Hanna 2 Fairfield
Base Max Base Max Base Max Base Max
Cations (mg/l)
Ammonium (NH4) 1 72 2.3 15 1 10
Boron (B) 0 0.5 0.06 1.5 0.06 0.3 0.3
Calcium (Ca) 36 220 15 32 20 200
Iron (Fe) 0.01 37 0.04 8 6
Lead (Pb) 0.001 0.041 0.03 0.03 0.03 0.1
Magnesium (Mg) 10 60 9 15 5 15
Manganese (Mn) 0.06 0.06 0
Zinc (Zn) 0.2 0.9
Anions (mg/l)
Cyanide (Cn) 0 290 940
Sulphate (SO4) 150 1 230 400 1 600 4 1 150
Thiocyanate
Thiosulfate
Organics
Benzene (/l) 4 192 607
DOC (mg/l) 4 230
Naphthalene (/l) 5 0 640
Phenols (mg/l) 0.001 450 270 0 20
Toluene (/l) 11 68 2 200
Xylene (/l) 1 10 1 000
Others
Total dissolved solids (mg/l) 700 340 1 700 3 300 350 2 300
pH (Standard unit) 8 6 8
Notes:
DOC: Dissolved organic carbon
Source: Adapted from Ahern and Frazier (1982)
79
2.5.4.7.2 Metals
Also see Produced water from shales (Section 2.5.4.6.2).
According to Booth et al. (1999), As, B, Cd, Mo, Hg, Se and Pb in South African coals are of the greatest
environmental concern, with Cr and Ni of moderate concern, and Li and Sb of minor concern.
Wagner and Hlatshwayo (2005) compiled a table, based on different studies, to compare the trace
element concentration of South African coals with coals found across the globe (see Table 2.23).
From the table, it can be seen that South African coals have noticeably higher arsenic, chromium,
cobalt, nickel and vanadium concentrations when compared to average global concentrations.
TABLE 2.23: COMPARISON OF TRACE ELEMENT CONCENTRATION OF SOUTH AFRICAN COALS WITH OTHER
GLOBAL COALS (PPM)
Australian
Witbank South South USA/ thermal Average Average
Trace element Global range
no. 2 seam African coals African coals USGS a export coals global values global values
(mg kg-1)b
Antimony (Sb) 0.47 1.2 0.47 0.0510 3.0 1.0 0.09
Arsenic (As) 4.6 0.98.2 24.0 1.26 0.580 5.0 9.0 0.7
Cadmium (Cd) 0.39 0.47 0.067 0.13 0.6 0.2 0.03
Chromium (Cr) 28 25 1263 15.0 15.9 0.560 10 17.0 1
Cobalt (Co) 7.9 7.8 3.314 6.1 4.48 0.530 5 6.0 0.2
Copper (Cu) 9.7 10.9 4.216 16.0 9.8 0.550 15 17.0 1
Lead (Pb) 10 10.1 1.925 11.0 6.8 280 25 9.0 0.7
Manganese
30 0.11 51.4 5300 50 76.0 6
(Mn)
Mercury (Hg) 0.327 0.17 0.042 0.021 0.12 0.1 0.01
Molybdenum
<12.7 3.3 1.71 0.110 5 2.1 0.1
(Mo)
Nickel (Ni) 17 15.5 6.932 14.0 11.5 0.550 15 17.0 1
Selenium (Se) 0.9 <0.40.9 2.8 0.5 0.210 3 1.6 0.1
Vanadium (V) 27 1743 22.0 20.6 2100 25 28.0 1
Zinc (Zn) 10 18.1 3.216 53.0 12.0 5300 50 28.0 2
Notes:
a: Arithmetic mean
b: Average value of 10 different thermal coal exports
Source: Adapted from Wagner and Hlatshwayo (2005)
80
2.5.4.7.3 Naturally occurring radioactive material (NORM)
Unconventional and conventional coal deposits tend to be enriched in radioactive material. Coal is
often a favourable location for uranium to be present at elevated concentrations (OReilly, 1982).
Coal from the United Kingdom, United States, Australia and India can contain up to 4 ppm uranium,
coal from Germany up to 13 ppm, and from Brazil and China up to 20 ppm. Thorium generally has
concentrations of three times the uranium concentration. Furthermore, uranium and thorium
concentrations in coal ash can be up to ten times that of burnt coal. Other radionuclides such as lead
210 and potassium 40 may also be at noteworthy concentrations in solid residue.
Lower rank coals such as brown coals, subbituminous coals and lignites, are more effective in
adsorbing metals during coalification and will therefore contain higher NORM concentrations when
compared to higher ranked coals (Karangelos et al., 2004). Therefore, it is expected that the
groundwater contained in the dull coals of the Vryheid Formation in the Waterberg/Ellisras Basin
would have high NORM concentrations.
2.5.4.7.4 Organics
In a study by Orem et al. (2014) on the organic substances in formation and produced water from CMB
coal bed plays across the USA, it was found that PAHs had the highest concentration of all the different
organic compounds analysed for.
Other organic compound classes present in the produced and formation water included: heterocyclic
compounds, alkyl phenols, aromatic amines, alkyl aromatics (alkyl benzenes, alkyl biphenyls), long-
chain fatty acids, and aliphatic hydrocarbons (Orem et al., 2014).
Of the PAHs observed, the predominant PAHs observed were two-ring (naphthalene, phenanthrene
and anthracene) and alkylated two-ring compounds.
2.5.4.7.5 Composition of coal produced/formation water in the Karoo Supergroup
According to Pinetown and Boer (2006), the general water quality from coal collieries in South Africa
is generally acidic (due to the production of sulphuric acid as a result of reaction with iron sulphides
such as pyrite) and contain many dissolved metals such as zinc, lead, arsenic, copper, iron and
aluminium.
By considering the mineralogical composition of a formation, one can deduce what chemical
constituents might be dissolved in the produced/formation water of the specific formation as t he
chemical nature of water is influenced with which it is in contact (Pinetown and Boer, 2006).
81
The main mineral components of the coal formations in the South Africa are:
Quartz (SiO2 )
Clay minerals, such as:
Kaolinite (Al2 Si2 O5 (OH)4 )
Illite ((K,H3 O)(Al,Mg,Fe)2 (Si,Al)4 O10 [(OH)2,(H2 O)])
Montmorillonite ((Na,Ca)0,3 (Al,Mg)2Si4 O10(OH)2 n(H2O))
Sulphide minerals
Pyrite (FeS2 )
Carbonate minerals, such as:
Calcite (CaCO3 )
Dolomite (Ca,Mg(CO3 )2 )
Ankerite Ca(Fe2+,Mg,Mn)(CO3 )2
Siderite Fe2+(CO3 )
Phosphate minerals, such as:
Apatite Ca 5 (PO4 )3 (OH,F,Cl) (Pinetown and Boer, 2006).
South African clay is dominated by clay minerals, mainly kaolinite and illite, followed with smaller
amounts of quartz, carbonates, dolomite and siderite (Gaigher, 1980, cited by Pinetown and Boer,
2006). Therefore, formation water from South African coals might have high concentrations of
aluminium, silica, potassium, sodium, calcium, magnesium, iron and chloride.
2.5.4.8 Description of geological preferential flow paths
When establishing a groundwater baseline, it is necessary to be aware of the presence, type, extent
and orientation of the different geological preferential flow features in the study area, as the baseline
should be receptor focussed and these features may serve as pathways towards potential receptors
which may use potable groundwater for irrigation or domestic purposes. These features should,
therefore, be identified during the geological investigations and targeted during the drilling stages of
the baseline investigation as will be discussed in Section 3.6 and Section 3.8, respectively.
By selecting and installing boreholes into these features would enable the boreholes to be used as
early warning detection systems for contaminant migration towards potable groundwater resources
during monitoring. This section will discuss the different geological preferential flow features which
may serve as pathways for potential fluid and/or gas migration towards potable groundwater
resources due to hydraulic fracturing and UCG projects in South Africa. Each geological feature will be
discussed briefly and the possible pathway(s) for fluid and gas migration explained.
82
2.5.4.8.1 Dolerite dykes and sills
Dolerite dykes and sills are magmatic intrusions which were emplaced between 183182 Ma
immediately before the Lesotho (Drakensberg) eruption, as part of the Karoo large igneous province
(Svensen et al., 2007). In the western Karoo Basin the Ecca group was intruded by 120 m thick planar
sills, which heated the sedimentary strata which it intruded and led to metamorphic reactions in the
aureoles and the expansion of pore fluids, which in turn led to phreatic eruptions and formation of
hydrothermal vents which are presently exposed in the central part of the Karoo (see Sub-section
2.5.4.8.3) (Jamtveit et al., 2004).
Researchers believe that due to the apparent lack of dolerites near the town of Graaff-Reinet, this part
of the Karoo basin would be the best place for shale gas exploration and development (Scheiber-Enslin
et al., 2014).
It is estimated that the dolerite sills cover approximately 390 000 km2 of the MKB, with a volume of
367 000 km3 (Svensen et al., 2007; Svensen et al., 2012) (see Figure 2.26). From Figure 2.26 the
geographical distribution of the different intrusions into the Karoo Basin of South Africa can be seen.
Figure 2.26: Distribution of different intrusions in the Karoo Supergroup
The areal extent of the dolerite intrusion is limited to the south of the Karoo basin by northward tilting
sediments of the Karoo, which is due to tectonic activity in the Cape region.
83
P o s s i b l e p a th w a y f o r f l u i d a n d g a s m i g r a ti o n
Studies have shown that heating the shale layers by dolerite intrusion (up to 1 000 C), due to contact
metamorphism of carbon-rich sediments with the sills, can result in the conversion of organic matter
to gas (mostly CH 4 and CO2 ) (McClintock et al., 2008; Svensen et al., 2007). If this gas migrated upward
and became trapped by an overlying sill (Talma and Esterhuyse, 2013) it could cause a potential
blowout at the surface if drilled through, and serve as a pathway for gas to migrate into shallow fresh
groundwater resources.
Large volumes of gas have been recorded close to dolerites, possibly in the fractures surrounding the
dolerite which were created due to heating of organic matter (Rowsell and De Swardt, 1976). These
fractures might serve as possible pathways for gas migration out of the production zone towards the
surface and into fresh groundwater resources.
According to Chevallier and Woodford (1999), when an inclined dolerite sheet passes upward into a
flat lying sill (outer sill), the overlying sediment is uplifted, which creates open fractures adjacent to
the sheet (at low levels). These fractures can serve as potential pathways for fluid and gas migration
towards the surface and into fresh groundwater resources.
In a 2013 study, Van Tonder et al. predicted with the use of a model that it would take pollutants less
than two months to travel from the fractured reservoir (horizon) via a connected fault zone or dyke
(dolerite dyke) to an abstraction borehole, 6 km from the wellpad.
If a hydraulic fracturing or UCG study area is under artesian conditions (south of the Great Escarpment)
pollutants may potentially migrate upwards in the Karoo formations. Therefore, if contaminated fluid
reaches a fault and/or dolerite dyke which is connected to the surface, the pollutants may possibly
reach potable groundwater sources or even the surface (KGEG, 2013; Van Tonder et al., 2013).
2.5.4.8.2 Breccia pipes
Both Breccia pipes and hydrothermal vents are formed through dolerite sill intrusions. There are
thousands of breccia pipes in the Karoo Basin, of which most occur in the western Karoo Basin
(Svensen et al., 2007) (see Figure 2.26). The pipes were formed during dolerite magma intrusion
events 182.5 0.4 million years ago (Svensen et al., 2007).
Breccia pipes are sub-vertical cylindrical structures which cut through sedimentary strata and were
formed due to gas pressure built-up during shale metamorphism due to contact of shale with sill
intrusions. Figure 2.27 presents a cross section of a breccia pipe and its relationship with a sill intrusion
and the metamorphic contact aureole.
84
In the western Karoo Basin the pipes are rooted in the contact aureoles of shales and consist mainly
of brecciated and baked (metamorphic) black shale (see Figure 2.27). From Figure 2.26 the
geographical distribution of breccia pipes in the Karoo basin of South Africa can be seen.
Figure 2.27: Schematic cross section of a breccia pipe
These pipes served as pathways for gas to escape to the atmosphere (Svensen et al., 2007), and may
potentially serve as pathways for fluid and gas migration toward the surface and groundwater
resources during hydraulic fracturing.
2.5.4.8.3 Hydrothermal vents
There are more than 500 mapped hydrothermal vent complexes in the Karoo Basin, but they mainly
occur in the Stormberg Group of the Karoo Supergroup (Jamtveit et al., 2004).
Hydrothermal vents are shallow (<1 km), semi-vertical, semi-circular cone-shaped structures with
surface diameters of hundreds of metres. The pipes of the vent complexes generally consist of
sandstone.
These vents are formed due to the contact of dolerite intrusions with sediment containing aqueous
pore fluids, leading to boiling of the pore fluids. The boiling of fluids causes overpressure and creation
of a cone-shaped hydrothermal vent complex through ascending fluid and vapour. This vapour and
gas driven system is able to brecciate consolidated sediments (Jamtveit et al., 2004). Figure 2.28
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illustrates an idealised hydrothermal vent complex with an upper and lower part. From Figure 2.26
the geographical distribution of hydrothermal vents in the Karoo basin of South Africa can be seen.
Figure 2.28: Diagram illustrating an idealised hydrothermal vent complex
Hydrothermal vents are abundant in the Stormberg Group, and could have acted as pathways for
thermogenic gas releases due to the contact of dolerite intrusion with shales. The sandstone pipes
and brecciated sediments next to the hydrothermal vent may potentially serve as potential pathways
for fluid and gas migration towards the surface and groundwater resources.
2.5.4.8.4 Kimberlite Intrusions
Kimberlite dykes or pipes consist of ultrabasic/ultramafic intrusive rocks (1 6001 700 Ma (oldest
kimberlites)) and occur as clusters of dykes/fissures and diatreme swarms with root zones and
blows/pipes (Gurney et al., 2005). There are two different groups of kimberlite dykes which are
divided based on age, distribution, petrography, whole rock geochemistry and isotopic/petrographical
information (Smith, 1983; Smith et al., 1985). Group I (10075 Ma) is found distributed across the
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Karoo Basin and across the world, whereas Group II (140144 Ma) kimberlite dykes are restricted to
the Kaapvaal craton (Allsopp et al., 1989; Skinner, 1989).
The geographical distribution of kimberlite dykes and associated fractures in the Karoo basin are
indicated in Figure 2.29. From the figure, several swarms or tectonic provinces can be distinguished,
each with its own kimberlite dyke trend directions, chemical characteristics and geological controls.
Figure 2.29: Distribution of Cretaceous kimberlite dykes (red lines and dots) in and outside of the Main Karoo Basin
Joints that are found parallel to the kimberlite fissures may act as potential preferential pathways for
fluid movement. The main control on fluid movement would be the reactivated faults that
accompanied the emplacement of kimberlite magmas (Woodford and Chevallier, 2002).
Another potential pathway for fluid movement is through or alongside heterogeneous and brecciated
kimberlite pipes/diatremes which are similar to breccia pipes/plugs (Hawthorne, 1975; Woodford and
Chevallier, 2002).
2.5.4.8.5 Faults
Faults are fractures in rock material along which a measurable displacement across the fracture plane
occurred due to compressional or extensional stresses (Park, 1997).
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According to the RSA DMR (2012), the major threat to groundwater resources in the vicinity of the
hydraulic fracturing operation is the migration of hydraulic fracturing fluids along pre-existing
fractures of the Cape Fold Belt towards groundwater resources. This statement can be interpreted as
referring to faults, as well as fractures, as fractures have a lower hydraulic conductivity than faults (as
they are generally smaller), and also that in geohydrology, faults are often referred to as fractures, as
it is not of interest for hydrogeologists to know if displacement occurred along a fracture plane. (See
Section 2.5.4.8.6 for more information on fractures).
Faults occur throughout the entire Karoo Basin, and in South Africa, each fault system owing their
origin to different geological processes, or a combinational of different geological processes such as
compressional and/or extensional events.
Faults may serve as potential pathways for fluid and gas migration towards the surface and
groundwater resources (Sury et al., 2004), as many thermal springs rise along these faults to the
surface through the Ecca and Beaufort (Woodford and Chevallier, 2002), such as the Brandvlei and
Gamka valley thermal springs, where faults rooted in the Cape Supergroup are the pathways for the
water to the surface (Kent, 1949).
Also, geological folds may contain faults in the hinge zones of anticlines and synclines, due to loss of
cohesion associated with longitudinal strain in the fold hinge zone. This loss of cohesion may lead to
preferential flow paths (extensional fractures or normal faults) through which fluid may migrate,
similar to the transport mechanism associated with mesothermal lode gold deposits (Cox, 1999).
A study by Van Tonder et al. 2013 predicted that it would take pollutants less than 2 months to travel
from the fractured reservoir (horizon) via a connected fault zone or dyke (dolerite dyke) to an
abstraction borehole, 6 km from the hydraulic fracturing wellpad (Van Tonder et al., 2013).
2.5.4.8.6 Fractures, joints and mineralised veins
Fractures or joints are the most common geological features and may be seen in any rock
exposure/outcrop and in the crests of folds. Fractures are cracks that were formed due to loss in
cohesion of the rock material. Joints can be found parallel or perpendicular to the bedding or layered
rock. Parallel joints can be found parallel to bedding planes due to pressure release because of the
pressure from the overlying layers, whereas perpendicular joints can be formed in the hinges of folds
due to cohesion failure.
The most common joints that are found near a dolerite dyke, kimberlite pipe and breccia pipes are
cooling joints, which normally form parallel to the intrusion. Fractures or joints can be filled with, for
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example, calcite or quartz, creating mineralised veins (KGEG, 2013; Park, 1997). In the Beaufort Group
sandstones, vertical joints are well-developed. These joints may be permeable as high-yielding
boreholes have been drilled into these bodies (Woodford and Chevallier, 2002).
Karoo Basin mineralised veins, mostly filled with calcrete/calcite, are the products of tectonically
reactivated dolerite dykes due to Cretaceous kimberlite activity or by more recent master jointing.
The reactivation may result in sub-vertical fissures within the country rock, or within the dyke. These
fissures (veins) generally have a width of up to 150 mm (Woodford and Chevallier, 2002).
Fractures, joints and mineralised veins, although generally small, may serve as potential pathways for
fluids and gas to migrate towards the surface and groundwater resources (Sury et al., 2004).
2.6 POTENTIAL GROUNDWATER IMPACTS ASSOCIATED WITH HYDRAULIC

FRACTURING AND UNDERGROUND COAL GASIFICATION EXTRACTION
TECHNIQUES
The rapid increase in unconventional gas development around the world has brought wells and related
infrastructure to remote areas and closer to population centres which has caused public concern
about the possible negative impacts of unconventional gas development to the environment.
When establishing a groundwater baseline for unconventional gas projects it is necessary to be aware
of the different potential groundwater impacts, sources of contamination and migration pathways
associated with hydraulic fracturing and UCG operations. The pathway a contamination source may
follow towards a potential receptor should be intercepted during drilling, as the boreholes intersecting
these pathways may serve as early warning detection systems during groundwater monitoring after
the unconventional gas operation has commenced.
The potential impacts presented in this section do not to attempt to predict which of the impacts are
most likely to occur or to predict the magnitude of a potential impact on the groundwater resources.
The sources are from both peer reviewed and non-peer reviewed literature, as some of the potential
impacts to groundwater may be speculative and not yet proven or disproven. Further, some of the
potential impacts listed here are unlikely to occur at a specific site, but the risk still exists and is
therefore mentioned for comprehensiveness.
The literature that is cited here is limited by the publication date of this dissertation. Therefore, t his
review of the literature should only be viewed as a summary of what is known to date.
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This section will, first, focus on the different potential groundwater impacts associated with hydraulic
fracturing operations, and secondly, focus on the potential groundwater impacts associated with UCG
operations, followed by similar geology-related issues associated with hydraulic fracturing and UCG
operations, and, finally, concludes with a hypothetical case study where contaminant migration was
simulated.
2.6.1 Potential groundwater impacts due to hydraulic fracturing operations

The major mechanisms by which shale gas development through hydraulic fracturing can lead to
contamination of groundwater resources are:
Deficiencies in the well casing or cement which can lead to unintended movement of liquids or
gases along the outside of the production well or out of the production well into drinking water
resources.
Movement of gases or liquids through geological formations from the production zone.
Intersecting gas pockets during drilling, which can cause migration of volatiles, and blowouts at
surface.
Surface spills of fluids or solids (drilling fluids, fracturing fluids, produced water, hydrocarbons and
solid waste).
Disposal/discharge of insufficiently treated wastewater into groundwater through abandoned
boreholes.
After production, due to the artesian and sub-artesian conditions in the Karoo, the well pressures
will return to equilibrium conditions, which can cause migration of different chemicals along
geological features (faults, dykes) and along compromised casings (Birol et al., 2012; Krupnick
et al., 2014; USEPA, 2006; Van Tonder et al., 2013).
The RSA DMR (2012) highlighted the following four major concerns of hydraulic fracturing operations
in South Africa: the volumes of water required relative to the resources of the region; potential water
resource contamination; disposal of wastewater (flowback and produced water); and hydraulic
fracturing fluid transport to and from the well sites.
The potential groundwater resource impacts associated with hydraulic fracturing operations which
will be discussed are divided into the following four categories:
Potential impact of water acquisition.

Potential contamination due to surface handling and transportation issues.
Potential contamination due to issues related to wastewater management and disposal.
Potential contamination due to well-related issues.
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Impacts are defined as any change to the quantity or quality of water resources, and potential impacts
are defined as any change to the quantity or quality of water resources that could logically occur as
the result of a mechanism or potential mechanism that has not yet been observed. In addition, where
possible, it is important to identify the mechanics which are responsible or potentially responsible for
any impacts.
2.6.1.1 Water acquisition for hydraulic fracturing operations
South Africa is classified as a water scarce country. It is regarded as the 30th most water scarce country
in the world (National Water Strategy, 2012). About 75% of the countrys water use is from
groundwater, and 94% of the Karoos water use is from groundwater which is used for domestic,
livestock and agricultural purposes (Greeff, 2012). The dependence of groundwater in the region,
together with the fact that the Karoo is a predominantly dry region, makes sourcing for water of the
required volumes for hydraulic fracturing problematic (Vermeulen, 2012).
The lack of water in the semi-arid Karoo presents a concern that hydraulic fracturing might deplete
the source area of its fresh water because of the high volumes of water required for hydraulic
fracturing. Due to the water scarcity, commercial gas production involving hydraulic fracturing in the
Karoo could prove to be uneconomical (Warren, 2013).
According to USEPA (2015b), the water used for hydraulic fracturing generally comes from surface
water sources such as rivers, dams and streams and from groundwater and reused wastewater from
hydraulic fracturing operations. Because water transport costs are high the industry tends to acquire
water from the nearest sources (Kargbo et al., 2010).
According to Vermeulen (2012), a number of possible water sources exist, namely:
Use of local groundwater supplies, which includes water from 4 000 breccia plugs in the western
Karoo.
Use of seawater, or desalinated seawater.
Transportation of surface water from unknown sources, by railway, road pipes, or a combination
thereof.
Water from the Orange River.
The following table is a summary of the volume of water used per well obtained from various sources.
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TABLE 2.24: SUMMARY OF THE VOLUME OF WATER USED PER WELL
Source Average volume of water per well (m 3)
Rivard et al. (2012) 19 791.7

Arthur et al. (2008) 13 248.9
Peduzzi and Harding Rohr Reis (2013) 22 500.0
Satterfield et al. (2008) 11 356.2
Kargbo et al. (2010) 20 500.0
USEPA (2010b) 13 248.9
United States Department of Energy (2009) 11 250.0
Collins (2010) 18 500.0
Average volume of water 16 291.9
Based on the average of 16 291.9 cubic metre per well, a wellpad with eight wells could use 130 395.7
cubic metre (130 395 700 l) within two to three months, which is the same volume of water needed
to fill 52 Olympic-size swimming pools, irrigate 26 ha of land or meet the needs of New York City for
seven minutes (CCA, 2014).
2.6.1.2 Surface handling and transportation
Surface handling and transportation issues which may possibly contaminate surface water bodies and
groundwater resources include spills and leaks on and near the drilling site such as spills from storage
tanks, leaks from storage ponds and pits, blowouts, faulty connections of pipes and hoses, hose and
line failure, blender malfunction, improperly tested parts on the manifold, spills from high-pressure
pump trucks and spills and leaks from the wellhead, and spills and leaks away from the drilling site,
such as transportation spills via trucks and pipes.
In a study conducted by Koppelman et al. (2012) it was suggested that accidental release of hydraulic
fracturing fluid at the surface poses a greater contamination risk to groundwater than the actual
hydraulic fracturing process. A study by USEPA (2015b) concluded that one third of spills on or near
the wellpad were the result of equipment failure. Peduzzi and Harding Rohr Reis (2013) adds to this
by suggesting that surface handling errors, such as accidental spills of fluids and/or solids are the
largest threat to groundwater contamination. Therefore, to decrease the threat to groundwater it is
essential that the equipment used during hydraulic fracturing operations are regularly inspected and
undergo sufficient maintenance, and that human error is eliminated as far as possible. Table A 1 in
Appendix A presents a summary of the potential issues related to surface handling and transportation
issues related to hydraulic fracturing operations.
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2.6.1.3 Wastewater management and disposal
Wastewater is the water that is generated at the wellpad, including flowback water, produced water
and drilling fluid (Finkel and Hays, 2013; Rahm et al., 2013). According to Rozell and Reaven (2012),
wastewater management and disposal are the largest drinking water resource contamination risks.
Issues related to wastewater management and disposal which may possibly contaminate surface
water bodies and groundwater resources, include leachate from radioactive drill cuttings, deep well
injection, discharged wastewater into streams from municipal and industrial wastewa ter treatment
facilities, direct discharge of untreated fluid into streams and rivers, land application of treated
wastewater, direct discharge of untreated wastewater into rivers, spills of wastewater at the
treatment plant, and disposal of drilling mud and drill cuttings on-site.
In a study conducted by Rahm (2011), it was concluded that industrial treatment, deep well injection
and reuse of wastewater are more likely to be utilised by operators than the use of municipal
treatment facilities; this is due to public concern that municipal treatment facilities are not able to
treat high TDS wastes. Table A 2 in Appendix A presents a summary of the potential issues related to
wastewater management and disposal issues related to hydraulic fracturing operations.
2.6.1.4 Well-related impacts
Incorrect well construction, unforeseen accidents during drilling, well casing leaks, and deterioration
of cement during production or after well abandonment, can lead to boreholes becoming conduits for
man-made and naturally occurring fluids. These fluids can contaminate groundwater resources due to
naturally occurring vertical pressure gradients which force the fluids along the well and through
induced and naturally occurring fractures, and fractures in the cement annulus (Kang et al., 2014; King
and King, 2013; Watson and Bachu, 2009).
The possible gas and liquid migration towards the surface and groundwater resources might occur
due to a single mechanism or as a combination of different mechanisms; for example, flaws in cement
may expose the casing to corrosive fluids (Jackson et al., 2013).
Peduzzi and Harding Rohr Reis (2013) pointed out in their study that leakage of hydrocarbons or
chemicals from the underground production zone (pay zone) is unlikely, but possible, with increased
probability with decreased distance between the production zone and the groundwater resource.
According to Davies et al. (2014), well failures can occur in any type of hydrocarbon borehole due to
injecting fluid into a reservoir, producing hydrocarbons, or while the well is being drilled. It is
estimated that 675% of wells experience zonal isolation (cement) or structural integrity failures, and
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that deviated wells (which deviate from vertical to horizontal) used for hydraulic fracturing of shales,
might fail at higher rates than conventional vertical wells (Ingraffea et al., 2014; Jackson, 2014).
Fluids that might potentially migrate include both fluids that are injected into the well (including leak-
off) and formation fluids (including brine and natural gas) (USEPA, 2015b). Table A 3 in Appendix A
presents a summary of the potential well-related issues relating to hydraulic fracturing and UCG
operations.
2.6.2 Potential groundwater impacts due to underground coal gasification

operations
Groundwater contamination due to UCG operations is considered the most serious risk associated
with UCG operations (Kapusta et al., 2013). The potential for groundwater contamination associated
with UCG operations has, however, caused public concern, because, during gasification, different
gasification compounds such as phenols and PAHs may migrate from the gasification zone and
contaminate the groundwater resources (Burton et al., 2006).
The major mechanisms through which UCG operations can lead to groundwater contamination are:
Land subsidence due to the removal of material from the underground coal formation. This may
cause pathways to form (such as induced fracture zones). The induced fractures which were
formed in the overlying formations may serve as preferential pathways for fluid and gas migration
towards groundwater resources.
Dispersion and penetration of contaminants from the coal seam to the surrounding rock layers
through diffusion and penetration.
Leaching of contaminants from underground residue by natural groundwater influx after the
gasification process (Ahern and Frazier, 1982; Booth, 2002; LIU et al., 2007; Sury et al., 2004).
This section is a review of the potential impacts to groundwater from chemical and nonchemical
stressors associated with UCG operations and also describes likely exposure pathways. The potential
groundwater resource impacts associated with UCG operations are divided into two categories:
Potential impact of water acquisition.

Potential contamination due to issues related to underground coal gasification.
Limited evidence suggests that UCG operations do produce significant environmental consequences
(Burton et al., 2006). A European UCG trail was conducted without any environmental contamination
during and after the operation. Therefore, it is assumed that if UCG is conducted correctly, no serious
environmental risks are expected (LIU et al., 2007).
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Many of the issues related to hydraulic fracturing operations may also occur at UCG operations, such
as the following well-related issues: incorrect construction practices, gas migration up the annulus and
unforeseen accidents during drilling (Sury et al., 2004). Table A 3 in Appendix A presents a summary
of the potential well-related issues related to hydraulic fracturing and UCG operations.
Further, with regard to wastewater management and disposal issues related to UCG operations, one
of the main potential sources of groundwater and surface water contamination is from the post-
processing effluent (wastewater) which is produced during the production phase. This effluent is
collected in the different modules of the surface gas processing system and, if not treated
appropriately, can pose serious environmental risks (Kapusta et al., 2013).
2.6.2.1 Water acquisition for underground coal gasification operations
During the UCG process, water is consumed to produce hydrogen and carbon dioxide during
gasification reactions, in particular the water-shift reactions. The water is from the coal seam and
from the surrounding strata (Van der Riet, 2008; Verma et al., 2014). This consumption decreases the
amount of water present in the subsurface.
It is believed that the hydraulic head of the overburden will also decrease near the cavity zone due to
water ingress from the overburden into the cavity (Sury et al., 2004).
After site decommissioning, the air/oxygen injection is stopped, there will be a drop in generator
pressure which potentially creates an increase of groundwater influx into the created cavity (Bahl
et al., 2014), which may result in a lowering of groundwater levels.
The average amount of water used during gasification of a single coal seam would be very site specific
and depend on the surrounding groundwater pressure of the cavity, the amount of water required
during gasification, and the operator who controls the influx of the groundwater (Linc Energy, 2006).
For example, after gasification was stopped at the Hanna I UCG trial site in Wyoming; USA, the cavity
contained 1 140 000 l influx water, while the Hanna III test site contained 644 000 l influx water (Sury
et al., 2004).
2.6.2.2 Potential contamination due to issues related to underground coal gasification
As mentioned previously, the groundwater contamination risk associated with UCG operations is quite
low, if proper management and construction practices are followed. Land subsidence which occurs
due to cavity collapse of burned coal is considered to pose the largest risk to groundwater. After
subsidence has occurred, fractures and/or faults are created in the overlying strata which may connect
to potable groundwater resources; these fractures and/or faults may serve as migration pathways for
stray gas and fluid migration from the gasification zone to potable groundwater resources (Burton
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et al., 2006; LIU et al., 2007). This risk is, however, decreased with increased UCG depth and distance
between the groundwater resources and the gasified coal seam. See Table A 4 in Appendix A for a
summary of the potential contamination issues unique to UCG operations.
2.6.3 Similar potential groundwater impacts associated with hydraulic

fracturing and underground coal gasification operations
2.6.3.1 Geological pathways
Geological considerations which may result in potential groundwater contamination include fluid
and/or gas migration along preferential flow paths such as faults, pipes, veins, joints, fractures,
dolerite dykes and sills. The possible liquid and gas migration towards the surface and groundwater
resources might occur due to a single mechanism or as a combination of different mechanisms,
therefore, stresses in one mechanism could lead to stresses in another. For example, induced fractures
containing contaminants, which reach an abandoned well could contaminate the groundwater
resources through gas migration along the wellbore. Also, migrating gas from the induced fractures
could also migrate through a fault which intercepts the abandoned well, and lead to contamination of
the groundwater through the fault, if the fault is connected to a groundwater resource.
See Section 2.5.4.8 for the description of the different geological preferential flow paths which might
be encountered in the Karoo basins of South Africa. See also Table A 5 in Appendix A for a summary
of potential groundwater contamination due to geology-related issues for hydraulic fracturing and
UCG operations.
2.6.4 Hypothetical case study in a Karoo aquifer

A study by Van Tonder et al. (2013) focused on determining the potential impact that hydraulic
fracturing would have on groundwater in the Karoo Basin. A two-dimensional numerical model (for
flow in the vertical direction) and a two-dimensional mass transport model (for flow in the horizontal
direction) was used to simulate what would happen if hydraulic fracturing fluid was released into fresh
groundwater through preferential flow paths in the cement annuli of the gas well and subjected to
different flow controls. They used the SOEKOR CR 1/68 deep exploration borehole as a hypothetical
well with 10 wells drilled around it, where hydraulic fracturing would take place.
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Their findings are summarised below:
Leaks (upward flow through cracks) from damaged/compromised annuli can take place at a rate
of between 0.00024 l/s to 1.87 l/s (in openings of 0.5 mm).
From the two-dimensional numerical model it was found that an area as large as 300 ha could be
contaminated in a downstream groundwater flow direction from the wellpad over a period of 30
years (with no abstraction boreholes in action) (see Figure 2.30). From the figure the following
could be noted:
The contaminant would have travelled 2.8 km from the wellpad after 5 years (mostly
downstream; the same applies to the other scenarios).
The contaminant would have travelled 6.8 km from the wellpad after 10 years.
A second scenario is of an active abstraction borehole at the Cranemere farm (see Figure 2.31).
From the figure the following could be noted:
A third scenario is of a fault intersecting the Cranemere abstraction borehole (see Figure 2.32).
From the figure the following could be noted:
The contaminant would have travelled 6.9 km from the wellpad after 10 years and reached
the Cranemere abstraction borehole 6 km downstream of the wellpad.
Furthermore, it was found that if an abstraction borehole (6 km from the wellpad) intersect a
fracture (along a fault or dyke), which intersects or is connected to the shale reservoir, the
contaminant will reach the abstraction borehole in less than two months, as flow velocities along
a fracture can be as high as 120 m/day (3 600 m/month) and even higher flow velocities are
expected along faults and dolerite intrusions.
Hydraulic fracturing in South Africa cannot be done in the same manner as in other countries.
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Figure 2.30: Simulated movement of pollutants with an input concentration of 100% at the Cranemere wellpad,
under natural conditions (no active pumping)
Figure 2.31: Simulated movement of pollutants with an input concentration of 100%, where an abstraction borehole at
the Cranemere farm house is introduced, with an abstraction rate of 0.5 l/s
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Figure 2.32: Simulated movement of pollutants with an input concentration of 100% ; where a fault (green line) crosses the
area, the pollutant that reaches the abstraction borehole after 10 years has a con centration of 10%
From this simulation, it is conceivable that it may also apply to UCG operations if effluent wastewater
were to be discharged from a leaky casing and flow through induced or naturally occurring fractures.
This simulation is significant as it can be used to establish a preliminary study area size for both
hydraulic fracturing and UCG groundwater baseline establishment studies (see Section 3.5).
2.7 CONCLUSION
This chapter discussed the difference between conventional and unconventional gas and provided a
summary of how natural gas is formed. The different types of natural gas resources and how much of
these resources are available globally was presented. The chapter also discussed the hydraulic
fracturing and UCG extraction techniques which may be used in South Africa for which a groundwater
baseline methodology was established. The contaminants which may be associated with these
extraction techniques, along with the flow paths these contaminants may follow were also discussed.
The geology and geohydrology of the Karoo Basin and sub-basins were described, specifically focusing
on the Ecca Group formations, as it is the group which is targeted for its shale and coal gas resources.
This was followed by a summary of the different potential groundwater impacts, sources of
contamination and migration pathways associated with hydraulic fracturing and UCG operations.
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Chapter 3
GROUNDWATER BASELINE ESTABLISHMENT METHODOLOGY FOR
HYDRAULIC FRACTURING AND UNDERGROUND COAL
GASIFICATION PROJECTS
3.1 INTRODUCTION
No methodology for establishing a groundwater baseline for unconventional gas extraction projects
in South Africa has been constructed yet. Establishing a standard methodology, based on best
practices and recommendations made in similar studies, would aid in collecting high quality
representative data at different hydraulic fracturing and UCG sites around South Africa.
The overall aim of this study was therefore to fill this gap and establish a groundwater baseline
methodology for unconventional gas projects in South Africa, specifically focussing on hydraulic
fracturing and underground coal gasification operations.
The sections that follow will discuss the different phases of the proposed methodology for establishing
a groundwater baseline for hydraulic fracturing and UCG projects in South Africa, and in doing so
attempt to provide answers to questions that have not been fully answered in the existing literature
on establishing a groundwater baseline for unconventional gas projects, such as:
During which phase of the unconventional gas project should the baseline be established?
What information should be collected before conducting a sampling event?
What size should the study area be?
How should potential groundwater sampling locations be selected?
How frequently should groundwater samples be collected?
Is drilling of dedicated monitoring boreholes required to collect representative groundwa ter
samples?
What chemical parameters should be analysed?
How to collect representative groundwater samples?
What water quality standards are required when interpreting chemical constituents that have
been analysed?
To answer these questions and to construct the proposed groundwater baseline establishment
methodology, literature were reviewed regarding baseline establishment for oil and gas projects
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(hydraulic fracturing, CBM, and UCG) as well as the industrys best practices on conducting geological
and geohydrological field investigations and collecting representative groundwater samples.
After the proposed baseline methodology has been constructed, the methodology will be compared
to three South African unconventional gas case studies. Case Studies One and Two were based on
establishing groundwater baselines for UCG projects. Case Study Three was based on determining
whether sub-thermal spring waters (>25 C) were suitable sampling alternatives for deep Karoo
(hydraulic fracturing). Case Study Three was included as the findings of the study were used to modify
the sampling parameters of the established baseline methodology.
After the proposed baseline methodology has been compared to the three case studies, suggestions
will be made on how the studies could have been improved based on the established baseline
methodology in order to obtain more useful and representative results. This will be followed up with
a discussion of the areas where the established baseline methodology could have been improved or
refined based on the practices and results/findings of the case studies. Based on these improvements
and modifications a final baseline establishment methodology for an unconventional gas project for
South Africa will be formulated and presented in the form of a flow diagram.
It should be noted that this dissertation does not go into the details of constructing conceptual and
numerical models, conducting geophysical work, or performing tests to determine aquifer
parameters. Numerous books, reports and articles have been written on these subjects and will only
be mentioned in the context of establishing a groundwater baseline for hydraulic fracturing and UCG
projects.
3.2 PURPOSE OF THE BASELINE

There are many proponents and opponents of hydraulic fracturing and UCG. The disagreement about
the groundwater risks associated with unconventional gas projects persists because determining the
cause(s) of groundwater contamination is challenging.
There are several factors that contribute to this difficulty. First, contamination of groundwater can be
caused by a wide variety of human and natural activities. Second, the presence of contamination is
not always known, which means that if contamination is found, it may have been present for a long
time. Third, and most important, if contamination is found after an unconventional gas activity has
occurred, it is difficult for investigators to determine whether the contamination was introduced by
the unconventional gas activity or if the contamination existed prior to the activities.
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Therefore, it is crucial to establish a groundwater baseline prior to any unconventional gas activities
to be able to determine the source of the potential contamination. It would be in the best interest of
the public and the drilling companies to analyse for a wide variety of chemical constituents, including
general geochemical constituents such as nitrate, which would most probably not be introduced into
the groundwater by the unconventional gas companies. If nitrate contamination is, however, found in
the groundwater during baseline establishment, the unconventional gas companies cannot be held
accountable if the monitoring values fall within the natural concentration ranges established during
the groundwater baseline establishment phase (Hall, 2014).
To establish a groundwater baseline prior to unconventional gas activities would have the following
main benefits:
It would help resolve disputes regarding the causes of groundwater contamination.

Documenting the existing groundwater conditions of the site.
Early detection of changes in natural water quality and quantity trends due to unconventional gas
activities, which can be used to design appropriate management and mitigation systems before
adjacent groundwater users are impacted.
Groundwater quantity ranges can be established which can be used to indicate potential releases
or changes to the groundwater system.
The data could lead to more informed policy and regulatory decision-making.
Help alert the landowner regarding existing water quality problems.
Gain a better understanding of the natural temporal and spatial variations in groundwater levels
and quality (Edmunds and Shand, 2008; Hall, 2014; OBrien et al., 2013).
The goal of establishing a groundwater baseline, irrespective of the size of the study area, is to acquire
high quality data that utilises reproducible, simple and accurate techniques. High quality data refers
to data of sufficient:
accuracy, which depends on the correct choice of baseline tools and procedures which would
minimise subsurface and sample disturbance from collection to eventual analysis;
precision, which depends on the repeatability of sampling and analytical protocols, which can be
assured or improved by the replication of sample analyses including field and laboratory
standards; and
completeness, which is the ratio of the valid analytical results to the minimum sample number
(Puls and Barcelona, 1996).
The baseline sampling programme should be designed to establish groundwater quality conditions
around gas production wells before drilling activities have been conducted. The programme should
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be cost-effective and simple yet practical to obtain high quality data (Colorado Oil & Gas Association
[COGA], 2011; Colorado Oil & Gas Conservation Commission [COGCC], 2013).
The following sections are arranged according to the suggested order in which a groundwater baseline
has to be established for hydraulic fracturing and UCG projects. The sections are ordered in a manner
to achieve the following outcomes: to discuss what information needs to be collected to establish a
groundwater baseline before conducting any investigations; to determine what information needs to
be collected during the investigations; how to collect the information; what planning has to be done
before the initial and subsequent sampling events; and what to do with the data of the sampling
events.
3.3 DESCRIPTION OF THE METHODOLOGY

In this section the proposed methodology for establishing a groundwater baseline for hydraulic
fracturing and UCG projects in South Africa is presented and the different activities described briefly.
The different activities will then be discussed in more detail in their own sections.
There are many different opinions on when the groundwater baseline should be established. The
literature reviewed suggested that the groundwater baseline should be established at least 12 months
before the first production well is installed (COGA, 2011; Senior, 2014; Wyoming Oil and Gas
Conservation Commission [WOGCC], 2014). However, it is suggested that the groundwater baseline
should be established 3 years before the first production starts to account for lag times in groundwater
recharge and changes in chemistry.
3.3.1 Overview of the proposed methodology

Figure 3.1 illustrates the proposed groundwater baseline methodology for hydraulic fracturing and
UCG projects in South Africa in the form of a flow diagram.
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Note:
The green coloured boxes indicate the different activities for establishing the groundwater baseline and the yellow boxes pro vide rationales for undertaking the specific activity.
Figure 3.1: Summary of the proposed groundwater baseline methodology for unconventional gas projects in South Africa
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3.3.1.1 Description of the different activities
3.3.1.1.1 Desk study
During the desk study all the available literature on the geological, hydrological, geohydrological, and
potential receptors should be collected. The aim of the desk study is to construct a preliminary
conceptual site model; to determine where data gaps exist; to gain a better understanding of the
natural groundwater system spatially and temporally; to determine which potential receptors are
present in the vicinity of the unconventional gas operation; and, if possible, establish preliminary
groundwater quality and quantity ranges for the different hydrostratigraphic units in the study area.
Constructing a conceptual site model would aid in planning the different investigations to fill any
existing data gaps.
3.3.1.1.2 Defining the preliminary baseline study area size
Before conducting the geological and geohydrological investigations, the preliminary baseline study
area should be defined, based on whether the study is a regional or local investigation. The purpose
of defining the size of the preliminary study area is to establish boundaries within which future
investigations will take place (such as geological, geohydrological, hydrological, and groundwater
baseline sampling investigations).
3.3.1.1.3 Planning the geological and geohydrological investigation
Planning should be done before embarking on the geological and geohydrological investigations. The
purpose of the planning is to evaluate the available data; determine where data gaps in the study area
exist; determine how the data can and should be collected; acquire information on the owners of the
properties and boreholes in the study area; ask for permission to investigate the available boreholes
and to enter the property; acquire the required equipment and documentation; arrange meetings
with borehole and property owners; and arrange for transport and accommodation.
Some of the logistics of planning the geological and geohydrological investigation include the
following:
Acquire information on the owners of the properties and boreholes in the study area: Obtaining
contact details of property and borehole owners is not always an easy task. In South Africa, the
borehole location and owner details may be acquired from the National Groundwater Association
(NGA). The property owner information may be acquired from the Department of Water and
Sanitation (DWS), local farmer associations, land registry offices, managers working at silos and
establishments such as the Boer Republican Electoral Commission.
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Contact the owners of the properties and boreholes: After obtaining the contact details of the
property and borehole owners, the owners need to be contacted via email or telephone. The
purpose of the investigation, the group or company funding the investigation and the method of
the investigation should be explained to the owner.
After explaining the different investigations, the owner needs to be asked for permission to enter
the property; to temporarily remove any installed borehole equipment to be able to conduct
downhole logging (if required); to bypass any equipment and filtering systems installed onto the
borehole during groundwater sampling; and to install dedicated bladder pumps on abandoned
boreholes for groundwater sampling.
Before undertaking the investigation, and permission has been granted to conduct the different
investigations, meetings should be arranged with the property or borehole owners on when the
investigation(s) can be undertaken.
Acquire the required field equipment and documentation: The field equipment and
documentation that will be required depends on the type of field tests that will be performed by
the hydrogeologist, the geologist or the geophysicist, or the hydrogeologist skilled in all these
disciplines.
When meeting with the property owner, a letter of intent should be provided that should contain
the purpose of the investigation, the method of the investigation and the client for whom the
investigation is conducted. The owner of the property should be given a copy of the letter, and a
copy signed by the owner should be collected.
When collecting groundwater samples, a field sampling data sheet should be completed for each
sample collected. On the second page of the field sampling data sheet, additional information can
be recorded which the sampler deems noteworthy, such as the weather, location, local
topography, time of sampling, use of the well (Weight and Sonderegger, 2001).
Arrange for transport and accommodation: When selecting a vehicle, it is suggested to first use
satellite images and aerial photographs together with topographic maps to determine which
vehicle will be best suited for the type of terrain at which the investigation will take place.
When selecting accommodation, it is best to choose lodging which has good security systems in
place to prevent equipment from being stolen from the vehicle or from the room.
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3.3.1.1.4 Geological investigation
Geological investigations are required to fill missing geological data gaps in the study area by
conducting investigations such as surface geophysical surveys, borehole inspection (or hydrocensus),
and borehole logging. By filling the data gaps, the boundary conditions of the study area, as well as
the conceptual site model, can be updated.
3.3.1.1.5 Geohydrological investigation
Geohydrological investigations are required to fill missing geohydrological and hydrological data gaps
in the study area by conducting investigations such as aquifer tests to determine the hydraulic
properties of the different geological formations in the study area. Other geohydrological test s include
determining the location, rate and duration of groundwater recharge and discharge for numerical
modelling purposes; inspecting the presence and conditions of hydrological boundaries for
groundwater numerical model and aquifer test planning purposes; and determining the direction of
groundwater flow also for groundwater numerical model and aquifer test planning purposes.
However, before conducting aquifer tests, it is proposed that the geological formations present in the
study area need to be classified as preliminary hydrostratigraphic units. By classifying the formations
as preliminary hydrostratigraphic units would simplify the conceptual site model and would assist in
selecting existing, and drilling new boreholes on which to perform aquifer tests.
3.3.1.1.6 Update of preliminary conceptual site model and gap analysis
After the geological and geohydrological investigations have been undertaken, all the collected
relative information is used to update the preliminary conceptual site model. This is done to highlight
areas where data gaps exist. The highlighted areas are targeted during the drilling phase to collect
additional data to fill the data gaps with supplementary geological and/or geohydrological
investigations.
3.3.1.1.7 Drilling new boreholes
New dedicated boreholes should be drilled into each hydrostratigraphic unit in areas where the
existing boreholes cannot be used to supply sufficient geological and geohydrological information in
the study area and/or are not constructed to be able to use the preferred sampling device to collect
representative groundwater samples from the hydrostratigraphic unit of interest.
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3.3.1.1.8 Planning for the initial and subsequent sampling events
During planning for the initial and subsequent sampling events the following must first be completed:
selecting which physiochemical parameters to measure; selecting which chemical parameters to
analyse for; selecting which sampling device and methods to use; selecting the sampling frequency;
establishing quality assurance and quality control measures; and selecting a laboratory(s) to do the
chemical analyses.
3.3.1.1.9 Initial and subsequent sampling events
After planning for the initial and subsequent sampling events, the initial and subsequent sampling
events can be undertaken. During each sampling event the same sampling sequence, procedure and
methods should be followed in order to collect comparable data. Before samples can be collected,
dedicated bladder pumps should be installed into the selected boreholes and purged. After the
samples have been collected, the samples should be preserved and shipped to the selected
laboratory(s). If the same sampling equipment is re-used at multiple sites, the sampling equipment
should be decontaminated prior to use to prevent cross-contamination.
The laboratory analytical data should be validated by the laboratorys section head and by an
independent experienced quality assurance chemist for the correctness of the results. After the results
have been deemed reliable, the results may be presented graphically to identify chemical relationships
and to recognise any chemical changes in space and time.
3.3.1.1.10 Establishing a groundwater baseline
The groundwater baseline is established by determining the quantity ranges and the maximum and
minimum values for the different chemical parameters analysed for during the groundwater sampling
events, including the water levels measured for each hydrostratigraphic unit in the study area.
3.4 DESK STUDY

During the desk study the available geological, hydrological, geohydrological, and potential receptors
literature and information should be collected. The desk study plays an essential part in planning for
the next phases of establishing a groundwater baseline (Brassington, 2007). The aim of the desk study
(literature review) is to determine where data gaps exist; to gain a better understanding of the natural
groundwater system spatially and temporally; to determine which potential receptors are present in
the vicinity of the unconventional gas operation; to determine which features or structures may serve
as pathways for contamination migration towards potential receptors; and to establish preliminary
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groundwater quality and quantity baseline ranges (if possible) for the different hydrostratigraphic
units in the study area before any unconventional gas activities have taken place.
An essential part of any baseline establishment is to construct a preliminary conceptual site model
from the available information. The conceptual model is a simplified version of reality; it is a model
based on assumptions because a complete reconstruction of the study area is not feasible and even
less practical. A conceptual model is used to tie together all the available geological and
geohydrological information and present the key features of the physical system. Gathering
information for the construction of a preliminary conceptual site model is the basis of all
geohydrological investigations. By using a conceptual model, a clear picture of the study area can be
presented. From the preliminary conceptual site model, data gaps can be identified where further
investigation is required (Brassington, 2007).
In addition to being used to identify areas where data gaps exist, the preliminary conceptual site model
can also be used to present the potential sources of contamination; the pathways which the
contaminants may migrate; and also the potential receptors which may be affected by the
contaminants. Therefore, the preliminary conceptual site model can be used to help select boreholes
for aquifer test and groundwater sampling purposes, as it is suggested that the groundwater baseline
should be receptor focussed.
The preliminary conceptual site model should be updated with new information as the groundwater
baseline establishment process continues in order to create the final conceptual site model, which is
used as input for numerical models.
The information that needs to be collected during the desk study is described in the following
sections.
3.4.1 Geological information and/or data of the study area

Acquiring geological information and/or data from available literature on the study area is the first
step in creating a conceptual model of the study area. This information and/or data should be used to
determine which geological structures, groups and formations are present in the study area, and also
where these different geological features outcrop in the study area. The information can also be used
to determine the depths, thickness, lateral extent, and strike and dip of geological structures such as
faults. This information is necessary for determining which natural boundary conditions, and also
which preferential flow paths or barriers, are present or may be present in the study area. This
information should be used to design the preliminary conceptual site model.
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Geological information may include:
Geological cross sections of the regional and local study area.

Information on the type, location and extent of geological preferential flow and barrier features.
Geophysical data of the regional and local area.
Borehole logs (from geological core logs and/or from downhole geophysics) of the boreholes in
the regional and local study area.
Geological and geophysical maps, such as structural, metamorphic, igneous, sedimentary,
magnetic and gravity maps.
Geological reports on of the local and regional geology.
3.4.2 Geohydrological and hydrological information of the study area

The geohydrological and hydrological information on the study area is used to determine the
geohydrological properties of the hydrostratigraphic groups and formations present in the study area,
the properties of the preferential flow features and the boundary conditions. The geohydrological and
hydrological information may also be used to determine the direction of groundwater flow, recharge
and discharge areas, and water levels.
Geohydrological and hydrological information may include:
Types of local and regional boundary conditions: These boundaries are based on natural geological
and geohydrological boundaries such as dykes, rivers and groundwater divides, which should also
be taken into account when establishing the size of the study area.
Hydraulic properties of the formations present in the study area: This information includes
transmissivity, hydraulic conductivity, specific yield, specific storage, storativity, permeability and
porosity of the different geological formations. This information is used to determine which
geological formations are aquifers, aquicludes or aquitards.
Depth, thickness and type of aquifers present in the study area.
Hydraulic properties of preferential flow features in the study area such as faults and boundaries
alongside dolerite dykes.
Monitoring and production borehole data: This information includes water quality data, water
level data, borehole location, borehole owner, borehole construction (which includes borehole
depths, casing depths, depth and extent of screened intervals, casing diameters), equipment
installed and use of borehole (which includes rate and duration of use).
Groundwatersurface water interaction: If a river or dam is present in the study area, the
interaction between the groundwater and surface water needs to be determined.
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Hydrostratigraphic units, which are geological units with similar aquifer properties.
The local and regional groundwater recharge and discharge, which includes the area rate and
duration.
The quaternary catchment in which the study area is found.
Groundwater quality data of the regional and local groundwater: This information can be used to
determine the groundwater quality of the different hydrostratigraphic groups in the study area.
Structures or features which compartmentalise the groundwater system, such as faults or dolerite
intrusions.
The local and regional groundwater flow direction.
Groundwater resources determined from water balance models.
Hydraulic head correlation, which refers to the correlation between the water level elevation and
the surface water elevation in metres above mean sea level. If a good correlation exists, it can be
assumed that the groundwater level follows the natural gradient.
3.4.3 Other information

Topographic maps should be acquired to determine the surface elevation above sea level. These
maps can be used to determine if a correlation between the water level elevation and surface
elevation exists and if groundwater is discharged into the surface water bodies, or vice versa.
Property borders (farm borders) can be used to determine what the land is used for and also to
determine to whom the property belongs.
Aerial photographs, together with contour maps, can be used to determine regional drainage
channels.
Aerial photographs, satellite imagery, hyperspectral scanners, radar methods and laser scanners
(all remote sensing tools) can be used to investigate regional and local geological structures,
determine the dip and strike of beds, locate faults, fractures and joints, and may also be used to
assess the homogeneity of rocks.
Land use maps.
Long-term climatic data can be used to determine when the most groundwater recharge through
precipitation would occur, and when water levels may potentially decrease due to abstraction
from boreholes for irrigation (Brassington, 2007; U.S. Army Corps of Engineers [USACE], 1999).
This information is available from many different sources, as well as from institutions such as the
Department of Water and Sanitation; Groundwater Resource Information Project (GRIP); Southern
African Development Community (SADC); Water Research Commission (WRC) as well as geological
surveys.
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After the available information and/or data has been collected, a preliminary three-dimensional
conceptual site model can be created, which incorporates the defining processes (for example
recharge, surface wateraquifer interaction, preferential flow paths and unsaturated flow), geological
and geohydrological units.
3.5 AREAL EXTENT OF THE PRELIMINARY BASELINE STUDY

Before any preparation for the field investigations can be done, the preliminary size for the baseline
study area should be defined. The purpose of the preliminary study area is to establish boundaries in
which future investigations should take place. To define the actual study area size requires considering
boundaries which may act as buffers or conduits for potential contamination flow. These boundaries
may be determined with the help of the desk study, geological mapping, geophysics, borehole logging
and aquifer tests (Kndel et al., 2007; Kruseman and De Ridder, 1990).
The scale of the baseline assessment (regional or local) determines the size of the study area. The
study can either be for a regional baseline assessment, in which case the location at which gas
production will occur, is not known, but the prospective area of interest in the exploration area is
known; or a local baseline assessment, in which case the exact location where gas production will
occur, is known.
3.5.1 Regional baseline study size

A regional study size can be based on geohydrological structures, administrative regions, mapping
sheets or quaternary catchments (drainage regions) (Mazor, 2003). When establishing a size for the
regional baseline study, it is essential to incorporate physical features (for example, impermeable
formations and large surface water bodies) and hydraulic features (for example, groundwater divides
and streamlines), which may serve as buffers or conduits for flow (Brassington, 2007).
It is suggested that for a regional baseline study, a group of quaternary catchments, with similar
groundwater and geohydrological (aquifer type primary or secondary aquifer) characteristics should
be used and expanded by incorporating features such as large water bodies, water infrastructure such
as water pipelines and geological features which may serve as buffers or conduits for groundwater
flow. An example of such a regional baseline study is presented in Figure 3.2. The red square within
catchment N21D indicates the location where the hypothetical wellpad is situated.
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Figure 3.2: Illustrating the different quaternary catchments, drainage-rivers, large water bodies and dolerite intrusions
which fall in the hypothetical study area near Graaff-Reinet
As can be seen from Figure 3.2 the catchments which will be included in the study area are N21A,
N14D, N13C, N13B, N13A, N12C, N11B, N21B, N21D, and N21C.
These quaternary catchments in Figure 3.2 are included because (a) they are part of a major fractured
aquifer system, with similar geohydrological characteristics, as indicated in the Aquifer Classification
of South Africa map (Republic of South Africa, Department of Water Affairs [RSA DWA], 2012); (b)
there are geological features present in each of the quaternary catchments (dolerite intrusions) which
may act as conduits for groundwater flow; (c) some of the catchments have major water features such
as dams which may serve as buffers or conduits for flow; and (d) the drainage system covers all of the
selected catchments, which may serve as pathways for contamination migration.
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3.5.2 Local baseline study size
When calculating the appropriate size for the local baseline study, the most significant aspect to
consider is the size of contamination one would expect from the unconventional gas project, and also
the physical/hydraulic boundaries which may serve as buffers or conduits for flow. For the local
baseline study size, it is recommended to work within a single quaternary catchment area, if there are
no geological features or other relevant features that cross the quaternary catchment boundary, in
which case more catchments may need to be included.
3.5.2.1 Hydraulic fracturing
Baseline testing of water sources should be within some distance from the wellhead, or within some
distance of a point along the entire length of a horizontal lateral well, or from the most distant point
to which fractures will propagate, if this information is known during groundwater baseline
establishment.
Most states in the USA require testing of water sources within a specific distance from the wellhead,
rather than testing all the water sources within a projected distance of the lateral or projected fracture
length. This appears to be the soundest approach as the cost of sampling all the available water
sources within a specified distance, either the entire length of the lateral or the length of the fractures,
would be too substantial. Table 3.1 and Figure 3.3 provide the required distances for baseline water
sampling from the wellhead required by different states and companies in the USA.
TABLE 3.1: BASELINE WATER SAMPLING DISTANCE REQUIRED BY DIFFERENT STATES OR COMPANIES IN THE
UNITED STATES OF AMERICA
Company or state Radius (m) From Sampling source
Canadian Association of 250 Wellhead Domestic water wells

Petroleum Producers
Wyoming 400 Wellhead Water sources
Ohio 460 Wellhead Water wells
Illinois 500 Wellhead All water sources
Centre for Sustainable Shale 760 (or greater

Wellhead Water
Development, Pennsylvania depending on geology)
Colorado 800 Wellhead Water sources (max 4)
Average radius: 530 m
Note: The colours correspond to the colours used in Figure 3.3.

Source: Adapted from Hall (2014)
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Figure 3.3: Baseline water sampling distance required by different states and companies
In a study by Van Tonder et al. (2013) (see Section 2.6.4), it was determined for a case setting in the
Karoo fractured rock aquifers, South Africa, that if hydraulic fracturing fluid was released into
groundwater through preferential flow paths in the cement annuli of the gas well, the contaminant
could travel, under the most favourable case scenario, 2.8 km downstream of the gas well after five
years, and under the worst-case scenario, 6 km in less than two months, as flow velocities along
fractures can be as high as 3 600 m/month, and even higher flow velocities are expected along faults
and dolerite intrusions.
Therefore, for local groundwater baseline testing, a distance of 5 km radius from the furthest point of
potential horizontal drilling is suggested for hydraulic fracturing operations under South African
fractured aquifer conditions, as horizontal drilling can range from 600 to 3000m (Hyne, 2012; Johnson
and Johnson, 2012) and induced fractures from hydraulic fracturing operations may potentially
intercept naturally occurring fractures and faults which may be connected to shallow potable aquifer
systems (Lavoie et al., 2014; Myers, 2012; Rozell and Reaven, 2012; RSA DMR, 2012; USEPA, 2015b).
3.5.2.2 Underground coal gasification
In a study conducted by Campbell et al. (1978) on the effects of UCG on groundwater quality at the
Hoe Creek experimental UCG site near Gillette, Wyoming, in the USA, it was determined that after
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only seven days of coal gasification the water quality up to 30 m from the gasification zone (outside
of the gasification burn boundary) had been affected.
At the Hoe Creek test site contaminants migrated 60 m from the test site; these contaminants were
mostly escaped gases (Stephens, 1981, cited in Sury et al. 2004). In a test study at the Rocky Mountain
1 Test site in Hanna, Wyoming, in the USA, it was recorded that after increasing the hydrostatic
pressure, the groundwater quality changed beyond the furthest monitoring point (120 m away from
the wellhead) (Boysen et al., 1990, cited in Sury et al., 2004).
As the fluids and gases may migrate from the UCG production zone through similar pathways as in
hydraulic fracturing operations, a local groundwater baseline testing of 5 km radius from the furthest
point in the coal seam which will undergo gasification is proposed for UCG operations.
3.6 GEOLOGICAL AND GEOHYDROLOGICAL INVESTIGATIONS

Conducting the geological and geohydrological investigations are the fourth and fifth proposed steps
in establishing a groundwater baseline for unconventional gas projects. During the desk study, and
the geological and geohydrological investigations, the potential receptors and the potential pathways
along which contaminants may migrate, should be identified.
What follows is the suggested sequence of collecting the required information and data in the study
area, followed by short informative, non-detailed, descriptions on how the geological and
geohydrological investigations should be conducted.
3.6.1 The sequence for conducting the geological and geohydrological

investigations
Figure 3.4 illustrates the suggested sequence for conducting the geological and geohydrological
investigations.
From the diagram, it can be seen that before undertaking a geological investigation, the data from the
previous geological investigation should be used for planning the subsequent investigation. The
diagram also indicates that the groundwater flow direction which has been determined during the
geohydrological field investigation, is used during the aquifer test planning. It can also be seen that
the groundwater level and flow direction data are the only data that is used for planning the aquifer
test; the rest of the data is collected for numerical modelling purposes.
Furthermore, it can be seen from the diagram that after conducting a field investigation and before
continuing with the subsequent investigation, that the collected data from the current investigation
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is first taken to the office to update the information that is known of the study area. By doing this, it
would help in assisting the planning of the subsequent field investigations.
The diagram also shows that before conducting a field investigation, the owner of the
property/borehole is contacted to explain the investigation, ask for permission to conduct the
investigation and then arrange a meeting with the owner.
Depending on the size of the preliminary study area and the duration of the different geological and
geohydrological field investigations, after collecting the different information, the field crew may
return to the office, evaluate the geological and geohydrological information and return to the field
to continue with the subsequent investigations.
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Note:
The green coloured boxes indicate steps that take place in the office and the brown boxes indicate steps that take place from the field during the geological and geohydrological field
investigations.
Figure 3.4: Flow diagram of the sequence of conducting the geological and geohydrological investigation
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3.6.2 Planning the geological and geohydrological investigations
The purpose of planning for the geological and geohydrological investigations is to evaluate the
available data, establish where data gaps in the study area exist, determine how the data can and
should be collected, determine the order in which to collect the necessary data, acquire information
on the owners of the properties and boreholes in the study area, ask for permission to investigate the
available boreholes and to enter the property, acquire the required equipment and documentation,
arrange meetings with borehole and property owners, and arrange for transport and accommodation.
Before leaving for the initial site visit, the following questions need to be answered:
Where do data gaps exist in the preliminary study area?

What data gaps can be filled during the initial site visit?
How can these data gaps be filled?
What equipment will be needed to fill these data gaps?
Only the topics that answer the questions listed in Section 3.1 which have not been fully answered in
previous publications on establishing a groundwater baseline for unconventional gas projects, will be
discussed in detail in the following sections, while only a short description will be provided regarding
the other topics which have been answered in previous publications.
3.6.2.1 Determining if geological and/or geohydrological investigations are required
Depending on the amount of information available in the literature, the data gaps can be filled by
interpolating the information from known data points using interpolation techniques such as kriging,
or may be reasonably inferred. If not, geological and/or geohydrological investigations need to be
conducted to fill the data gaps.
In order to fill the existing geological and geohydrological data gaps, the results from the different
field tests need to be compared, combined and correlated with each other and with the existing
available data.
The field tests that are typically conducted to fill the geological data gaps are:
Surface geophysical surveys.

Borehole inspection (or hydrocensus).
Borehole logging.
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The field tests that are typically conducted to fill the geohydrological data gaps are:
Geohydrological field investigations.

Aquifer tests (pumping tests and slug tests).
Before any field test can be conducted, information on the borehole and property owners needs to
be acquired.
3.6.3 Remote sensing

After reviewing the available literature and identifying data gaps where further investigations are
required, remote sensing of the area is required before any field tests are conducted to plan the field
investigation. As remote sensing is inexpensive, it is usually the tool first used for hydrological
investigations, to indicate surface features of interest and for planning purposes (Singhal and Gupta,
2010).
Aerial photographs and satellite images should be used to provide an overview of the topography and
infrastructure of the study area. Furthermore, aerial photographs and satellite images, together with
topographic and geological maps, can be merged and used to prepare base maps of the study area
with all the necessary information listed on the maps, such as farm homes; property boundaries;
geological structures such as dolerite dykes; faults and fractures; and infrastructure such as buildings,
roads and railways (Kndel et al., 2007).
Remote sensing is also a useful tool for identifying lineaments and fracture zones along which
groundwater may flow; identifying drainage patterns; recharge and discharge zones; to determine
whether rivers in the study area are gaining or losing rivers. Remote sensing can also be used to map
the zones of effluent and influent seepage, for water budget calculations and modelling.
3.6.4 Conducting the field investigations
3.6.4.1 Surface geophysical survey
The purpose of the surface geophysical survey is to identify and gain information on the different
formations which do not outcrop at the surface, or are covered with weathered material. The
information includes determining the extent, thickness, depth and orientation of the different
formations and structures below the surface. This information is required to update the preliminary
conceptual site model, and most importantly, for selecting areas/positions where boreholes should
be installed for future groundwater observations, borehole log investigations, aquifer pumping tests
and groundwater sampling/monitoring (Kndel et al., 2007; Singhal and Gupta, 2010).
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There are many different surface geophysical techniques which are used for different purposes and
may be used in conjunction with one another, or exclusively, depending on the time and budget
constraints. The different geophysical techniques supplement each other as different techniques are
sensitive to different physical parameters.
The following list is a summary of conventionally used surface geophysical techniques, which may be
used during groundwater baseline studies, together with their applications:
Magnetic method: Used to delineate geological features such as dolerite intrusions and kimberlite
fissures. The method can also be used to investigate boundary conditions and approximate the
strike and dip of structures (Hoover et al., 1995; Kearey et al., 2002; Lowrie, 2007; Wonik and Olea,
2007; Woodford and Chevallier, 2002).
Gravity method: Used to detect fractures and faults and lithological and structural changes
(Hoover et al., 1995; Wonik and Olea, 2007; Woodford and Chevallier, 2002).
Direct current resistivity method: Used to estimate the depth, thickness and properties of
aquifers, aquitards and aquicludes. The method can also be used to detect fractures and faults; to
map groundwater preferential flow features; to assess a formation homogeneity; and also to
detect cavities (Hoover et al., 1995; Kndel et al., 2007; Singhal and Gupta, 2010; Wonik and Olea,
2007).
Electromagnetic methods: Generally used in groundwater surveys to detect fractures and faults;
to determine the depth and lateral extent of different formations; and also to assess the
homogeneity of a formation (Hoover et al., 1995; Kndel et al., 2007; Wonik and Olea, 2007;
Woodford and Chevallier, 2002).
Seismic methods: Used in investigations to locate local and regional geological structures. The
method may also be used to determine the depth of bedrock and determine lithological
subdivisions (Hoover et al., 1995; Lowrie, 2007; Wonik and Olea, 2007).
3.6.4.2 Borehole inspection
The purpose of borehole inspection (or hydrocensus) is to determine the condition of the exist ing
boreholes in the study area to be able to select appropriate boreholes for:
borehole logging;
aquifer testing;
determining where new boreholes need to be installed; and
ultimately selecting boreholes for groundwater sampling and field measurement purposes to
establish a groundwater baseline.
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During borehole inspection (or hydrocensus), all the boreholes in the study area should be inspected,
even where no data gaps exist, as the boreholes with known construction and geological details may
have been abandoned or sealed, destroyed, or have collapsed. Therefore, it is vital to not assume that
a borehole is available for borehole logging, pumping tests and sampling based on previous
information.
After arranging meetings with the property/borehole owners, the boreholes can be inspected. On
arrival at the property, the owner should be presented with the map of the borehole positions and
asked if there are any other boreholes on his/her property which are not indicated on the map. If
there are, the owner should then be asked to accompany the investigator to all the boreholes listed
and those not listed on the map so that they can be inspected.
I n s p e ct i n g t h e b o r eh o l e
When arriving at a borehole, the information sheet presented in Appendix B should be completed
(hydrocensus form).
M e a s u ri n g w a t e r l e v e l a n d d e p t h o f t h e b o re h o l e
The easiest way to measure the water level and depth of the borehole is by using an electric water
level meter, for instance, a coaxial water level meter or a flat-tape water level meter such as a Solinst
(Model 101). In boreholes with pumps installed, the pumps should be deactivated for at least two to
three hours before the water level is measured. Where possible, only static water levels should be
measured.
C o l l e c t i n g w a t e r f o r f i e l d m e a s u re m en t s
The purpose of collecting water for field measurements is to gain information on the general water
quality of the groundwater in the area and should be used to decide on the sequence of groundwater
sampling during the initial sampling event. Boreholes suspected to be less contaminated, based on
the field measurements, should be sampled first to minimise equipment and sample contamination.
A disposable polyethylene bailer can be used to collect water from the boreholes for field
measurements. After collecting the water, and discharging it into a clean plastic container, field
measurements should be taken with a manufacturer specified calibrated water quality measuring
device such as an Aquaread Aquameter with AP-800 Aquaprobe or the Hanna HI98129
pH/Conductivity/TDS tester.
Alternatively, water discharged from the pump into a clean plastic container can also be used if a bailer
cannot be used. During collection of the water and taking measurements, latex gloves should be worn
to prevent cross-contamination and to protect the sampler from any harmful contaminants.
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Borehole logging can be conducted as soon as the above-mentioned information on the boreholes
indicated on the map and any new boreholes have been collected. Alternatively, borehole logging can
be conducted during borehole inspection. It depends on the investigators preference and what the
more logic decision would be, based on the field conditions and budget.
3.6.4.3 Borehole logging
Before conducting borehole logging, the available geological and geophysical data should be reviewed
to determine where data gaps exist. After determining where data gaps exist, the condition of the
boreholes should be reviewed to determine which type of borehole logging tool can be used, as some
tools cannot be used in boreholes lined with polymerising vinyl chloride (PVC) casings, or in dry
boreholes.
In addition to surface geophysical techniques, downhole borehole geophysical techniques (logging)

and other borehole logging tools such as camera logging, can also be used to fill data gaps. Borehole
logging tools are useful for confirming the results and interpretations made from surface geophysical
investigations and may help to determine where features such as faults or fractures occur (Singhal
and Gupta, 2010; Sury et al., 2004).
Borehole logging can help in determining the location and geometry of different geological features
such as joints and fractures which may not be detected by using surface geophysics. Borehole logging
can also be used to determine the lithology, thickness and extent of formations, porosity,
permeability, density, specific yield, local and regional groundwater flow direction and patterns,
moisture content, source of water, and also the chemical and physical characteristics of groundwater
and geological formations, from either a single borehole log, if possible, or by correlating logs from a
number of boreholes in the study area (Fetter and Willard, 2001; Kearey et al., 2002; Keys, 1996;
Wonik and Olea, 2007).
In addition to identifying geological features at depth, borehole logging can be used to provide
information on the conditions of the borehole, such as casing depth, cementation and screened
intervals and depth.
Borehole logging is useful because drill logs are not always available, of poor quality or incomplete;
therefore, geophysical logs can be used to provide continuous depth records of the different
formations properties (Fetter and Willard, 2001; Harvey and Lovell, 1998; Wonik and Olea, 2007).
The following list is a summary of borehole logging methods, which may be used during groundwater
baseline studies, together with their applications:
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Gamma-ray logging method: Used to determine the porosity of layers and fractures; to determine
the location of the saturated zones; to determine the borehole construction and conditions; and
also be used for lithological classification of formations (Fetter and Willard, 2001; Kearey et al.,
2002; Keys, 1996; Wonik and Olea, 2007; Woodford and Chevallier, 2002).
Neutron-neutron method: Used to determine the porosity of a layers; to determine the specific
yield of unconfined aquifers; to determine the infiltration rate under specific circumstances; and
can also be used for lithological classification of formations (Fetter and Willard, 2001; Kearey et
al., 2002; Keys, 1996; Wonik and Olea, 2007).
Electrical methods: Used to determine the formation water resistivity (which is used to derive the
formation permeability); to identify the boundaries between shale horizons; to locate coal seams;
to identify fracture and fault locations; to determine the strike and dip of penetrated strata,
fractures and fissures; to determine grain sizes; to identify well screens; and also to test casing
seals (Fetter and Willard, 2001; Keys, 1996; Wonik and Olea, 2007).
Electromagnetic methods: Used to determine the formation water saturation; to determine the
annulus material composition; and can also be used to for lithological classification of formations
(Fetter and Willard, 2001; Wonik and Olea, 2007).
Optical methods: Used to identify joints, fractures and fault zones, and other geological features;
to determine borehole construction and conditions; and can also be used to determine the
borehole diameter and water volume (Fetter and Willard, 2001; Wonik and Olea, 2007).
Caliper log method: Generally used to determine borehole properties and also to determine the
secondary permeability of fractures faults and solution openings (Fetter and Willard, 2001; Keys,
1996; Wonik and Olea, 2007).
M e t h o d s f o r d e t er m i n i n g t h e p r o p er ti e s o f w a t e r
TEMP (temperature) and SAL (salinity) techniques: Used to provide an indication of vertical
movement of water in wells; to determine the depth at which water inflows and outflows occur;
to determine casing leaks; to determine the degree of water mineralisation; to distinguish
between different aquifer systems; and to determine the regional groundwater flow patterns
(Fetter and Willard, 2001; Wonik and Olea, 2007).
Groundwater flow meter: Used to determine the groundwater flow velocity and groundwater
flow direction (Woodford and Chevallier, 2002).
Multi-parameter probe: To determine different water parameters such as pH, temperature and
redox potential (Wonik and Olea, 2007).
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Tracer tests: Used to determine the groundwater flow velocity and groundwater flow direction;
and also to determine casing leaks (Fetter and Willard, 2001).
3.6.4.4 Classifying formations as hydrostratigraphic units
Before conducting aquifer tests, the geological formations present in the study area need to be
classified as preliminary hydrostratigraphic units. A hydrostratigraphic unit is a combination of rocks
with similar geohydrological properties (Voigt and Radschinski, 2007).
The formations should be converted into preliminary hydrostratigraphic units based on their hydraulic
conductivity and lithology. If the hydraulic conductivity of the formation is not known, it can be roughly
estimated using Figure 3.5 to classify the units as preliminary hydrostratigraphic units based on
lithology of the formation.
This concept is illustrated in Table 3.2 where formations of the Beaufort Group, which form part of
the Karoo Supergroup, are combined to form single hydrostratigraphic units based on their general
lithologies.
The purpose of classifying the formations as preliminary hydrostratigraphic units is to combine

formations with similar geohydrological properties, to simplify the conceptual site model and to assist
in selecting existing, and drilling new boreholes on which to perform aquifer tests; to determine the
hydraulic properties of each hydrostratigraphic unit which would serve as inputs into the numerical
model.
After aquifer tests have been conducted on the preliminary hydrostratigraphic units, the units can be
refined and updated based on their calculated site-specific hydraulic properties to produce the final
hydrostratigraphic units for the site.
With the aim of establishing a groundwater baseline for the study area, it is proposed that
groundwater samples should be collected from each hydrostratigraphic unit present in the study area.
By collecting groundwater samples from each hydrostratigraphic unit in the study area would allow
establishing quantity ranges for each analysed chemical constituent for each hydrostratigraphic unit.
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Figure 3.5: Average hydraulic conductivity and permeability of different lithologies
126
TABLE 3.2: SUGGESTED HYDROSTRATIGRAPHY OF THE STORMBERG AND BEAUFORT GROUPS
Group Formation Lithology Hydrostratigraphic unit
Clarens Mainly sandstones Clarens aquifer
Stormberg Elliot Mainly mudstones Elliot aquitard
Molteno Mainly sandstones Molteno aquifer
Medium-grained sandstones
Burgersdorp
and mudstones
Burgerberg aquifer
Beaufort Katberg Mainly sandstones
Balfour Fine sandstones and mudstones Balfour aquitard
Source: Adapted from Woodford and Chevallier (2002)
Furthermore, it is proposed that groundwater samples should only be collected from the target coal
or shale zone and from the hydrostratigraphic units above the target coal or shale zone, as t he
groundwater baseline should be receptor-focused, and the groundwater in the overlying units may
likely be used for irrigation, domestic and industrial purposes during the time of groundwater
baseline establishment or in the future and may potentially be affected by unconventional gas
activities.
The reason why it is not proposed to establish a groundwater baseline for hydrostratigraphic units
below the target coal or shale zone is because it is suggested that the baseline should be receptor
focussed. Most of the water that will likely be used by potential receptors for irrigation, domestic and
industrial purposes is expected to be from shallow aquifers with groundwater at a depth between 5 m
and 30 m, based on the groundwater depth map for South Africa (Musekiwa and Majola, 2013). As
the coal zones targeted for UCG operations have to be at a minimum depth of 150 m (Creedy et al.,
2001), and the shale zones targeted for hydraulic fracturing operations have to be at a minimum depth
of 1 000 m (Kuuskraa et al., 2013), it would serve no purpose to establish a groundwater baseline for
hydrostratigraphic units below the target coal or shale zones as these hydrostratigraphic units are not
likely to be utilised for irrigation, domestic and industrial purposes. Furthermore, it is a known fact
that groundwater salinity increases with depth, due to high contact time of groundwater with aquifer
materials, and with increasing salinity, its usability for irrigation, domestic and industrial purposes
decreases with depth (Singhal and Gupta, 2010; Todd and Mays, 2005).
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3.6.4.5 Geohydrological field investigation
The following information needs to be gathered during the geohydrological field investigation for
water budget calculations, numerical modelling, and aquifer test planning purposes:
1. Inspect the presence and condition (depth, water stage, dimensions, orientation) of hydrological
boundaries in the study area such as rivers, dams and lakes for groundwater numerical model
and planning the aquifer test(s). This can be done by utilising remote sensing.
2. Determine the location, rate, duration and time (spatial and temporal variability) of groundwater
recharge and discharge for the water balance and groundwater numerical model. Recharge,
discharge and groundwater-surface water interactions can be determined from the following:
Information from soil surveys, rainfall, run-off and evapotranspiration.

Recharge can be estimated by using the following:
Chloride method.
Saturated Volume Fluctuation (SVF) method.
Cumulative Rainfall Departure (CRD) method.
EARTH Model.
Discharge can be estimated by using:
Groundwater Risk Model.
Ecological Optimality Model.
Recharge and discharge through the streambed can be measured by using seepage meters.
Recharge and discharge can also be measured using a current or permanent stream gage to
measure the water flow in the stream.
Borehole abstraction data gathered from the borehole inspection phase of the geological
investigations can be used to determine groundwater discharge.
Stream hydrographs can be used to determine groundwater recharge and discharge.
By determining the depth of the surface water body together with the groundwater elevation
(by installing piezometers at different depths close to the surface water features), it can be
determined if water is discharged from the aquifer to the surface water body, or from the
surface water body to the aquifer.
Surface watergroundwater interaction can also be determined by using tracers, stream
gauging, chemical mass balance, seepage meters, piezometers, crest-stage gauges and
Parshall flumes (Becker et al., 2004; Fetter and Willard, 2001; Singhal and Gupta, 2010; Weight
and Sonderegger, 2001).
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For more information on estimating groundwater discharge, refer to Jolly et al. (2011), and for
more information on estimating groundwater recharge, refer to Xu and Beekman (2003).
3. Determine the direction of groundwater flow this can be done by installing piezometers into
different aquifers, if the aquifer systems are known, and measuring the hydraulic head of each
aquifer (Fetter and Willard, 2001). The groundwater level and groundwater flow direction data
can be expressed as water table maps and/or sections, which may be used during borehole
selection for aquifer test and numerical modelling purposes (Singhal and Gupta, 2010).
For more information on inspecting surface water features, determining groundwater recharge,
discharge and groundwatersurface water interaction, refer to Weight and Sonderegger (2001).
3.6.4.6 Aquifer tests
Aquifer tests can be conducted after reviewing the available literature, identifying data gaps where
further investigation is required, and boreholes selected. The purpose of the aquifer test is to
determine the hydraulic properties of the preliminary hydrostratigraphic units.
Generally, an aquifer test comprises the following tests: pumping tests, slug tests, packer tests and
tracer tests. According to Singhal and Gupta (2010), when conducting a regional investigation, such as
when the location of the wellpad(s) is not known, pumping tests are the preferred method for
determining the hydraulic characteristics of the aquifers because pumping tests are used to provide
representative values of hydraulic parameters for larger volume of rock mass around the borehole,
whereas in local investigations, such as when the location of the wellpad(s) is known, packer tests and
slug tests are satisfactory because they can be used to determine hydraulic parameters in the
immediate vicinity of the borehole.
These different tests can be conducted in conjunction with one another, for example, packers can be
installed to isolate a specific formation for slug, pumping and tracer tests. Tracer tests can be used in
conjunction with pumping tests to determine the groundwater flow parameters and interconnectivity
between different formations.
Each method has its own practical limitations, such as slug tests which results are not representative
of the entire aquifer, and can therefore not be used to assign transmissivity and hydraulic conductivity
values to the entire aquifer or to determine aquifer heterogeneity. These practical limitations need to
be known and well understood before selecting a method. The method that will be used might also
depend on geological and financial constraints (Kndel et al., 2007).
After conducting the aquifer tests on each of the preliminary hydrostratigraphic units, and
determining the hydraulic properties of each unit, the hydrostratigraphy of the study area can be
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finalised. This hydrostratigraphic unit column is necessary for selecting aquifers for the groundwater
sampling events and updating the conceptual model.
3.6.4.7 Borehole aquifer test design
To select boreholes for aquifer tests, the information gathered during the borehole inspection from
the geological investigation should be used. The position of the boreholes and the location of the
wellpad (if known) should be plotted on hydrostratigraphic, geology and topography maps for
planning purposes.
The selected boreholes for aquifer tests (abstraction and observation boreholes in the case of
pumping tests) should ideally be located in areas which are not significantly affected by man-made
stresses, and are away from existing discharging boreholes to avoid any possible interference.
Observation boreholes should generally be located down-gradient from the wellpad, with fewer
observation boreholes located up-gradient of the abstraction borehole. This is necessary to evaluate
the heterogeneity and anisotropy of the aquifers. The observation boreholes downstream and
upstream will provide information on the storativity and transmissivity downstream and upstream of
the abstraction borehole, respectively (Singhal and Gupta, 2010).
In order to collect the hydraulic characteristics of a single aquifer, the borehole casing should either
cover the upper and lower formations (not the aquifer of interest), the slots in the casing should
stretch over the entire thickness of the aquifer of interest, or the aquifer should be isolated by using
packers.
When planning a pumping test, ideally, one abstraction borehole and at least three observation
boreholes at different distances from the abstraction borehole are required. This will help in analysing
the test data from both distance-drawdown and time-drawdown methods and will help identify the
boundary conditions.
The abstraction borehole should have a diameter of at least 150 mm so that a submersible pump can
be installed. The observation wells should have diameters large enough to accommodate the electrical
depth sounders (or automatic water level recorders).
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3.6.4.7.1 Selecting boreholes for pumping tests
The selected boreholes on which pumping tests will be conducted should ideally be constructed as
follows:
The abstraction borehole should tap the complete thickness of the aquifer to avoid partial
penetration effect (if not possible due to thick aquifers, the necessary corrections to the
drawdown data should be made).
Observation boreholes should ideally be installed at the same depth and tap the same aquifer as
the abstraction borehole.
The observation boreholes should be located in different directions at different distances from
the abstraction borehole in order to observe the drawdown during the pumping test in all
directions.
The selected boreholes should intersect aquifers containing fractures as these fractures are the
source of groundwater to boreholes in fractured rock aquifers (Woodford and Chevallier, 2002).
If it is suspected that interconnection between different aquifers exists due to leakage, some of
the observation wells tapping the upper and lower aquifers should also be selected. This is
necessary in order to know the vertical component of flow in fractured aquifers.
When selecting boreholes, it is essential to be aware of the potential geological preferential flow
paths and barriers, as they may serve as pathways for contamination towards potable
groundwater-bearing zones or cause a damming effect, respectively.
Preferential flow paths and barriers should be targeted as they may potentially indicate
contamination migration from unconventional gas projects during monitoring (OBrien et al.,
2013).
If possible, boreholes installed into specific preliminary hydrostratigraphic units should be chosen
to be able to determine the hydraulic characteristics of a specific unit.
Boreholes with known construction information close to the wellpad should be chosen, if the
location of the production well is known.
Higher priority should be given to domestic and irrigation boreholes close to households, as the
sampling programme should be receptor-focused, and is required for higher accuracy modelling
of potential contamination migration.
In the upper weathered unconfined aquifer of the Karoo, the selected abstraction borehole should
be fully penetrating and have its screened interval in the lower half of the aquifer where the flow
lines are mainly horizontal, in which case the observation boreholes must be selected (installed)
at half the saturated thickness of the aquifer from the abstraction borehole in a lateral direction.
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In the lower consolidated confined aquifers of the Karoo, the selected abstraction borehole should
be fully penetrating and have its screened interval across the entire thickness of the aquifer.
Alternatively, because the confined aquifers of the Karoo are hard rock aquifers, the borehole can
be and open-end type borehole with the casing extending to above the aquifer of interest.
If the location of the wellpad and chemical storage facilities (in the case of hydraulic fracturing
operations) is known, boreholes should be selected in a radial pattern with at least two boreholes
up-gradient of the wellpad (one shallow, one deep), with the majority of the boreholes down-
gradient in the direction of groundwater flow, if the groundwater flow direction can be calculated,
is known, or can be reasonably inferred.
operations) is known, the majority of the shallow boreholes should be located down-gradient,
close to the wellpad and storage facilities, with the majority of the deep boreholes located down
gradient close to the production wells (Singhal and Gupta, 2010).
3.6.4.7.2 Selecting observation boreholes for pumping tests
The selected observation boreholes for pumping tests should ideally be spaced as follow:
The observation well spacing for pumping tests depends on the rate and duration of the test, the type
of aquifer and hydraulic properties of the aquifer. Table 3.3 presents the observation well spacing that
has been suggested by Singhal and Gupta (2010).
TABLE 3.3: SUGGESTED SPACING OF THE OBSERVATION WELLS
Distance between abstraction Distance within which

Aquifer condition Borehole condition borehole to nearest observation borehole should
observation borehole be located
Unstratified confined or Fully penetrating 11.5 times aquifer thickness 20200 m in confined aquifer,
unconfined aquifer 20100 m in unconfined
aquifer
Thick or stratified Fully penetrating 35 times aquifer thickness 100300 m in confined

confined or unconfined aquifer, 50100 m in
aquifer unconfined aquifer
Confined or unconfined Partially penetrating 1.52 times aquifer thickness 35200 m in confined aquifer,
aquifer 35100 m in unconfined
aquifer
Source: Adapted from Singhal and Gupta (2010)
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One of the observation boreholes should be located outside the cone of depression to assess the
effects of natural causes on water-level fluctuation to be able to make corrections to the drawdown
data.
In fractured formations, such as those in the Karoo, multiple observation wells which tap the pumped
interval, and also the highly and less transmissive horizons, should be selected. Piezometers installed
into different aquifers can also be used to monitor the water levels of different aquifers, and also to
be able to determine the water qualities of the different aquifers during sampling (Singhal and Gupta,
2010).
3.6.4.8 Other tests which may be conducted
The hydraulic properties of rock material can also be estimated by different laboratory techniques.
Indirect methods can be used to determine the hydraulic conductivity from the grain-size distribution
of unconsolidated material such as the top weather formation of the Karoo. Direct methods such as
hydraulic transient flow can be used to determine hydraulic conductivity, and permeability and
specific storage of fractured rocks; mechanical transient flow can be sued to determine permeability
and specific storage of specimens such as clays; and steady or quasi-steady flow tests can be used to
determine the hydraulic conductivity of coarse-grained and tight formations (Singhal and Gupta,
2010).
To be able to conduct these tests, samples will need to be collected from borehole core logs and from
surface outcrops during the initial geological or geohydrological field visits (Singhal and Gupta, 2010).
3.6.4.9 Conclusion
By comparing, correlating and integrating the different data from the geological and geohydrological
investigations and data from the existing literature, a better understanding of the subsurface geology
and geohydrology can be acquired. The correlation of the data from different sources is more reliable
than data from individual sources (Fetter and Willard, 2001; Singhal and Gupta, 2010).
3.7 UPDATING THE PRELIMINARY CONCEPTUAL SITE MODEL AND GAP

ANALYSIS
After collecting all the relative geological and geohydrological information on the study area, the
preliminary conceptual site model needs to be updated with the new information. The purpose of
updating the model is to determine what information is known and to highlight areas where data gaps
exist.
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These areas will be targeted during the drilling phase when new boreholes are drilled in order to
collect additional data to fill these data gaps with supplementary geological and/or geohydrological
investigations.
3.8 DRILLING NEW BOREHOLES
3.8.1 Purpose of drilling new boreholes
After highlighting areas in the study area where data gaps exist, new boreholes should be drilled to be
able to fill the data gaps with additional geological and/or geohydrological investigations. These newly
installed boreholes should also be constructed sufficiently to be used for groundwater sampling during
groundwater baseline establishment and monitoring (Moore, 2011).
Dedicated boreholes should be drilled if it was determined during the desk study and the geological
and geohydrological investigations that the available boreholes in the study area
are not sufficient for providing information on the geohydrological and geological conditions of
the study area;
do not meet the requirements suggested for selecting boreholes for pumping test and
groundwater sampling; and
do not supply sufficient information/data which can be interpolated and interpreted to fill the
data gaps.
It is suggested to drill new boreholes into each hydrostratigraphic unit encountered in the study a rea,
from the surface down to the production zone. By doing this, data gaps can be filled, and groundwater
samples can be collected from each hydrostratigraphic unit that can be used to establishing natural
chemical quantity ranges for each unit. This, in turn, can be used to differentiate the units from one
another by analysing for the chemical parameters listed in Section 3.9.4.
Furthermore, installing boreholes at different depths is required to differentiate between potential

shallow source terms (agricultural and domestic practices and surface spills), and deeper source terms
(gas production) during monitoring (Gradient, 2013). Drilling new dedicated boreholes into different
hydrostratigraphic units are suggested to offer the best chance of obtaining representative samples
of the conditions of the aquifers.
3.8.1.1 Borehole construction
When drilling through several hydrostratigraphic units it is essential that the hydrostratigraphic units
which water quality is not of interest is cased-off to prevent mixing of groundwater from different
aquifers (Edmunds and Shand, 2008). The screened interval should be installed into the
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hydrostratigraphic unit of interest and the filter-pack should be installed on the outside, opposite the
screen. A bentonite seal should be installed above the filter pack to further prevent water from the
overlying hydrostratigraphic units to travel down the annulus, mix with the water of the
hydrostratigraphic unit of interest and lead to non-representative sample collection (Weaver et al.,
2007). See Figure 3.6 for the construction of the dedicated borehole to be able to collect
representative groundwater samples from the hydrostratigraphic unit of interest.
Figure 3.6: Dedicated borehole construction
3.8.2 Drilling phase
The boreholes which are used to fill the geological and geohydrological data gaps may and/or should
also be used for groundwater sampling to establish natural groundwater quantity ranges for each
hydrostratigraphic unit, and also for future monitoring purposes.
Generally, the existing boreholes in the study area may not be constructed to be able to use the
preferred sampling method or may not intersect the hydrostratigraphic units from which groundwater
samples will need to be collected. Therefore, the drilling method and the construction and design of
the newly drilled boreholes (position of the boreholes in the study area) should be of such a nature
135
that the boreholes can be used to fill the missing geological and geohydrological data gaps and can be
used to collect groundwater samples from each hydrostratigraphic unit.
When drilling (and selecting existing) boreholes for baseline establishment it is essential to drill
boreholes which may be used to detect anthropogenic contamination migration towards identified
potential human and/or groundwater receptors. Other potential receptors may include towns,
settlements, abstraction boreholes, sensitive ecological receptors and sensitive human receptors such
as hospitals and residences.
When drilling new boreholes for baseline establishment, monitoring and exploration purposes, it is
crucial to not create migration pathways from deep geological formations to shallower formations
through the newly drilled borehole. To prevent creating a migration pathway after drilling through a
hydrostratigraphic unit which is not of interest for data collection and/or sampling from a specific
borehole, the hydrostratigraphic unit should be cased-off (by installing solid casing) and cemented
into place (cement should be installed around the entire length of the solid casing) before drilling
further towards the hydrostratigraphic unit of interest for data collection and/or sampling purposes.
The following is a list of suggestions on drilling new boreholes to fill the geological and geohydrological
data gaps. These newly drilled boreholes should ideally be used for groundwater sampling and
monitoring purposes. The suggestions listed in Section 3.6.4.7 on selecting boreholes for aquifer tests
should also be taken into account when drilling new boreholes.
Local investigation
The boreholes need to be drilled in a radial pattern of less than 50 m downstream from the
wellpad, in the direction of groundwater flow. These boreholes should be drilled into different
hydrostratigraphic units, with fewer dedicated boreholes drilled upstream of the wellpad.
The boreholes need to be drilled near or into potential preferential flow paths (such as known
fracture networks), downstream of the wellpad in the direction of groundwater flow in a radial
pattern, with fewer dedicated boreholes drilled upstream of the wellpad.
Boreholes should be drilled downstream of the wellpad in the direction of groundwater flow in a
radial pattern near or next to geological features which may cause a damming effect of migrating
contaminants such as dolerite and kimberlite intrusions.
Deep boreholes should be drilled close to the production wells, and shallower boreholes should
be drilled close to the surface facilities no further than 500 m and ideally less than 50 m in either
case.
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Regional investigation
Three dedicated boreholes for each hydrostratigraphic unit should be installed throughout the
entire study area. By doing this, regional groundwater quantity ranges for each hydrostratigraphic
unit can be established. As the main aim is to establish a groundwater baseline for the study area,
boreholes for aquifer tests to determine the hydraulic parameters for the different units can be
installed at a later stage when the location of the wellpad is known, to prevent excessive
expenditure.
Co n c lusion
The number of dedicated boreholes drilled, depends on the budget of the project, the amount of
boreholes that need to be drilled to collect groundwater samples from each hydrostratigraphic unit ,
and the amount of data gaps that exists in the study area.
The proposed minimum requirement for the installation of the monitoring network, is the drilling of
a dedicated borehole into each hydrostratigraphic unit downstream of the wellpad, with one
dedicated borehole upstream of the wellpad to the depth of the production zone. Also, one dedicated
borehole for each geological feature downstream of the wellpad.
When selecting locations to drill dedicated boreholes, it is vital to be receptor-focussed. These

dedicated boreholes can be used as early warning indicators of contaminant migration.
3.8.3 Borehole geohydrological logging
The following should be recorded as part of the geohydrological logging to obtain maximum
information during drilling of new holes:
Chip or core samples should be collected (depending on the drilling method used) and described
to construct the geologic log to determine/estimate the aquifer type and determine the depth
and thickness of the aquifer.
Penetration/drilling rate (min/m) in relation to depth (m) should be assessed as it gives an
indication of the hardness of the rock.
Water level in the drilled hole should be recorded as a function of the borehole depth (It will not
be possible if rotary or reverse rotary drilling is used).
The discharge rate and depth of the water strikes should be recorded.
Water quality readings for the different water strikes should be recorded. See Section 3.9.4.2 for
the water quality readings that need to be taken.
Water samples should be collected from the different formation water strikes for chemical
analyses of major ions and trace elements (provided no drill fluids are used during the drilling).
137
Measure the final depth of the drilled hole, to check if the hole was at the planned depth (fully
penetrating the aquifer).
Measure the length of the casing and slotted casing that will be placed in the hole.
Inspect the installation depth of the casing and slotted casing, to check if the screen and casing
are at the predetermined installation depth (cover the specific hydrostratigraphic unit(s) and is
screened over the specific hydrostratigraphic unit).
Measure the diameter and length of the surface casing.
Measure the final (collar) height of the surface casing and cap height extends above the ground.
Further, water quality samples can be taken for major ion and trace element chemistry to
determine areas of interest (Gradient, 2013; Moore, 2011; Wilde et al., 2005).
For a more complete list, refer to Fetter and Willard (2001) as well as Weight and Sonderegger (2001).
3.9 THE INITIAL AND SUBSEQUENT SAMPLING EVENTS

The initial and subsequent sampling events are the ninth step in establishing a groundwater baseline
for hydraulic fracturing and UCG operations. After conducting the geological and geohydrological
investigations and drilling new boreholes, the initial and subsequent sampling events can be
undertaken.
Before the initial and subsequent sampling events are undertaken, planning needs to be done for
selecting sampling parameters, selecting sampling methods, selecting boreholes for sampling,
determining a sampling frequency and selecting a laboratory(s) for sample analysis.
What follows is the suggested sequence for planning and conducting the initial and subsequent
sampling events.
3.9.1 The sequence of planning and conducting the initial and subsequent
sampling events
Figure 3.7 illustrates the suggested sequence of conducting the initial and subsequent sampling
events. The diagram shows that before conducting any of the sampling events, the owner of the
property/borehole should be contacted to explain the purpose investigation, asked for permission to
conduct the investigation and then arrange a meeting with the owner. Lastly, the diagram shows that
the required field equipment can be collected before contacting the owners of the properties and
boreholes.
138
Note:
The green coloured boxes indicate steps that take place from the office; the brown boxes indicate steps that take place from the field; and the grey boxes indicate the steps that take place
during and after the geohydrological investigation in the office.
Figure 3.7: Flow diagram of the sequence of conducting the initial and subsequent sampling events
139
3.9.2 Planning for the initial and subsequent sampling events
During planning for the initial and subsequent sampling events the following needs to be done:
selecting which physiochemical parameters to measure; selecting which chemical parameters to
analyse for; selecting which sampling devices and methods to use; selecting the sampling frequency;
establishing quality assurance and quality control measures and selecting a laboratory(s) for the
chemical analysis.
In the following sections suggestions for each of these activities are provided, specifically focusing on
the activities that have uncertainties which have not been fully addressed in the existing literature on
establishing a groundwater baseline for unconventional gas projects. Publicly available literature on
each of these activities have been extensively reviewed in order to provide suggestions.
3.9.3 Selecting sampling parameters and field measurements

When selecting parameters to analyse for, it is essential that a list of indicator parameters (parameters
which indicate contamination) be chosen, because it would be too expensive for most companies and
industries if all of the chemical parameters that may be present in the natural or contaminated
groundwater systems are selected.
Therefore, a workable number of chemical parameters need to be selected. These parameters must
be tailored according to the contamination that is likely to occur due to unconventional gas
operations, and the natural groundwater one would expect in a specific area (Nielsen and Nielsen,
2006).
For the purpose of selecting parameters, the following information was gathered:
Literature on potential groundwater contaminants from unconventional gas projects, such as

hydraulic fracturing fluids, drilling fluids, produced/formation water from shales and coal, and
UCG by-products.
Similar previous investigations on groundwater baseline studies on unconventional gas projects.
Natural background groundwater values to be expected in Karoo aquifers.
After consolidating the different chemical parameters, a refining process was followed, where specific
parameters were selected based on the purpose of sampling and analysing for the different chemical
parameters. From this process, a proposed list of chemical parameters was formulated together with
rationales for selecting the specific parameters. Only parameters that were not redundant (i.e. one
parameter which may sufficiently represent a wider class of contaminants or serve the same purpose
during interpretation of the analytical results) were selected.
140
The following topics will be covered in this section:
Groundwater chemistry of shales.

Groundwater chemistry of coal before and after UCG operations.
Previous studies on unconventional gas project baseline establishment.
Hydraulic fracturing fluid constituents.
Drilling fluid constituents.
Natural background groundwater values of Karoo aquifers.
3.9.3.1 Groundwater chemistry of shales
When selecting parameters to analyse for, it is essential to be site specific, as groundwater chemistry
depends on the geologic formation(s) in which it is found. From Section 2.5.4.3 on the macro-chemical
constituents of the Karoo aquifers and Section 2.5.4.6 on the chemistry of shale groundwater, the
following constituents are considered important for analysis during groundwater baseline
establishment for hydraulic fracturing operations in South Africa as they may potentially be present
in the shale groundwater and the shales of South Africa (specifically, the shales of the Karoo Group).
The parameters which were chosen to be analysed for are presented Table 3.4.
These parameters were chosen based on the following:
The water type of different shale formations (not South African shales).
The composition of produced water from different shale formations around the world.
The composition of formation water in typical South African shales.
NORM concentration in Karoo aquifers.
Dissolved gases from spring water in the Karoo.
TABLE 3 .4 : POTENTIAL CONSTITUENTS EXPECTED TO BE PRESENT IN SHALE GROUNDWATER AFTER HYDRAULIC

FRACTURING O P ERATIO NS
Parameters
Major anions
Ammonium as N (NH 4+-N)
Bicarbonate (HNO3)
Chlorine (Cl)
Fluoride (F)
Fluorine (F)
Nitrate (NO3)
Phosphate (PO4)
Sulphate (SO42)
Major cations
Sodium (Na +)
Calcium (Ca +)
Potassium (K +)
141
Parameters
Magnesium (Mg+)
Silica (Si)
Trace elements
Aluminium (Al)
Arsenic (As)
Barium (Ba)
Boron (B)
Bromine (Br)
Cadmium (Cd)
Chromium (Cr)
Cobalt (Co)
Copper (Cu)
Iron (Fe)
Lithium (Li)
Manganese (Mn)
Mercury (Hg)
Nickel (Ni)
Selenium (Se)
Strontium (Sr)
Uranium (U)
Vanadium (V)
Zinc (Zn)
Dissolved gases
Methane (CH 4)
Helium (He)
Carbon dioxide (CO2)
Nitrogen (N2)
Argon (Ar)
Ethane (C2H6)
Propane (C3H8)
Butane (C4H10)
VOCs
Benzene
Toluene
Ethylbenzene
Xylenes (o-xylene, m + p-xylene, total xylene)
Acetone
Carbon disulphide
Chloroform
Isopropylbenzene
Naphthalene
Phenols
C0-C5
SVOC + PAHs
1,2-Diphenylhydrazine
1,4-Dioxane
2,4-Dichlorophenol
2,4-Dimethylphenol
2-Methylnaphthalene
2-Methylphenol
3-Methylphenol
4-Methylphenol
142
Parameters
Acetophenone
Benzidine
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)fluoranthene
Benzo(g,h,i)perylene
Benzo(k)fluoranthene
Benzyl alcohol
Bis(2-Ethylhexyl) phthalate
Butyl benzyl phthalate
Dibenzo(a,h)anthracene
Di-n-butyl phthalate
Di-n-octyl phthalate
Diphenylamine
Fluoranthene
Fluorene
Indeno(1,2,3-cd)pyrene
N-Nitrosodiphenylamine
N-Nitrosomethylethylamine
Phenanthrene
Pyrene
Pyridine
Radioactive constituents
Radium-226, 228
Uranium-235, 238
Thorium-232
Radon-222
Potassium-40
3.9.3.2 Groundwater chemistry of coal before and after underground coal gasification
operations
From Section 2.5.4.3 on the macro-chemical constituents of the Karoo aquifers and Section 2.5.4.7 on
the chemistry of coal groundwater, the following constituents are considered important for analysis
during groundwater baseline establishment for UCG operations in South Africa as they may be present
in the coal groundwater and coals of South Africa, specifically the coals of the Karoo and Waterberg
basins, or they may potentially be produced during UCG operations. The parameters which were
chosen to be analysed for, are presented in Table 3.5. These parameters were chosen based on the
following:
The water type of different coal formations.

The composition of produced/effluent water from coal at UCG operations.
The composition of formation water in typical South African coals and coals around the globe.
NORM concentration in Karoo aquifers.
Dissolved gases from spring water in the Karoo.
143
TABLE 3 .5 : POTENTIAL CONSTITUENTS WHICH ARE EXPECTED TO BE PRESENT IN COAL GROUNDWATER AFTER
UNDERGRO UND CO AL GAS IFICATIO N O P ERATIO NS
Parameters
Major anions
Bicarbonate (HNO3)
Chlorine (Cl)
Sulphate (SO42)
Ammonium (NH 4+)
Nitrate (NO3)
Fluoride (F)
Major cations
Calcium (Ca +)
Magnesium (Mg+)
Potassium (K +)
Silica (Si)
Sodium (Na +)
Trace elements
Aluminium (Al)
Antimony (Sb)
Arsenic (As)
Boron (B)
Cadmium (Cd)
Chromium (Cr)
Cobalt (Co)
Copper (Cu)
Cyanide (Cn)
Iron (Fe)
Lead (Pb)
Lithium (Li)
Manganese (Mn)
Mercury (Hg)
Molybdenum (Mo)
Nickel (Ni)
Selenium (Se)
Titanium (Ti)
Uranium (U)
Vanadium (V)
Zinc (Zn)
Dissolved gases
Nitrogen
Butane (C4H10)
Ethane (C2H6)
Helium (He)
Methane (CH 4)
Propane (C3H8)
VOCs
144
Parameters
Benzene
Carbon disulphide
Chloroform
Ethylbenzene
Naphthalene
Toluene
Xylenes (o-xylene, m- + p-xylene, total xylene)
Phenols
C0-C5
SVOC + PAHs
Acenaphthene
Acridine
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Carbazole
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
Indole
Isoquinoline
Phenanthrene
Pyrene
Pyridine
Quinoline
Radioactive constituents
Radium-226, 228
Uranium-235, 238
Thorium- 232
Radon-222
Potassium-40
3.9.3.3 Previous studies on unconventional gas projects
From the groundwater baseline establishment literature reviewed related to hydraulic fracturing,
UCG, oil and gas, and unconventional gas projects, there are many different chemical constituents
that have been analysed for. The different chemical constituents that different studies have analysed
for during hydraulic fracturing and UCG projects, are presented in Appendix C.
145
Table 3.6 is a summary of the constituents that the different companies and groups analysed for, or
recommendations of parameters to be analysed for during groundwater baseline establishment for
hydraulic fracturing, UCG, oil and gas, and unconventional gas projects, together with the percentage
a specific constituent was analysed for or was recommended to be analysed for.
TABLE 3.6: LIST OF PARAMETERS ANALYSED FOR DURING GROUNDWATER BASELINE ESTABLISHMENT FOR
UNCONVENTIONAL GAS PROJECTS
Times listed in Percentage of Percentage of
Times listed in
literature relevant constituents in the constituents in the
Constituent literature relevant
to hydraulic studies/ studies/
to UCG (n = 14)
fracturing (n = 20) literature reviewed literature reviewed
Characteristics
Total dissolved solids (TDS) 17 85 12 86
pH 14 70 11 79
Electrical conductivity 14 70 10 71
Alkalinity as HCO3- 8 40 8 57
Alkalinity (total, bicarbonate, and
4 20 3 21
carbonate; as CaCO3)
Dissolved inorganic carbon (DIC) 4 20 1 7
Alkalinity as CaCO 3 15 0 0
Acid neutralizing content (ANC) 1 5 0 0
Chemical oxygen demand (COD) 1 5 0 0
Hardness as CaCO 1 5 0 0
Major cations
Calcium (Ca +) 18 90 12 86
Sodium (Na +) 17 85 12 86
Magnesium (Mg+) 17 85 11 79
Potassium (K +) 15 75 10 71
Silica (Si) 5 25 2 14
Major anions
Chloride (Cl -) 16 80 10 71
Sulphate (SO42-) 14 70 11 79
Orthophosphate/phosphate as P 12 60 4 29
Fluoride (F-) 8 40 5 36
Nitrite and nitrate as nitrogen 6 30 2 14
Nitrate (NO3-) 4 20 2 14
Bicarbonate (HNO3-) 5 25 3 21
Nitrate, dissolved as N 5 25 3 21
Nitrite, dissolved as N 5 25 1 7
Ammonia as N 4 20 1 7
Ammonia (NH 3) 2 10 4 29
Nitrite (NO2-) 1 5 0 0
Nitrate and nitrogen 1 5 0 0
Trace metals
Barium (Ba) 19 95 9 64
Strontium (Sr) 17 85 8 57
Selenium (Se) 16 80 8 57
Arsenic (As) 14 70 5 36
146
Times listed in
to UCG (n = 14)
Iron (Fe) 14 70 10 71
Chromium (Cr) 13 65 6 43
Manganese (Mn) 11 55 9 64
Lead (Pb) 12 60 5 36
Boron (B) 11 55 7 50
Aluminium (Al) 10 50 2 14
Antimony (Sb) 10 50 2 14
Cadmium (Cd) 10 50 4 29
Cobalt (Co) 10 50 5 36
Copper (Cu) 10 50 3 21
Nickel (Ni) 10 50 2 14
Silver (Ag) 10 50 1 7
Zinc (Zn) 10 50 3 21
Molybdenum (Mo) 9 45 2 14
Beryllium (Be) 8 40 0 0
Uranium (U) 7 35 0 0
Bromide (Br-) 5 25 5 36
Lithium (Li) 6 30 2 14
Mercury (Hg) 6 30 3 21
Vanadium (V) 6 30 2 14
Thallium (TI) 4 20 0 0
Thorium (Th) 3 15 0 0
Titanium (Ti) 3 15 1 7
Rubidium (Rb) 2 10 1 7
Tungsten (W) 2 10 0 0
Cyanide (Cn) 0 0 4 29
Dissolved gases
Ethane (C2H6) 16 80 10 71
Methane (CH 4) 16 80 10 71
Propane (C3H8) 12 60 5 36
Carbon dioxide (CO2) 2 10 4 29
Ethylene (C2H4) 3 15 0 0
Fixed Gases C1-C6 3 15 0 0
Argon (Ar) 2 10 0 0
Hexane (C6H14) 2 10 0 0
Hydrogen sulphide (H 2S) 3 15 1 5
Nitrogen (N2) 2 10 0 0
Oxygen (O2) 2 10 0 0
Iso-butane (C4H10) 1 5 0 0
N-butane (C4H10) 1 5 0 0
Propylene (C3H6) 1 5 0 0
Radon (Rn) 1 5 1 7
Ethene (C2H4) 0 1 7
Free gases
Ethane (C2H6) 2 10 0 0
Methane (CH 4) 2 10 0 0
147
Times listed in
to UCG (n = 14)
VOCs
Benzene 11 55 10 71
Toluene 11 55 9 64
Ethylbenzene 11 55 8 57
Xylenes (Total) 10 50 11 79
Acetone 0 0 1 7
SVOCs
sVOCs (in general) 3 15 1 7
Acridine 0 0 1 7
Indolines 0 0 1 7
Pyridine 0 0 0 0
Polycyclic aromatic hydrocarbons
Naphthalene 4 20 2 14
Acenaphthene 1 5 2 14
Acenaphthylene 1 5 2 14
Anthracene 1 5 1 7
Benzo(a) anthracene 1 5 2 14
Benzo(a)pyrene 1 5 2 14
Benzo(b)fluoranthene 1 5 2 14
Benzo(k)fluoranthene 1 5 1 7
Chrysene 1 5 2 14
Fluoranthene 1 5 2 14
Fluorene 1 5 2 14
Indeno(1,2,3-c,d)pyrene 1 5 2 14
Phenanthrene 1 5 2 14
Pyrene 1 5 1 7
Benzo(ghi)perylene 1 5 1 7
Dibenzo(ah)anthracene 1 5 1 7
Phenols
Phenols 2 10 5 36
2-Methylphenol (o-Cresol) 0 0 1 7
3-Methylphenol (m-Cresol) 0 0 1 7
4-Methylphenol (p-Cresol) 0 0 1 7
Liquid hydrocarbons
Total petroleum hydrocarbons 7 35 4 29
Diesel range organics 4 20 1 7
Gasoline range organics 4 20 1 7
Crude oil 1 5 0 0
Hexane 1 5 0 0
Iso-pentane 1 5 0 0
N-pentane 1 5 0 0
Glycols
Diethylene glycol 1 5 0 0
Triethylene glycol 1 5 0 0
Alcohols
Isopropanol 2 10 0 0
148
Times listed in
to UCG (n = 14)
Methanol 1 5 0 0
Ethanol 1 5 0 0
Propanol 1 5 0 0
Isotopes
13CCH4 8 40 2 14
DCH4 8 40 5 36
18OH2O 5 25 2 14
DH2O 5 25 2 14
Isotopes of DIC ( 13C) 4 20 1 7
11B 2 10 0 0
13C C2H6 2 10 0 0
(87Sr /86Sr) 1 5 0 0
DC2H6 1 5 1 7
13CCO2 1 5 1 7
13C 1 5 0 0
12C 1 5 2 14
14C 1 5 0 0
Radioactivity
Gross-alpha radioactivity 8 40 2 14
Gross-beta radioactivity 8 40 2 14
Radon-222 5 25 0 0
Radium-226 4 20 0 0
Radium-228 2 10 0 0
Alpha radioactivity 1 5 0 0
Beta radioactivity 1 5 0 0
Gamma radioactivity 1 5 0 0
Lead-210 1 5 0 0
Potassium-40 1 5 0 0
Thorium-230 1 5 0 0
Thorium-228 1 5 0 0
Thorium-232 1 5 0 0
Uranium-238 1 5 0 0
CFC-11 1 5 0 0
CFC-12 1 5 0 0
CFC-13 1 5 0 0
Other
Low molecular weight acids 1 5 0 0
Pesticides 1 5 0 0
Polychlorinated biphenyls (PCB) 1 5 0 0
Bacteria 1 5 0 0
149
From the table the following is noted:
The characteristics most sampled/recommended to be analysed, for both hydraulic fracturing and
UCG projects are TDS, pH, EC and Alkalinity as HCO3 .
The major ions most analysed/recommended to be analysed, for both hydraulic fracturing and
UCG projects are calcium, sodium, magnesium, potassium, chloride, sulphate, phosphate and
fluoride.
The trace metals most analysed/recommended to be analysed, for hydraulic fracturing projects
are barium, strontium, selenium, arsenic, iron, chromium, manganese, lead and boron. Barium
and strontium were most analysed/recommended to be analysed.
The trace metals most analysed/recommended to be analysed for UCG projects are barium,
strontium, selenium, iron and manganese. Barium, iron and manganese were most
analysed/recommended to be analysed for. Further, cyanide was analysed/recommended to be
analysed only for UCG projects.
The dissolved gases most analysed/recommended to be analysed for, for both hydraulic fracturing
and UCG projects are ethane and methane, with propane of less importance.
Free gases, glycols, alcohols, low molecular weight acids, pesticides, polychlorinated biphenyls
(PCBs) and bacteria were not of much importance.
Organics such as SVOCs (PAHs, phenols, petroleum hydrocarbons) were analysed/recommended
to be analysed for, in most studies, of which VOCs such as BTEXs were analysed/recommended to
be analysed for the most, for both hydraulic fracturing and UCG projects. Furthermore, it can be
noted that phenols were analysed/recommended to be analysed for by mostly UCG projects,
which might be because phenols (and also PAHs) are major contaminants associated with the UCG
gasification projects (Ahern and Frazier, 1982).
Isotopes were analysed/recommended to be analysed for in some of the studies, of which 13 CCH4
and D CH4 are considered the most important for both hydraulic fracturing and UCG projects.
Radioactivity and silica concentration are also parameters which were generally not
analysed/recommended to be analysed for. Furthermore, it can be noted that radioactivity was
one of the main parameters generally a more significant parameter in hydraulic fracturing studies
than for UCG studies.
It should be noted that during the time of writing there were not as many publicly available literature
on groundwater baseline studies and recommendations for groundwater baseline studies for UCG
projects as there were for hydraulic fracturing operations. However, Ahern and Frazier (1982) (who
was also referenced in Table 3.6), conducted a literature review of more than 300 articles on
groundwater pollution associated with UCG, of which 56 contained information on the water quality
150
at UCG sites. From the literature review the following was noted: Of the parameters listed in Table
3.6, the following parameters showed an increase of at least five to ten times the baseline values
within the Hoe Creek 1, UCG site, inside and outside the burn zone: ammonium, boron, calcium,
bromide, lithium, cyanide, magnesium, potassium, sulphate and phenols. At the Hanna 2, UCG site,
the aluminium concentration increased almost 100 times the baseline value during UCG operation
(Ahern and Frazier, 1982). Of these parameters, ammonium, cyanide, boron and phenols have
historically been shown to be major contaminants from UCG operations (Dennis, 2006).
According to Ahern and Frazier (1982), at the Texas UCG test, ammonium, sulphate, phenols and other
unspecified constituents were analysed before gasification to establish a baseline. The monitoring
results after gasification indicated that all the constituents analysed for had increased due to
gasification. The most prominent compounds produced were phenols and PAHs (mostly two - and
three-ring PAHs).
3.9.3.4 Hydraulic fracturing fluid constituents
Based on the literature review, no single chemical has been identified as having been used in all of the
hydraulic fracturing wells in the USA. Hydrochloric acid, methanol and hydrotreated light petroleum
distillates were the only three chemicals to be used in more than half of the sites in the USA; each of
these chemicals can be used for different purposes, and are not necessarily used for one specific
purpose.
Therefore, it would be senseless to analyse for a specific additive type, for example, corrosion
inhibitors, as many different chemicals can be used as corrosion inhibitors. It would also be pointless,
financially, to analyse for each different type of chemical which might possibly be used during
hydraulic fracturing. Furthermore, because of the use of indefinite chemicals during the hydraulic
fracturing treatment process, it would not be logic to analyse for specific chemicals.
From Section 2.3.5.2 on hydraulic fracturing additives, the following constituents are considered
essential for sampling and analysis during groundwater baseline establishment for hydraulic fracturing
operations in South Africa as they are either present in the most and least mobile chemicals used in
hydraulic fracturing fluid, or were the most used chemicals in hydraulic fracturing fluid. See Table 3.7
for constituents found in hydraulic fracturing fluid. There are many different types of PAHs used in
hydraulic fracturing fluid, but naphthalene is predominately used.
These parameters are based on the following:
Constituents found in the most and least mobile chemicals used in hydraulic fracturing fluid.
Constituents found in the most used chemicals in hydraulic fracturing fluid.
151
TABLE 3.7: CONSTITUENTS FOUND IN HYDRAULIC FRACTURING FLUID CHEMICALS
Parameters
Major anions
Chloride (Cl )
Phosphate (PO4)
Ammonium (NH 4+)
Ammonia (NH3)
Sulphate (SO42)
Major cations
Sodium (Na +)
Magnesium (Mg+)
Potassium (K +)
Aluminium (Al)
Bromide (Br )
Boron (B)
Silica (Si)
Alcohols
Methanol
Isopropanol
Ethanol
VOC
BTEX
SVOCs
Glycols
Ethylene glycol
Polyethylene glycol
Naphthalene
Phenols
Nonyl phenol ethoxylate
Petroleum hydrocarbons
Gases
Ethane (C2H6)
Nitrogen (N2)
3.9.3.5 Drilling fluid constituents

When it comes to the drilling fluid used for hydraulic fracturing and UCG operations, the same could
be said as for the fluid used in hydraulic fracturing treatment fluid, that the type of drilling fluid that
will be used is not known. From Section 2.3.5.5 on drilling fluid/mud chemicals, the following
constituents are considered essential for sampling and analysis during groundwater baseline
establishment for hydraulic fracturing operations in South Africa. See Table 3.8 for the recommended
parameters to be analysed for.
These parameters are based on:

Constituent found in typical water-based and nonaqueous-based drilling fluid.
152
TABLE 3.8: CONSTITUENTS FOUND IN TYPICAL WATER-BASED AND NONAQUEOUS-BASED DRILLING FLUID
Parameters
Major anions
Chloride (Cl )
Sulphate (SO42)
Bicarbonate (HNO3)
Major cations
Sodium (Na +)
Calcium (Ca +)
Potassium (K +)
Zinc (Zn)
Bromide (Br )
Iron (Fe)
Titanium (Ti)
Aluminium (Al)
Manganese (Mn)
TPHs
Glycols
Silica
3.9.3.6 Natural background groundwater values of Karoo aquifers
When selecting parameters to analyse for, it is necessary to consider natural levels of constituents.
Naturally occurring constituents can be used as potential chemical indicators of contamination, as it
was already noted that many hydraulic fracturing fluids and drilling fluids contain constituents that
occur naturally in groundwater, such as phosphorus. It is essential to analyse for these naturally
occurring constituents before any unconventional operations can occur, to establish a baseline against
which future groundwater monitoring results can be compared for signs of contamination.
From the sub-section on the distribution of Major constituents in Karoo aquifers, work done by Kent
(1949) on thermal springs in South Africa, and work done by Geel et al. (2013) on the Ecca shales of
the Karoo Supergroup, the following list of chemical parameters was chosen based on the
groundwater chemistry of sedimentary rocks of the Karoo, and the major chemical constituents of
groundwater in the Karoo (see Table 3.9).
153
TABLE 3 .9 : NATURAL GROUNDWATER Q UALITY OF THE K AROO, WITH RANGES WHICH CAN BE EXPECTED
DURING ANALYSIS
Constituent Range
Cations (mg/l)
Calcium (Ca +) 5300
Sodium (Na +) <201 200
Magnesium (Mg+) <30200

Manganese (Mn)
Zinc (Zn)
Iron (Fe)
Potassium (K +) 1020
Aluminium (Al)
Vanadium (V)
Nickel (Ni)
Chromium (Cr)
Silica (Si)
Anions (mg/l)
Carbonate (CO3-2)
Sulphate (SO42-) <103 000
Bicarbonate (HNO3-)
Chloride (Cl -) <201 200
Nitrate as N (NO3--N) 020
Fluoride (F-) <0.72

Radionuclides (ppm)
Uranium -238, 235, 234
Radon- 222
Radium- 228, 226
Lead-210
Thorium- 232
Pollonium-201
Potassium-40
Radiocarbon
Gases
Nitrogen (N2)
Argon (Ar)
Helium (He)
Methane (CH 4)
Ethane (C2H6)
Propane (C3H8)
Butane (C4H10)
Stable isotopes (gases)
3H
1H
154
Constituent Range
2H
12C
13C
16O
18O
15N
Note:
: No data available
No trace elements, organic compounds and dissolved gas concentrations for the entire basin were
available. Only a few analyses existed and did not allow for any regional generalisation (Woodford and
Chevallier, 2002).
3.9.4 Selected parameters to be analysed for during groundwater baseline

establishment for hydraulic fracturing and underground coal
gasification projects
Specific parameters need to be chosen to correctly define the groundwater sources, without collecting
redundant data which is used, for example, to indicate contamination, which could more easily be
determined by analysing for other constituents.
The analytical results can then be compared to the baseline value ranges, and a likely cause for the
change, if any, in the concentrations can be identified, whether the changes are natural (for example,
increase in chloride due to aquitard diffusion), seasonal, mixing of groundwater between different
layers (for instance, the shale or coal formation water to near-surface potable aquifer systems) due to
unconventional gas projects, or contamination of the water with hydraulic fracturing fluid, drilling fluid
or mobilised formation or produced water from unconventional gas projects. Therefore, it is in the
best interest of the drilling company to have such data in the case that contaminants appear, to be
able to indicate that such contaminants may have already been present, before unconventional gas
drilling activities started, and cannot be held accountable.
Table 3.10 provides a list of chemical constituents that are suggested to be analysed for during
groundwater baseline establishment for hydraulic fracturing and UCG operations on a regional and
local scale together with their target water quality ranges (TWQRs) or maximum contaminant levels
(MCLs).
155
TABLE 3 .1 0 :SUGGESTED P ARAMETERS TO BE ANALYSED FOR D URING GROUNDWATER BASELINE
ESTABLISHMENT FO R HYDRAULIC FRACTURING AND UNDERGROUND COAL GASIFICATION
O P ERATIO NS WITH THEIR SP ECIFIED WATER Q UALITY STANDARDS
Parameter TWQR / MCL (mg/l)

Major cations
Calcium (Ca +) 32
Magnesium (Mg+) 30
Potassium (K +) 50
Sodium (Na +) 100
Silica (Si) NG
Major anions
Chloride (Cl ) 100
Sulphate (SO42) 200
Nitrate (NO3) 6
Bicarbonate (HNO3) NG
Carbonate (CO32) 50
Phosphate (PO4) NG
Ammonium as N (NH 4+-N) 1.0
Nitrate as N (NO3-N) *10
Nitrite as N (NO2-N) *1
Trace metals
Aluminium (Al) 0.15
Antimony (Sb) *0.006
Arsenic (As) 10
Barium (Ba) *2
Beryllium (Be) *0.004
Boron (B) NG
Bromide (Br -) NG
Bromine (Br) NG
Cadmium (Cd) 5
Chromium (Cr) 0.1
Cobalt (Co) NG
Copper (Cu) 1 000
Cyanide (Cn) *0.2
Iron (Fe) 100
Lead (Pb) 10
Lithium (Li) NG
Manganese (Mn) 50
Mercury (Hg) 0.001
Molybdenum (Mo) NG
Nickel (Ni) NG
Rubidium (Rb) NG
Selenium (Se) 20
Silver (Ag) *100
Strontium (Sr) NG
Thallium (Ti) *2
Thorium (Th) NG
Titanium (Ti) NG
Tungsten (W) NG
Uranium (U) 70
Vanadium (V) 0.1
Zinc (Zn) 3
156
Dissolved gases
Argon (Ar) NG
Carbon dioxide (CO2) NG
Ethane (C2H6) NG
Helium (He) NG
Hydrogen sulphide (H 2S) NG
Methane (CH 4) NG
Nitrogen (N2) NG
Propane (C3H8) NG
Radon (Rn 222) *300 pCi/l AMCL
Xenon (Xe) NG
Krypton (Kr) NG
Neon (Ne) NG
Dissolved stable isotopes
DH2O NG
DCH4 NG
DC2H6 NG
18OH2O NG
13CCO2 NG
13CCH4 NG
13CC2H6 NG
34Ssulphate NG
18Osulphate NG
87Sr /86Sr NG
Isotopes of DIC ( 13C) NG
Radioactive isotopes
Alpha radioactivity 0.5
Beta radioactivity 1.38
Organics
VOCs
Benzene *0.005
Toluene *1
Ethylbenzene *0.7
Xylenes (o-xylene, m- + p-xylene, total *10
xylene)
Isopropylbenzene NG
Chloroform *0.08
Carbon disulphide NG
Acetone NG
SVOCs
1,2-Diphenylhydrazine NG
1,4-Dioxane NG
7,12-Dimethylbenz(a)anthracene NG
Acetophenone NG
Benzidine NG
Benzyl alcohol NG
Bis(2-Chloroethyl)ether NG
Bis(2-Ethylhexyl) phthalate *0.006
Butylbenzylphthalate NG
Diethylphthalate NG
Di-n-butylphthalate NG
157
Di-n-octylphthalate NG
Diphenylamine NG
Hexachlorobenzene *0.001
N-Nitrosodiphenylamine NG
N-Nitrosomethylethylamine NG
Phorate NG
Pyridine NG
PAHs
1,2,3,4-Tetrahydro-naphthalene NG
1-Methyl-7-(1-
NG
methylethyl)phenanthrene
1-Methylnaphthalene NG
Acenaphthene NG
Acenaphthylene NG
Anthracene NG
Benzo(a)anthracene NG
Benzo(a)pyrene *0.0002
Benzo(b)fluoranthene NG
Benzo(g,h,i)perylene NG
Benzo(k)fluoranthene NG
Chrysene NG
Decahydro-4,4,8,9,10-
NG
pentamethylnaphthalene
Dibenzo(a,h)arthracene NG
Dimethylnaphthalene NG
Fluoranthene NG
Fluorene NG
Indeno(1,2,3-cd)pyrene NG
Methylnaphthalene NG
Methylphenanthrene NG
Naphthalene NG
Perylene NG
Phenanthrene NG
Pyrene NG
Tetramethylphenanthrene NG
Phenols
2,3-Dimethylphenol (2,3-Xylenol) 1
2,4-Dichlorophenol *0.07
2,6-Dichlorophenol 1
2,4-Dimethylphenol (2,4 Xylenol) 1
2-Methylphenol (o-Cresol) 1
3-Methylphenol (m-Cresol) 1
4-Methylphenol (p-Cresol) 1
Alkylphenol ethoxylates 1
Butylphenol 1
Hydroxybenzene 1
Methoxy-methylphenol 1
158
Nonylphenol ethoxylate 1
Nonylphenols 1
Octylphenol 1
p-tert-butyl-phenol 1
Tert-butyl-phenol 1
Trichlorophenol 1
TPH (C6-C40) NG
Notes:
*Based on EPA MCL value
NG: No guideline available
AMCL: Alternative Maximum Contaminant Level
The TWQR for different chemical constituents presented are according to the South African manual
for Drinking Water Standards (RSA DWAF, 1996) where available. Where no South African Drinking
Water Standards were available, contaminant levels from USEPA (2012) were listed. These
contaminant levels are the maximum contaminant levels (MCLs), which are the permissible level of a
contaminant in drinking water, according to USEPA (2012). The MCLs represent enforceable drinking
water standards.
These parameters were chosen on the basis of (a) establishing the geochemical baseline values for a
specific area; (b) determining the source of the parameters; (c) determining the chemical composition
of the different aquifer systems; (d) characterising the different water types in the study area; (e) the
potential occurrence of these parameters in groundwater from shale; (f) the use of the parameters
during interpretation of data; (g) determining the origin and age of the water; (h) determining the
source of potential methane; (i) determining spatial trends of the parameters; (j) compounds that may
occur at high concentrations naturally in the local and regional groundwater; (k) the potential for
these parameters to be used in hydraulic fracturing fluid and drilling fluid; (l) to better understand the
processes controlling the chemical composition of the aquifer; and (m) to settle disputes if arguments
were to occur after hydraulic fracturing operations.
The parameters selected are based on natural groundwater chemistry in the Karoo; flowback,
formation and produced water chemistry from coals and shales, from UCG, and hydraulic fracturing
operations, respectively; chemicals used in hydraulic fracturing operations; general drilling fluid
composition; and suggestions or practices from similar unconventional gas projects, groundwater
baseline studies and contamination studies.
The literature reviewed also suggest that a full contaminant scan can be performed during baseline
establishment, where an exhaustive list of chemical parameters are chosen to be analysed (Mazor,
2003). This would provide a comprehensive evaluation of the groundwater system in the area.
159
From the acquired data, specific parameters of interest can be chosen for follow-up sampling events
during the baseline establishment phase to provide more information on these specific parameters of
interest, and to cut sampling and analysis cost.
The following sections provide rationales for selecting the suggested parameters, followed by the
suggested sampling techniques.
3.9.4.1 Rationale for sampling and analysis of the different parameters
It is suggested that in the study area, the suggested parameters need to be analysed for from each
hydrostratigraphic unit, to create concentration ranges (maximumminimum) for each unit. These
natural ranges can then be used to distinguish the different units from one another (Fetter and
Willard, 2001), and can be compared to monitoring data to determine if potential groundwater
contamination due to unconventional gas operations has occurred.
3.9.4.1.1 Major ions
Major ions are generally used to determine the general character of the water and are the main
sources of salinity in groundwater and surface water. Major ions reflect the main mineral types and
the geochemical processes involved in water-rock interactions (Edmunds and Shand, 2008). When
selecting parameters to analyse for, major ions are regarded as the minimum requirements for any
sampling and analysis programme (Weaver et al., 2007).
Major ions are used to characterise the water type/hydrochemical facies of each hydrostratigraphic
group by using the trilinear/piper plots, and to do this, the major cations (potassium, calcium,
magnesium and sodium) and major anions (sulphate, chloride, bicarbonate and carbonate, and
nitrate) are required.
It should be noted that some ions may be classified as minor or major ions in some areas, ions such as
these are manganese, ammonium, nitrate, uoride, boron, iron, and hydrogen sulphide (Younger,
2009).
The dissolution of minerals in soil and bedrock with which water comes into contact, are the main
natural sources of major cations. The major cation concentrations in groundwater are almost always
greater than 1 mg/l. Calcium and magnesium are the product of dissolution from carbonate minerals
such as calcite and dolomite and gypsum which occur in different sedimentary formations in South
Africa. Many different silicate minerals are sources of calcium, magnesium, potassium and sodium due
to weathering (Younger, 2009).
160
The cations presented in Table 3.11 are suggested to be sampled and analysed for during groundwater
baseline establishment for hydraulic fracturing and UCG projects.
TABLE 3.11: LIST OF SUGGESTED CATIONS TO BE ANALYSED FOR
Major cations TWQR (mg/l)
Calcium (Ca +) 32
Magnesium (Mg+) 30
Potassium (K +) 50
Sodium (Na +) 100
Silica (Si) NG
Note:
The anions which generally occur in groundwater at concentrations greater than 1 mg/l are sulphate,
bicarbonate and chloride, with nitrate and carbonate concentrations seldom above 1 mg/l. However,
high levels of some anions may be found in certain environments depending on the geology and land
use, such as some shales recorded by Alley et al. (2011).
The anions presented in Table 3.12 are suggested to be sampled and analysed for during groundwater
baseline establishment.
TABLE 3.12: LIST OF SUGGESTED ANIONS TO BE ANALYSED FOR
Major anions TWQR / MCL (mg/l)
Chloride (Cl ) 100
Ammonium as N (NH 4+-N) 1
Bicarbonate (HNO3) NG
Carbonate (CO32) 50
Nitrate (NO3) 6
Nitrate as N (NO3-N) *10
Nitrite as N (NO2-N) *1
Phosphate (PO4) NG
Nitrate (NO3) 200

Notes:
161
3.9.4.1.2 Trace metals
Similar to major ions, trace metals in groundwater are from the dissolution of minerals in soil and
bedrock into water with which it comes into contact. Trace metal concentration in groundwater is less
than 1 mg/l (Hem, 1985).
As mentioned previously, there is little data available on trace element concentration distribution in
the Karoo Basin aquifers. A full list of trace metals could not be produced from the available literature.
It should be noted that although the data is not available, many different types of trace metals do
occur in the Karoo Basin aquifers (Woodford and Chevallier, 2002).
Some of the trace metals may originate from formation water, and some from the solid substrate
phase (formation rock) and are mobilised during unconventional gas operations (Orem et al., 2014).
Some of the trace metals, such as lithium, barium and strontium, may be present at high
concentrations in deeper groundwater, and could be used as indicators for deeper groundwater
(OBrien et al., 2013).
As can be seen from Table 3.13 beryllium, silver, thallium, thorium and tungsten are the only trace
metals which do not occur in either shale or coal formation water, hydraulic fracturing fluid, drilling
fluid, and in groundwater of the Karoo Basin, based on the literature reviewed. As already mentioned
these trace metals may occur in groundwater of the Karoo Basin aquifers on a regional scale; no
documentation on this is, unfortunately, available. Additionally, these trace metals may potentially
occur in shale and coal formation and produced water, they were however not listed in the literature
reviewed.
It is, therefore, suggested that all the trace metals from Table 3.13 be analysed for, or a full trace metal
scan can be requested by the laboratory, if it would not be too expensive.
Furthermore, it is suggested that if all the trace metals cannot be sampled and analysed for that at
least barium, strontium, selenium, arsenic, iron, chromium, manganese, lead and boron should be
sampled and analysed for as they were sampled or recommended to be analysed for by more than
50% of the studies on groundwater baseline establishment or monitoring for unconventional gas
projects.
The trace metals presented in Table 3.13 are suggested to be sampled and analysed for during
groundwater baseline establishment for hydraulic fracturing and UCG projects. The trace elements
that different studies have analysed for during hydraulic fracturing and UCG projects, are presented
in Appendix C.
162
TABLE 3.13: TRACE ELEMENTS IN DIFFERENT MEDIUMS AND STUDIES
Occurs in Occurs in
Occurs in
shale Occurs in Occurs in coal
solid residue
formation Suggested hydraulic Occurs in ground- formation TWQR /
Constituent by-products
and by studies fracturing drilling fluid water of the and MCL (mg/l)
and tar of
produced fluid Karoo produced
UCG
water water
Aluminium (Al) 0.15
Antimony (Sb) *0.006
Arsenic (As) 10.0
Barium (Ba) *2.0
Beryllium (Be) *0.004
Boron (B) NG
Bromide (Br) NG
Bromine (Br) NG
Cadmium (Cd) 5.0
Chromium (Cr) 0.1
Cobalt (Co) NG
Copper (Cu) 1 000
Cyanide (Cn) *0.2
Iron (Fe) 100.0
Lead (Pb) 10.0
Lithium (Li) NG
Manganese (Mn) 50.0
Mercury (Hg) 0.001
Molybdenum
NG
(Mo)
Nickel (Ni) NG
Rubidium (Rb) NG
Selenium (Se) 20.0
Silver (Ag) *100
Strontium (Sr) NG
Thallium (TI) *2.0
Thorium (Th) NG
Titanium (Ti) NG
Tungsten (W) NG
Uranium (U) 70.0
Vanadium (V) 0.1
Zinc (Zn) 3.0
Notes:
3.9.4.1.3 Dissolved gases
Some dissolved gases, such as noble gases, can be used as potential indicators of groundwater mixing
(Hiscock, 2005; Woodford and Chevallier, 2002). Other dissolved gases such as hydrogen sulphide
(H2 S), carbon dioxide (CO2 ), nitrogen (N2 ) are major components of shale and coal gas, and can
therefore be used as tracers for contamination from unconventional gas projects (Sury et al., 2004).
Hydrocarbon gases can be used to determine the source of methane; for example, if it was determined
during the groundwater baseline establishment phase that the source of methane from the shallow
163
boreholes was a biogenic source, and thermogenic gas is detected in these boreholes during
monitoring, it may be an indication that preferential flow features were created through
unconventional gas activities which allowed deep thermogenic gas to migrate towards the shallow
groundwater.
The dissolved gases presented in Table 3.14 are suggested to be sampled and analysed for during
groundwater baseline establishment for hydraulic fracturing and UCG projects; however, as a
minimum, only methane, ethane and propane is recommended to be included on a regular basis,
unless detailed assessment of biological activity and/or remedial processes post-closure are
considered. The dissolved gasses that different studies have analysed for during hydraulic fracturing
and UCG projects, are presented in Appendix C.
TABLE 3.14: LIST OF SUGGESTED DISSOLVED GASES TO BE ANALYSED FOR

Occurs in
Occurs in
coal
shale Occurs in Occurs in
formation TWQR /
formation Suggested by hydraulic Occurs in ground-
Constituent and AMCL
and studies fracturing drilling fluid water of the
produced (mg/l)
produced fluid Karoo
water and
water
produced gas
Argon (Ar) NG
Carbon dioxide (CO2) NG
Ethane (C2H6) NG
Helium (He) NG
Hydrogen sulphide
NG
(H2S)
Methane (CH 4) NG
Nitrogen (N2) NG
Propane(C3H8) NG
*300 pCi/l
Radon (Rn 222)
AMCL
Xenon (Xe) NG
Krypton (Kr) NG
Neon (Ne) NG
Notes:
AMCL: Alternative Maximum Contaminant Level
3.9.4.1.4 Dissolved stable isotopes
Isotope fractionation processes such as physical, chemical and biological processes, modify the
proportions of stable isotopes. By measuring the isotope ratios the processes which the water ha s
undergone can be identified (Quevauviller et al., 2009).
164
It was suggested by Steyl et al. (2012) and Molofsky et al. (2011) that before drilling for
unconventional gas sources, stable isotopes, as well as radioactive isotopes, need to be measured
during the groundwater baseline establishment phase. By comparing the data to the monitoring data
it can be determined if potential contamination has occurred as a result of unconventional gas
activities.
By establishing groundwater isotope ranges for different hydrostratigraphic groups during the
baseline establishment phase, would prove invaluable for determining if groundwater contamination
from unconventional gas projects occurred after or during the project lifetime.
Stable isotopes can be used to:
determine water movement patterns;

determine the biochemical history of gases;
determine geochemical processes;
determine the groundwater origin;
determine recharge of groundwater; and
determine the age of groundwater (Cheung and Mayer, 2009; Hiscock, 2005; Quevauviller et al.,
2009).
The dissolved stable isotopes presented in Table 3.15 are suggested to be sampled and analysed for
during groundwater baseline establishment for hydraulic fracturing and UCG projects.
TABLE 3.15: LIST OF SUGGESTED ISOTOPES TO BE ANALYSED FOR
Isotope TWQR / MCL (mg/l)
DH2O NG
DCH4 NG
DC2H6 NG
18OH2O NG
13CCO2 NG
13CCH4 NG
13CC2H6 NG
34Ssulphate NG
18Osulphate NG
87Sr /86Sr NG
Isotopes of DIC ( 13C) NG
Note: NG: No guideline available
165
3.9.4.1.5 Radioactive constituents
Radioactivity in groundwater is mainly produced from dissolved constituents and is due to radioactive
nuclides which can be either , or emitters. The main contributing nuclides of radioactivity in water
are uranium-238,235,234, radium-226, 228, radon-222, potassium-40, and to a minor extent, lead-
210, polonium-201 and throrium-230 (Focazio et al., 2001; Xu et al., 2012).
The rationales for sampling and analysing for radioactive constituents

To establish natural concentration ranges.
Radioactive constituents do occur in shale formation water, which may possibly contaminate
potable groundwater.
It was recommended by 10 out of 20 hydraulic fracturing studies to analyse for radioactive
constituents, of which 8 out of 20 studies recommended to analyse for gross alpha and gross beta
radioactivity.
It is suggested that instead of sampling and analysing for specific radionuclide species, that only gross
alpha and gross beta radioactivity is measured, which would include all the radionuclides present in
the groundwater, and to indicate if any radioactive contamination is present (Hem, 1985; Senior,
2014). This method is suggested on the basis that radioactive constituents are not normally used in
hydraulic fracturing fluid and drilling fluid. Therefore, it would be pointless to analyse for individual
constituents, whereas measuring for the total alpha and beta radioactivity would provide ranges
which would be expected from different hydrostratigraphic units.
The baseline values can be compared to monitoring values to determine if the unconventional gas
project increased the concentration of the radionuclides in the groundwater of the different
hydrostratigraphic units through mixing of produced water from shales or sandstones which may
contain high concentrations of radionuclides, with low concentrations of groundwater from the
different hydrostratigraphic units.
The radionuclides presented in Table 3.16 are suggested to be analysed for during groundwater
TABLE 3.16: LIST OF SUGGESTED RADIONUCLIDES TO BE ANALYSED FOR
Radionuclide TWQR (Bq/R)
Alpha radioactivity 0.5
Beta radioactivity 1.38
Note that only 2 of the 14 studies on groundwater baseline establishment for UCG operations have
sampled or recommended sampling for radioactive constituents (gross alpha and beta radioactivity).
166
It is, however, suggested to be analysed for, as radioactive constituents are carcinogenic, may cause
serious health issues if present at concentrations exceeding any health-based screening levels for
humans. Furthermore, relatively high concentrations of radioactive constituents may be found in
South African soil (Republic of South Africa, Department of Water Affairs and Forestry [RSA DWAF],
1996) and in groundwater (Xu et al., 2012).
3.9.4.1.6 Organics
Just like inorganic substances, organic substances in produced water may originate from the solid
phase associated with formation water (i.e. coal or shale), or they can be from organic chemicals
added during production and preparation at hydraulic fracturing operations, or they may be released
during the UCG gasification process, or may be from the solid residue left in the cavity after/during
gasification (Kapusta and Staczyk, 2011; Orem et al., 2014). Some organics such as pyridine, carbon
disulphide and naphthalene which occur frequently in hydraulic fracturing fluid can be used as tracers
for contamination from hydraulic fracturing fluid, whereas BTEX and 2,3-dimethylphenol (2,3-xylenol),
2,4-dimethylphenol (2,4-xylenol), 2,5-dimethylphenol (2,5-xylenol), 2,6-dimethylphenol (2,6-xylenol)
can be used as organic tracers of contamination from UCG flowback/produced water.
V o l a t i l e o r g an i c c o m p o u n d s ( V O C s )
VOCs are lightweight, synthetic organic compounds such as BTEXs (benzene, toluene, ethylbenzene,
and xylenes). VOCs generally have low solubilities in water, whereas BTEXs have higher solubilities in
comparison to other VOCs, thus they can migrate considerable distances from the source (Weaver
et al., 2007).
The rationale s for sampling and analysing for VOCs

BTEX can be found in surface and groundwater in close vicinity to natural oil, gas and coal deposits
(Leusch and Bartkow, 2010).
Benzene is a common constituent in hydraulic fracturing and UCG wastewater (LIU et al., 2007;
USEPA, 2015b).
Chloroform may be produced by shales and coals, and it is also one of the most abundant.
BTEXs can be used in hydraulic fracturing treatment as solvents, scale inhibitors, flow enhancers,
friction reducers, and non-emulsifiers (Waxman et al., 2011).
Acetone and carbon disulphide may occur in shale produced water, and can be used in hydraulic
fracturing fluids as a friction reducer (Hayes, 2009).
167
When analysing for VOCs, it is essential to use low-level analytical methods, as most of the VOC
concentrations in groundwater are less than 1 g/l. Zogorski et al. (2006) suggested using a detection
limit of 0.02 g/l for VOCs.
The VOCs presented in Table 3.17 are suggested to be sampled and analysed for during groundwater
TABLE 3.17: LIST OF SUGGESTED VOCs TO BE ANALYSED FOR

VOCs TWQR / MCL (mg/l)
Benzene *0.005
Toluene *1.0
Ethylbenzene *0.7
Xylenes (o-xylene, m- + p-xylene, total xylene) *10
Isopropylbenzene NG
Chloroform *0.08
Carbon disulphide NG
Acetone *0.005
Notes:
S e m i - v o l a ti l e o r ga n i c c o m p o u n d s ( S V O C s )
Semi-volatile organic compounds, also known as extractable compounds (Nielsen and Nielsen, 2006),
are hydrophobic and by definition moderately volatile (Lucius et al., 1992). SVOCs are organic
molecules which can have meaningful abundances in both the gas phase and condensed phase. They
occur as active ingredients in many products such as pesticides, personal care products, and cleaning
agents (Weschler and Nazaroff, 2008).
The most important type of SVOCs for unconventional gas groundwater baseline establishment are
total petroleum hydrocarbons (TPHs), polycyclic aromatic hydrocarbons (PAHs) and phenols which will
be covered separately.
The rationale s for sampling and analysing for SVOCs

SVOCs may be found in produced water of shales and coals.
SVOCs may be used in hydraulic fracturing fluid.
Pyridine is considered a useful monitoring compound at UCG operations (LIU et al., 2007).
The SVOCs presented in Table 3.18 are suggested to be sampled and analysed for during groundwater
Note that although PAHs, phenols and TPHs are classes of SVOCs, they are not included in the table
and are covered separately.
168
TABLE 3.18: LIST OF SUGGESTED SVOCS TO BE ANALYSED FOR
SVOC TWQR / MCL (mg/l)
1,2-Diphenylhydrazine NG
1,4-Dioxane NG
7,12-Dimethylbenz(a)anthracene NG
Acetophenone NG
Benzidine NG
Benzyl alcohol NG
Bis(2-Chloroethyl)ether NG
Bis(2-Ethylhexyl) phthalate *0.006
Butyl benzyl phthalate NG
Diethylphthalate NG
Di-n-butylphthalate NG
Di-n-octylphthalate NG
Diphenylamine NG
Hexachlorobenzene *0.001
N-Nitrosodiphenylamine NG
N-Nitrosomethylethylamine NG
Phorate NG
Pyridine NG
Notes:
In a study conducted by Coleman (2011), on the chemical composition of produced water from four
shale gas plays in the USA, SVOCs were generally not present at detectable concentrations. The most
frequently detected SVOCs were pyridine and phenolics. Additionally, quinoline, isoquinoline, indole,
acridine, carbazole, which are all N-heterocycles, may also be sampled and analysed for as they have
been found in effluent water during UCG experimental studies (Kapusta et al., 2013).
In a study by Hayes (2009) on the sampling of streams associated with the development of Marcellus
shales gas, it was determined that from a total of 112 SVOCs sampled from flowback and influent
water from hydraulic fracturing operations, 98% of the compounds were at non-detectable levels
(below 10 ppb). From the study, only bis (2-chloroethyl) ether and pyridine, were measured at levels
exceeding 1 ppm. Pyridine is a precursor of one of the hydraulic fracturing additives. Furthermore, the
Hayes (2009) study suggested not to sample for all the SVOCs but only for a select few.
P o l y c y cl i c a r o m at i c h y d ro c ar b o n s ( P A H s )
Naphthalene, anthracene and fluoranthene are among the most common PAH contaminants in the
groundwater system (Quevauviller et al., 2009), whereas naphthalene, phenanthrene,
benzo[b+k]fluoranthene, dibenz[a,h]anthracene, benzo[a]pyrene and chrysene may be associated
with produced water from coal and shales (Kapusta et al., 2013; Stearman et al., 2014).
169
The rationale s for sampling and analysing for PAHs
PAHs occur in coal and shale produced water and may be used in hydraulic fracturing fluid
(Kapusta et al., 2013; Orem et al., 2014; Sirivedhin and Dallbauman, 2004).
Naphthalene is one of the most frequently used chemicals in hydraulic fracturing fluid, and occurs
in coal and shale produced water (Kapusta et al., 2013; Stearman et al., 2014; USEPA, 2015b).
Naphthalene is considered a useful monitoring compound at UCG operations (LIU et al., 2007).
The PAHs presented in Table 3.19 are suggested to be sampled and analysed for during baseline
establishment for hydraulic fracturing and UCG projects.
TABLE 3.19: LIST OF SUGGESTED PAHS TO BE ANALYSED FOR

PAH TWQR / MCL (mg/l)
1,2,3,4-Tetrahydro-naphthalene NG
1-Methyl-7-(1-methylethyl)phenanthrene NG
Acenaphthene NG
Acenaphthylene NG
Anthracene NG
Benzo(a)anthracene NG
Benzo(a)pyrene *0.0002
Benzo(b)fluoranthene NG
Benzo(g,h,i)perylene NG
Benzo(k)fluoranthene NG
Chrysene NG
Decahydro-4,4,8,9,10-pentamethylnaphthalene NG
Dibenzo(a,h)arthracene NG
Dimethylnaphthalene NG
Fluoranthene NG
Fluorene NG
Indeno(1,2,3-cd)pyrene NG
Methylnaphthalene NG
Methylphenanthrene NG
Naphthalene NG
Perylene NG
Phenanthrene NG
Pyrene NG
Tetramethylphenanthrene NG
Notes:
170
Ph en o ls
Conventionally produced water from coal and shale may have a total phenol (C0C5 phenols)
concentration of 0.423 mg/l (Neff, 2002). Nonylphenol ethoxylate is commonly used in hydraulic
fracturing fluid as a foaming agent, non-emulsifier and resin curing agent, whereas phenolic resin may
be used as proppants, biocides, base fluids and to clean perforations. Other phenols that may
potentially be used in hydraulic fracturing fluid include bisphenol A, 2,4-dimethylphenol,
2-methylphenol (o-cresol), alkylphenol ethoxylates, butylphenol and octylphenol (USEPA, 2015b;
Waxman et al., 2011; Spellman, 2013).
Phenolic materials are one of the major organic contaminants associated with UCG (Campbell et al.,
1978). The following phenols are the liquid by-products of UCG: 2,3-dimethylphenol, 2,4-
dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethyl-phenol, 3,5-dimethylphenol,
2-methylphenol (o-cresol), 3-methylphenol (m-cresol), 4-methylphenol (p-cresol). These phenols are
recovered from the aqueous phase by solvent extraction (Weber and Weber, 2010). These phenols
would not naturally occur in shale produced water, and are therefore not necessary to analyse for in
groundwater baseline establishment projects for hydraulic fracturing operations, but are critical for
UCG projects.
The rationale s for sampling and analysing for phenols

Phenols are naturally occurring compounds that are found in coal and petroleum products, and
are formed by natural degradation of organic material and benzene (Michaowicz and Duda, 2007;
Schobert and Song, 2002).
Phenols are produced liquid by-products of UCG which may contaminate the groundwater
(Kapusta et al., 2013).
Phenols, together with BTEXs, are the most common organic contaminants in produced water
from oil and natural gas production projects, with a range of 0.00923 mg/l (Benko and Drewes,
2008).
O-cresol is considered a useful monitoring compound at UCG operations (LIU et al., 2007).
The phenols presented in Table 3.20 are suggested to be sampled and analysed for during
groundwater baseline establishment for hydraulic fracturing and UCG projects.
171
TABLE 3.20: LIST OF SUGGESTED PHENOLS TO BE ANALYSED FOR
Phenol TWQR / MCL (mg/l)
2,3-Dimethylphenol (2,3-Xylenol) 1.0

2,4-Dichlorophenol *0.07
2,6-Dichlorophenol 1.0
2,4-Dimethylphenol (2,4 Xylenol) 1.0

2-Methylphenol (o-Cresol) 1.0

3-Methylphenol (m-Cresol) 1.0
4-Methylphenol (p-Cresol) 1.0
Alkylphenol ethoxylates 1.0
Butylphenol 1.0
Hydroxybenzene 1.0
Methoxy-methylphenol 1.0
Nonyl phenol ethoxylate 1.0
Nonylphenols 1.0
Octylphenol 1.0
p-tert-butyl-phenol 1.0
Tert-butyl-phenol 1.0
Trichlorophenol 1.0
Note:
T o t a l p e t ro l e u m h y d ro c ar b o n s ( T P H s )
TPH refers to a large family of several hundred chemical compounds which originate from crude oil.
These compounds may include petrol, diesel fuel, paraffin, napthas, fuel oils, lubricant oils, aviation
gasoline and jet fuels. Petroleum and petroleum-derived products are a complex mixture of
hydrocarbons, plus other additives such as sulphur and nitrogen, and may range from very volatile C4
up to the heavy end C45+ (Weaver, 1953).
There are many analytical techniques which measure TPH concentrations in the environment, but
there is no single method that can measure the entire range (C1 C45+) (Weaver et al., 2007). Therefore,
it is suggested to analyse for the gasoline range (C6 C10 ), diesel range (C10 C28 ) and heavier range (C28 -
C45 ) organics. This analysis will provide a measurement for the light, intermediate and heavy end
hydrocarbons, it will include additional SVOCs, VOCs, oil and grease, and petroleum compounds not
suggested for sampling and analysis.
172
The rationale s for sampling and analysing for TPHs
Petroleum hydrocarbons occur in coal and shale produced water (Orem et al., 2014).
Petroleum hydrocarbons may be used in drilling fluid.
Surface spills of hydrocarbons may occur at UCG and hydraulic fracturing operations.
Petroleum hydrocarbons may be used in hydraulic fracturing fluid (DiGiulio et al., 2011).
The TPHs presented in Table 3.21 are suggested to be sampled and analysed for during groundwater
TABLE 3.21: RANGE OF TOTAL PETROLEUM HYDROCARBON TO BE ANALYSED FOR

TPH (C6-C45) NG
Note:
3.9.4.2 Rationale for sampling and analysis of field parameters
The purposes of collecting field measurements are the following:
To provide checks on laboratory data. Disagreement between field and laboratory data may
indicate erroneous field measurements or erroneous laboratory results, bad handling of samples
or mislabelling of samples. Agreement between field and laboratory measurements raises the
confidence in the data.
Certain parameters such as temperature or pH may change from the field to the laboratory.
Some of the analytes are physically or chemically unstable, and should be measured in the field,
such as pH, temperature and dissolved oxygen.
Provide immediate in-field information on water quality.
To check purging efficiency (Cheung and Mayer, 2009; COGA, 2011; Mazor, 2003; Weaver et al.,
2007).
The field parameters presented in Table 3.22 are suggested to be collected during groundwater
TABLE 3.22: SUGGESTED FIELD MEASUREMENTS

Parameter
pH
Electrical conductivity (EC) (mS/m)
Temperature C
Alkalinity (total, bicarbonate, and carbonate; as CaCO 3) (mg/l)
Dissolved oxygen (DO) (mg/l)
Redox potential (Eh) or oxidation-reduction potential (ORP)
173
3.9.4.2.1 pH
pH is used as an indicator for stability during borehole purging (Nielsen and Nielsen, 2006; Weaver
et al., 2007; Weight and Sonderegger, 2001; Wilde et al., 2005).
To compare field and laboratory pH measurements. Agreement between the two values indicates
that no secondary reaction, such as the loss of CO2 or biological activity, has occurred in the sample
bottle. If there is an agreement between the two values, it also indicates that the water chemistry
measurements in the laboratory are relevant to the water in the field. Deviations between these
two values may indicate that one of the measurements is wrong or that secondary reactions took
place. In such a case the sample preservation technique needs to be checked and improved, and
the sample holding time has to be shortened. Disagreement places a question mark on the
reported concentrations of biologically involved ions such as ammonium, sulphate, calcium,
bicarbonate and hydrogen (Mazor, 2003).
pH can be used to determine the concentration of carbonate and bicarbonate from the alkalinity
(Fetter and Willard, 2001).
The in situ pH is essential to reconstruct the potential mobility of constituents (Weaver et al.,
2007).
It is required for water-rock equilibrium calculations (Mazor, 2003).
Groundwater pH can increase or decrease due to unconventional gas operations (Ahern and
Frazier, 1982).
3.9.4.2.2 Electrical conductivity (EC)
EC is used as an indicator for stability during borehole purging (Nielsen and Nielsen, 2006; Weaver
Field EC concentration values should be plotted against laboratory TDS concentration values. If a
good correlation exists, it would indicate high quality data (Mazor, 2003).
EC depth profiles of non-pumped boreholes can be used to detect different water strata (Mazor,
2003).
Continuous monitoring in monitoring boreholes can be used to detect the arrival of contaminated
flowback or produced from unconventional gas projects (Mazor, 2003; Weaver et al., 2007).
EC values may change due to unconventional gas activities (Ahern and Frazier, 1982).
174
3.9.4.2.3 Redox potential (Eh)
Eh is used as an indicator for stability during borehole purging (Brassington, 2007; Weaver et al.,
2007; Wilde et al., 2005; Younger, 2009).
May be used to indicate the type of aquifer, for example, oxidising or reducing (Edmunds and
Shand, 2008; Weaver et al., 2007).
Knowledge of the in situ Eh is essential to evaluate the mobility of pollutants in the subsurface. An
EhpH diagram can be used for predictions on whether a species is mobile in an aquifer. This
requires accurate pH, temperature, and Eh measurements and therefore require field pH
measurements because pH measurements done in the laboratory a few days later may be
erroneous (Weaver et al., 2007).
Together with pH, Eh can be used to delineate contaminant plumes which have strong redox
gradients (Weaver et al., 2007).
3.9.4.2.4 Temperature (C)
Temperature is used as an indicator for stability during borehole purging (Nielsen and Nielsen,
2006; Wilde et al., 2005).
To better understand the groundwater system and to identify groundwater groups (Mazor, 2003).
It is required for waterrock equilibrium calculations (Mazor, 2003).
It can be used to determine the depth of groundwater circulation (Mazor, 2003).
It can be used to indicate mixing between different water sources. This, together with isotopic
measurements, are useful indicators of groundwater mixing which may be caused by
unconventional gas projects (Mazor, 2003; Moore, 2011).
Temperature has a strong effect on pH, for example, neutral pH at 30 C is not 7.0 but actually
6.82 (Wilde et al., 2005).
3.9.4.2.5 Dissolved oxygen (DO)
DO is used as an indicator for stability during borehole purging (Nielsen and Nielsen, 2006; Weaver
et al., 2007; Wilde et al., 2005).
A decrease in groundwater oxygen may indicate an increase in biological activity connected to the
arrival of polluting fluids (Mazor, 2003). Therefore, by measuring the DO of different
hydrostratigraphic groups and establishing ranges during the baseline establishment phase,
potential contamination due to unconventional gas activities can be determined during
monitoring.
175
The dissolved oxygen concentration is an indicator of the balance between oxygen-depleting and
oxygen-producing processes at the moment of sampling (Hem, 1985; Senior, 2014).
Can be used to determine the degree of aerobic/anaerobic conditions of an aquifer (Mazor, 2003).
Can be used to identify different water strata in depth profiles (Mazor, 2003).
Can be used to identify confined and unconfined aquifers during depth profiling, as confined
aquifers with old water likely have low oxygen concentrations, if no or limited mixing between
different aquifers occurs, due to oxygen consumption (Mazor, 2003).
Can be used to determine if mixing of different water types/sources occurred, through the
occurrence of oxygen together with hydrogen sulphide (Mazor, 2003; Vidic et al., 2013; Younger,
2009).
3.9.4.2.6 Alkalinity
Alkalinity has to be measured in the field, as CO2 is pressurised in groundwater, and upon exposure
to the atmosphere, some of the CO2 leaves the water which causes part of the HCO3 to break down
and could cause precipitation of carbonates, which would result in lower alkalinity than actually
found in the formation water (Mazor, 2003; Weaver et al., 2007; Weight and Sonderegger, 2001;
Younger, 2009).
Field measured alkalinity measurements are needed for the waterrock saturation calculations
(Mazor, 2003).
Alkalinity values have to have a positive correlation with the pH values; if not, it could indicate
faulty or inaccurate equipment used (Senior, 2014; Sloto, 2013).
3.9.4.3 Rationale for sampling and analysis of physical characteristics in the laboratory
The physical characteristics presented in Table 3.23 are suggested to be analysed for in the laboratory
during groundwater baseline establishment for hydraulic fracturing and UCG projects.
TABLE 3.23: SUGGESTED PHYSICAL CHARACTERISTICS TO BE ANALYSED FOR
Parameters
pH
Total dissolved solids (mg/l)
3.9.4.3.1 pH
pH is used as an indicator for stability during borehole purging (Nielsen and Nielsen, 2006; Weaver
176
To compare field and laboratory pH measurements. Agreement between the two values indicates
that no secondary reaction, such as the loss of CO2 or biological activity, has occurred in the sample
bottle. If there is an agreement between the two values, it also indicates that the water chemistry
measurements in the laboratory is relevant to the water in the field. Deviations between these
two values may indicate that one of the measurements is wrong or that secondary reactions took
place. In such a case, the sample preservation technique has to be checked and improved, and the
sample holding time has to be shortened. Disagreement places a question mark on the reported
concentrations of biologically involved ions such as ammonium, sulphate, calcium, bicarbonate
and hydrogen (Mazor, 2003).
pH can be used to determine the concentration of carbonate and bicarbonate from the alkalinity
(Fetter and Willard, 2001).
The in situ pH is essential to reconstruct the potential mobility of constituents (Weaver et al.,
2007).
It is required for waterrock equilibrium calculations (Mazor, 2003).
Groundwater pH can increase or decrease due to unconventional gas operations (Ahern and
Frazier, 1982).
3.9.4.3.2 Total dissolved solids (TDS)
Field EC concentration values should be plotted against laboratory TDS concentration values. If a
good correlation exists, it would indicate high quality data (Mazor, 2003).
TDS should be measured in the laboratory and not in the field, as the field measurements are only
an estimate made from the EC reading.
TDS provides the degree of water mineralisation (Younger, 2009).
See also Sub-section 3.9.4.2.2 for EC.
3.9.5 Selecting the sampling devices and sampling methods

After determining the chemical parameters to analyse for, the preferred sampling device needs to be
selected/determined. For the purpose of collecting the most representative samples possible, the
proper sampling device should be selected. If inappropriate sampling devices are chosen, it could have
significant negative long-lasting results, which may not be immediately apparent.
In order to collect representative samples, the sampling device should be capable of moving the
groundwater from the in situ conditions to the surface by causing the least impact on the physical and
chemical properties of the sample (for example, accuracy) in addition, the sampling device should be
used by different sampling team members during different sampling events and provide data which
177
can be compared to previous and subsequent sampling data (namely, precision) (Hudak, 2004; Nielsen
and Nielsen, 2006; Sundaram et al., 2009).
In some situations, it may not be feasible to use the sampling device which will provide the most
representative results. This may be due to financial constraints, unavailability of the device, or physical
constraints which prevent the utilisation of a specific device. In this section, the preferred and
alternative sampling devices for each chemical group, for example, major ions and dissolved gases, for
both shallow (0300 m) and deep (300>1 000 m) boreholes will be discussed. The selected
groundwater sampling devices are according to industry best practices referenced from books, reports
and manuals which cover the wide topic of groundwater sampling.
The sampling and purging devices chosen should be site-specific. Each sampling device has its own
unique set of advantages and limitations which should be taken into account when selecting the
sampling device for groundwater baseline establishment (Nielsen and Nielsen, 2006; Sundaram et al.,
2009).
The recommended sampling devices that will be suggested are based on the following assumptions:
The boreholes are dedicated boreholes (drilled into specific hydrostratigraphic units with the
overlying units cased off from the unit of interest).
The boreholes tap each hydrostratigraphic unit from the surface down to the production zone (0
3 000 m).
The minimum diameter of the boreholes is 75 mm.
The boreholes do not have production pumps installed.
Some of the criteria that need to be taken into account when selecting a sampling device includes
accuracy and precision of samples, flow-rate, lift capability, materials of construction of the device,
ease of operation, ease of decontamination, reliability and durability, portable versus dedicated
applications, price, and operating costs (Nielsen and Nielsen, 2006).
Note that the selected devices are suggestions on collecting representative groundwater samples. It
is therefore recommended to first consult the analytical laboratory tasked with analysing the samples,
before going to the field to confirm the methodology required by the laboratory. The sampling
procedures used should follow international protocols but should be modified for local conditions
(Edmunds and Shand, 2008).
178
3.9.5.1 Field determination
Field determination is required for parameters which do not store well, such as pH, temperature, and
alkalinity. These parameters should ideally be determined in the field during purging to check purging
efficiency if purging is required (Barcelona et al., 1985).
Table 3.24 presents the devices which are suggested to be used to collect representative field
parameters.
TABLE 3.24: P ARAMETERS THAT NEED TO BE TESTED IN THE FIELD
Parameter Device
Flow through cell or
pH
potentiometer
Electrical conductivity (EC) (mS/m) Flow through cell or EC meter
Flow through cell or
Temperature (C)
thermometer
Alkalinity (total, bicarbonate, and carbonate; as CaCO 3) (mg/l) Titration method
Dissolved oxygen (DO) (mg/l) Flow through cell or DO meter
Redox potential (Eh) or oxidation-reduction potential (ORP) Flow through cell

Source: from Weaver et al., 2007
3.9.5.2 Sampling devices
The following sampling devices are recommended to be used to collect samples at shallow (0300 m)
and deep (300>1 000 m) depths for the different chemical groups listed in Section 3.9.4.
3.9.5.2.1 Sampling devices (0 to 300 m)
D e d i c a te d p o s i t i ve d i s p l a ce m en t b l a d d er p u m p s
It is recommended to use dedicated positive displacement bladder pumps installed into different
boreholes tapping different hydrostratigraphic units, with hydrogeologic yield capabilities of the unit
exceeding 100 ml/min, to collect representative samples for major ions, trace metals, dissolved gases,
dissolved stable isotopes, radioactive isotopes and organic analysis (Barcelona et al., 1985; Nielsen
and Nielsen, 2006; Sundaram et al., 2009).
Positive displacement bladder pumps are the most reliable sampling mechanism for all chemical
parameters since they are simple in design and operation; they cause minimal chemical and physical
disturbance of the samples at low flow rates; they permit efficient in-line filtration of samples; and
the operational variables are easily controlled.
Positive displacement bladder pumps can easily be disassembled for cleaning and repairs in the field
and reassembly in the field. Furthermore, the bladder pump with all of its accessories (pulse controller,
179
air lines) price about R18 000 (Barcelona et al., 1985; Nielsen and Nielsen, 2006; Pohlmann et al., 1988;
Weaver et al., 2007).
Another key reason for suggesting bladder pumps for groundwater sampling is because they are able
to collect representative samples for dissolved gases and volatile organic compounds, which are the
most troublesome parameters to sample (Barcelona et al., 1985).
According to Nielsen and Nielsen (2006), dedicated bladder pumps should be installed into boreholes
tapping shallow (0300 m) hydrostratigraphic units for more than six sampling events. Further, it is
suggested that bladder pumps should be used for low-flow sampling (100 ml/min), where the
borehole is not purged before sampling, if it is found that purging is not required, see Sub-section
3.9.10.1.2.
Pumping rates should be no more than 100 ml/min. This is done to collect representative samples for
volatile organics and gas-sensitive parameters (Barcelona et al., 1985).
It may be expensive to install dedicated sampling equipment into each shallow borehole, but cost
saving will be realised through lowered operating costs associated with equipment setup and
decontamination, and collection of fewer quality control (equipment blanks) samples. Furthermore,
by installing dedicated sampling equipment, the equipment is not exposed to atmospheric conditions,
cross-contamination of different sampling points is virtually eliminated and most importantly, there is
no agitation of the water column associated with equipment deployment to collect the sample at the
sampling point (resulting in more representative samples) (Nielsen and Nielsen, 2006).
When sampling for radioactive isotopes, Weaver et al. (2007) advised to first consult the analytical
laboratory for their recommended sampling procedure and their required containers, preservation
and reagents. Weaver et al. (2007) further suggested that if, for some reason, a dedicated bladder
pump cannot be used to collect samples for SVOCs, PAHs, phenols and petroleum hydrocarbons
analysis, a submersible centrifugal pump can be used to collect representative samples for these
compounds. This is because there is less danger of volatilisation when sampling for these organic
compounds than for VOCs. It should be noted that positive displacement bladder pumps can only be
used effectively at a maximum depth of 305 mbgl (Nielsen and Nielsen, 2006).
D e d i c a te d p i s t o n p u mp s
Alternatively, dedicated piston pumps can be installed into different boreholes tapping different
hydrostratigraphic units, with hydrogeologic yield capabilities of the unit exceeding 100 ml/min, to
collect representative samples for major ions, trace metals, dissolved gases, dissolved stable isotopes,
radioactive isotopes and organic analysis (Barcelona et al., 1985; Nielsen and Nielsen, 2006; Weaver
180
et al., 2007). Similar to dedicated bladder pumps, installing dedicated pumps would reduce operating
costs.
The reason bladder pumps are preferred above piston pumps is because piston pumps are more
expensive than bladder pumps and piston pumps may cause pressure changes which may make it
unsuitable to collect representative samples for dissolved gas and volatile analysis (Barcelona et al.,
1983).
Nielsen and Nielsen (2006) and Barcelona et al. (1985) argued that piston pumps may be an even
better choice for sampling dissolved gases than bladder pumps, as piston pumps can deliver samples
at a controlled flow rate and are constructed of inert materials. Furthermore, Sundaram et al. (2009)
reported that dedicated piston pumps can be used to collect representative samples of all chemical
constituents up to 900 m or more.
Another advantage of using dedicated bladder and piston pumps is that they can be reliably used for
long-term monitoring after the baseline samples have been collected.
When sampling for VOCs, passive diffusion bags (PDBs) can also be used to collect representative
samples for specific VOCs. A PDB is a low density polyethylene lay-flat tube (Nielsen and Nielsen,
2006).
3.9.5.2.2 Sampling devices (300 to >1 000 m)
S y r i n ge s a m p l er s
Dedicated piston pumps can be used to collect representative samples from hydrostratigraphic units
as deep as 900 m. For deeper boreholes it is recommended to use syringe samplers to collect
representative samples for major ions, trace metals, dissolved gases, dissolved stable isotopes,
radioactive isotopes and organic analysis (Barcelona et al., 1989; Nielsen and Nielsen, 2006; Pohlmann
et al., 1988; Sundaram et al., 2009).
Syringe samplers are designed to capture and preserve in situ groundwater conditions by preventing
sample aeration and pressure changes due to degassing of volatile compounds or outgassing of
inorganic gases (Wilde et al., 2005). One major advantage of using syringe samplers is that the syringe
can be used as the sample container, which completely prevent degassing and aeration of the sample
(Nielsen and Nielsen, 2006). If the sample needs to be filtered, the one-minute time span exposure to
oxygen should not cause any discernible bias (Weaver et al., 2007). One of the major drawbacks of
using a syringe sampler for sampling, however, is that it is impractical to use for purging.
181
G r a b s a m p l i n g d e vi ce s
Alternatively, grab sampling devices such as duel check valve bailers, thief samplers (such as
Kemmerer) can be used to collect samples for major ions, trace metals, dissolved stable isotopes,
radioactive isotopes and organic analysis if the borehole has been adequately purged before sampling
and the hydrogeologic yield capabilities of the unit is less than 100 ml/min (Barcelona et al., 1985;
Nielsen and Nielsen, 2006). If it has been determined that purging is not required, dual check valve
bailers, thief samplers can be used without purging the borehole.
Barcelona et al. (1985) did not recommend using any type of grab sampler to sample for dissolved
gases at great depths, but suggested that thief or dual valve bailers may be used to collect adequately
representative samples. There are a number of different unconventional sampling devices used to
sample for dissolved gases at shallow and deep groundwater depths. These devices are, however, not
commonly used, and the limitations are not well-known. Furthermore, these devices may not be
available in South Africa, and may be too expensive to use. For more information on these sampling
devices, refer to Gascoyne (2002).
Furthermore, thief and duel check valve samplers can also be used to sample for VOCs (Pohlmann
et al., 1988). Bailers are not generally recommended for sampling organic compounds and air-
sensitive compounds; however, they may be the only feasible sampling option for sampling
groundwater at great depth. When using a bailer to collect samples, it is recommended to use
fluorocarbon polymer (TeflonTM) bailers when sampling for both organic and inorganic analytes.
C o m m e n ts
The sampling device and construction materials used to collect the groundwater samples need to be
chosen with great care. The device should not introduce any bias due to its construction materials,
pumping or collection method as many organic compounds are undesirable at even low
concentrations, such as chloroform with a maximum drinking water level of 0.1 mg/l (Weaver et al.,
2007).
The preferred materials of the pump accessories that come into contact with the collected water, in
order of preference, are TeflonTM, stainless steel, and polyethylene (Barcelona et al., 1985).
The preferred materials of the grab sampler which come into contact with the collected water, in
order of preference, are TeflonTM, stainless steel, and borosilicate glass (Barcelona et al., 1985). When
using bailer, thief, and syringe samplers, it is recommended to use a new device for each borehole. If
not feasible, the device should be thoroughly cleaned and decontaminated before reuse.
182
3.9.5.3 Sampling methods
The suggested sampling methods presented in Table 3.25 for the different chemical groups listed in
Section 3.9.4, are general practices from the literature reviewed.
The selected laboratory(s) which will conduct the chemical analysis should first be consulted before
selecting a sampling method for a specific chemical group, as the laboratory(s) may have their own
recommended methodology and procedures for sampling a specific group or parameter with regard
to sample collection procedures into the sample bottle, the type of container and material, the volume
required, preservation, filtration, storage, and holding times.
For more detailed sampling methods, procedures, and requirements, refer to Sundaram et al. (2009)
and Weaver et al. (2007).
183
TABLE 3.25: SUGGESTED SAMPLING METHODS AND PROCEDURES FOR THE DIFFERENT CHEMICAL GROUPS SUGGESTED TO BE ANALYSED FOR GROUNDWATER BASELINE
ESTABLISHMENT FOR UNCONVENTIONAL GAS PROJECTS
Sample collection procedure into
Parameter Filter Container Volume Sample preservation Storage Holding time
the sample bottles
Major ions
Major ions During sample collection, disposable Filtering is not required if the bore- Major ions can be Depends on the According to Weaver Stored in a cooler box The holding time
polyethylene gloves should be worn hole has been successfully purged (if collected in TeflonTM, selected laboratory(s) et al. (2007), sample or refrigerated at depends on the
by the sampler to prevent cross- it has been determined that purging plastic and glass and the analytical preservation is not ideally 4 C9 (Barcelona laboratory that will
contamination (Weaver et al., 2007). is required, see Sub-section sample bottles. method used required for major ions, et al., 1985; Weaver et analyse the samples
3.9.10.1.2.) before the samples were, TeflonTM and plastic (Barcelona et al., 1985; except for ammonium al., 2007). (Barcelona et al., 1985).
Rinse new bottles, including the cap,
three times with the sampled water taken except for phosphate which bottles are a better Weaver et al., 2007). and nitrate. The general holding
requires on-site filtration7 (Weaver et choice as glass can
before collecting the sample from The general minimum Ammonium and nitrate time for major ions is
al., 2007). break 8 (Weaver et al.,
the sampling device outlet/hose. If volume for major ions samples should be between 24 hours and
If the borehole has not been 2007).
reusing old bottles, pre-rinse the is between 50 ml acidified with analytical 6 months (Barcelona
bottles with diluted hydrochloric acid successfully purged, or no purging and400 ml (Barcelona grade H2SO 4 to a pH of et al., 1985; Johnston,
has been conducted, filtration is
and soak the bottles for a couple of et al., 1985; Johnston, <2 (Barcelona et al., 2007; Weaver et al.,
required. In such circumstances,
days in deionised water (Weaver 2007). 1985; Weaver et al., 2007).
filtration needs to be conducted in
et al., 2007). 2007). Furthermore,
the field as soon as possible after Barcelona et al. (1985)
The rate of flow for filling the sample collection (Barcelona et al., 1985).
suggested that samples
bottles with a pump should not
Barcelona et al. (1985) suggested for major cations are
exceed 500 ml/min for 250 ml bottles
that an in-line filtration module be preserved by field
or greater in volume (Wilde et al.,
used which is attached to the acidifying the samples
2005).
sampling pump and relies on the to a pH of <2 with
sampling pump pressure for its HNO 3.
operation. It is also suggested to use
a TeflonTM filter medium; glass fibres
are also appropriate. Furthermore,
the suggested nominal size of the
screen filter is a 0.45 M.
When using a syringe to filter the
samples it is suggested to use
disposable disk filters (with
polyester-reinforced polysulfone) or
disposable capsule filters (with
acrylic copolymer) (Wilde et al.,
2005).
7 Fluoride requires no filtration or preservation (Weaver et al., 2007).

8 Glass sample bottles cannot be used for sodium analysis (Weaver et al., 2007).
9 This is done to minimise the chemical alteration of samples before analysis.
184
the sample bottles
Trace metals
Trace metals Rinse new bottles, including the cap, Similar to filtering for major ions. Similar to containers The minimum sampling According to Weaver Similar to storage The general holding
three times with the sampled water. required for major volume is generally 100 et al. (2007), sample required for major ions. time for trace metals is
Filtration is required even if purging
If reusing old bottles, the bottles ions11. ml (Cheung and Mayer, preservation is one month, except for
has not been conducted (Barcelona
should be acid washed in advance to 2009; Johnston, 2007). required for trace iron which has a
et al., 1985).
prevent the solution of previously metals to keep the holding time of 24
precipitated metals such as Fe and metals in solution. hours (Barcelona et al.,
Mn (Weaver et al., 2007). Analytical grade nitric 1985; Johnston, 2007).
acid should be added
It is recommended to use a
to the sample bottle
processing chamber filled with inert
before filtering the
gas10. The sample bottle should be
water into the sample
filled from the bottom of the sample
bottle.
bottle up to overflowing using clean
sample tubing from the pump (Wilde Some laboratories
et al., 2005). It is crucial to fill the prefer that the samples
container completely to exclude air are not acidified in the
(Johnston, 2007). field, but rather in the
laboratory. Therefore,
The rate of flow for filling the sample
whether acidification of
bottles with a pump should not
samples should be
exceed 500 ml/min for 250 ml bottles
conducted in the field
or greater in volume (Wilde et al.,
or in the laboratory, it
2005).
should be confirmed
with the selected
laboratory.
Dissolved gases
Dissolved When collecting samples for Filtration is not required for sampling Borosilicate glass or The general sampling Preservation is Similar to storage 14 days (Cheung and
gases dissolved gases, it is also dissolved gases (Cheung and Mayer, stainless steel volume is 45 ml for generally not required required for major ions. Mayer, 2009).
recommended to use a processing 2009; Sundaram et al., 2009; Weaver (Barcelona et al., 1985). dissolved gases for sampling dissolved
chamber filled with inert gas. et al., 2007). (Barcelona et al., 1985). gases (Weaver et al.,
2007).
The sample collection procedure for
collecting dissolved gases as
described by Sundaram et al. (2009),
can be followed. The procedure aims
at preventing air contamination,
which is of utmost importance when
sampling for noble gases, as a single
bubble of air present in the collected
10 When groundwater is brought to the surface, it should undergo minimum exposure to the atmosphere as CO2 and aeration occur, which cause the pH to rise, and the Eh may tend towards oxidising
conditions which may cause the valence state of some metals to change to less solub le phases causing the metals to precipitate onto the sample bottle. Therefore , it is recommended to use a
processing chamber for sampling, to prevent aeration (Wilde et al., 2005).
11 Glass sample bottles should not be used for boron analysis (Barcelona et al., 1985; Weaver et al., 2007).
185
the sample bottles
sample may contain more noble
gases than the entire sample (Mazor,
2003).
Furthermore, the sample bottle has
to be kept well-closed to prevent any
evaporation and the rate of flow for
filling the sample bottles with a
pump should not exceed 500 ml/min
for 250 ml bottles or greater in
volume (Mazor, 2003; Wilde et al.,
2005).
Dissolved stable Isotopes
Dissolved Similar sampling procedure into the Filtration is not required for sampling Borosilicate glass or The general sampling Depends on the type of Similar to storage The holding time for
stable sample bottle as for dissolved dissolved stable isotopes13 stainless steel volume is between isotope. Generally, no required for major ions. different stable
isotopes gases12. (Sundaram et al., 2009; Weaver et (Barcelona et al., 1985) 50 ml and 3 l for preservation is isotopes is highly
al., 2007). or a McCartney glass dissolved stable required but it is variable but it is
bottle (Sundaram et al., isotopes (Mazor, 2003; recommended to generally between 90
2009). Sundaram et al., 2009). consult the laboratory days and one year
for guidance (Cheung and Mayer,
It is recommended to Sampling for 14C
(Sundaram et al., 2009).
consult the laboratory requires about 4060 l,
2009).
for guidance as depending on the
specialised containers alkalinity of the water
may be required and the analytical
(COGA, 2011). method used
(Sundaram et al.,
2009).
Gross alpha Similar sampling procedure into the No need to filter (Johnston, 2007), The sampling The general sampling The sample should be Similar to storage The general holding
and gross beta sample bottle as for major ions, especially in the case of radon containers for volume is 1 l for acidified to pH <2 with required for major ions. time for gross alpha
except for radon which requires a (Weaver et al., 2007). radioactive isotopes radioactive isotopes nitric acid (Johnston, and gross beta samples
similar sampling procedure into the are usually glass or (Nielsen and Nielsen, 2007). is 6 to12 months
sample bottle as for dissolved gases plastic which needs to 2006). (Johnston, 2007;
(Sundaram et al., 2009). be acid washed before Nielsen and Nielsen,
sample collection 2006; Weaver et al.,
(Johnston, 2007; 2007).
Weaver et al., 2007).
Organics
12 It is important that there are no air bubbles in the sample bottle (Sundaram et al., 2009).
13 Filtration may be required when sampling for stable isotopes of sulphur and oxygen in sulphate (Sundaram et al., 2009).
186
the sample bottles
Organics in Similar sampling procedure into the Filtration is not recommended for Amber or brown glass The required sample Generally, no sample Similar to storage The general holding
general sample bottle as for dissolved gases. organic compounds as the increased bottles should be used volume depends on the preservation is required for major ions. time for organic
handling required during filtering to reduce UV compound and thus required when compounds is less than
Additionally, care should be taken
may result in the loss of chemical degradation. Ideally, the analytical method sampling for organic 24 hours (Barcelona et
when sampling, handling and
constituents (Barcelona et al., 1985). TeflonTM-lined bottle used, but it generally compounds (Johnston, al., 1985).
transporting organic compounds as
caps should be used. varies between 25 ml 2007).
organic compounds may be toxic or
Alternatively, TeflonTM- and 2 l (Barcelona
pose a threat to human health at
coated fibreglass et al., 1985).
very low concentrations (Weaver
sheets can be used by
et al., 2007).
placing cut sheets over
The rate of flow for filling the sample the mouth of the bottle
bottles with a pump should not and cap, before
exceed 150 ml/min for 40 ml VOC screwing the cap on
vials and should not exceed 500 (Weaver et al., 2007).
mL/min for bottles 250 ml or greater
(Wilde et al., 2005).
VOCs Similar sampling procedure into the Filtration is not required (COGA, Amber glass with Generally, a sample The sample should be Similar to storage The general holding
sample bottle as for organics in 2011). TeflonTM cap-liners volume of 120 ml is acidified to a pH<2 with required for major ions. time is less than 14
general. (Weaver et al., 2007). sufficient (Cheung and hydrochloric acid days (COGA, 2011;
Mayer, 2009). (COGA, 2011). Weaver et al., 2007).
SVOCs Similar sampling procedure into the Filtration is not required (Johnston, Amber glass with Generally, a 1 l sample No preservation is Similar to storage 7 days (40 days
sample bottle as for organics in 2007). TeflonTM cap-liners volume is sufficient required (Weaver required for major ions. extracted) (Weaver
general. (Weaver et al., 2007). (Weaver et al., 2007). et al., 2007). et al., 2007).
PAHs Similar sampling procedure into the Filtration is not required (Johnston, Amber glass with Generally, 500 No preservation is Similar to storage 24 hours to 7 days
sample bottle as for organics in 2007). TeflonTM cap-liners 1 000 ml (Johnston, required (Weaver required for major ions. depending on the
general. Additionally, do not (Weaver et al., 2007). 2007) (Cheung and et al., 2007). specific PAH (Cheung
completely fill the container and do Mayer, 2009). and Mayer, 2009;
not pre-rinse the container Weaver et al., 2007).
(Johnston, 2007).
Phenols Similar sampling procedure into the Filtration is not required (Johnston, Teflon or amber glass Generally, between Analytical grade H2SO 4 Similar to storage 24 hours to 28 days
sample bottle as for organics in 2007). (Nielsen and Nielsen, 30 ml and 1 000 m or H3PO 4 to pH of <4 required for major ions. (Johnston, 2007;
general. Additionally, do not 2006; Weaver et al., (Cheung and Mayer, (Barcelona et al., 1985; Weaver et al., 2007).
completely fill the container and do 2007). 2009; Johnston, 2007). Nielsen and Nielsen,
not pre-rinse the container 2006).
(Johnston, 2007).
Petroleum Similar sampling procedure into the Filtration is not required (Johnston, Amber glass with Generally, 1 l sample Add 5 ml 50% HCl Similar to storage The general holding
hydrocarbons sample bottle as for organics in 2007). Teflon cap-liners volume is sufficient (Weaver, 1953). required for major ions. time is less than 28
general. (Weaver et al., 2007). (Weaver et al., 2007). days (Weaver et al.,
2007).
Other
Silica Similar sampling procedure into the Similar to filtering for major ions. Plastic Nalgene bottles Generally, 125 ml Similar preservation Similar to storage The general holding
sample bottle as for major ions. (Cheung and Mayer, (Cheung and Mayer, required for major ions. required for major ions. time: less than 28 days
2009). 2009). (Weaver et al., 2007).
187
3.9.6 Selecting boreholes for sampling
The following is a list of considerations which should be taken into account when selecting boreholes
for groundwater sampling for local and regional scale studies. These considerations are from practices
and suggestions made in reports and manuals on groundwater baseline studies and contamination
investigations for unconventional gas projects; and groundwater sampling manuals. Refer to Section
3.8.2 for some additional suggestions on selecting boreholes for groundwater sampling.
Before selecting a borehole for sampling, the owner of the borehole should be contacted to
explain the purpose and procedure of the sampling event and ask for permission to sample the
borehole, and also for permission to bypass any filtering systems installed on the borehole. If
permission is not granted to bypass the filtering system the borehole should not be considered
for sampling (Fross and Lyle, 2013; Sloto, 2013).
When selecting boreholes for sampling it is necessary to be aware of the potential geological
preferential flow features which may serve as pathways for contamination migration towards
potential receptors, including potable groundwater bearing zones. The design of the baseline
sampling programme should be based on the geological pathways (and potential receptors).
These pathways should be identified in the geohydrological conceptual site model. These
geological features should be targeted as they may indicate contamination from unconventional
gas projects during monitoring (OBrien et al., 2013).
Boreholes completed in the different hydrostratigraphic units should be chosen, with the borehole
casing preventing groundwater mixing between different hydrostratigraphic units. This is done to
acquire spatially representative groundwater quality of hydrostratigraphic units throughout the
entire study area. When selecting boreholes for sampling, it is essential that these boreholes have
good supporting geological information and construction details, such as the depth of the casing
and screened interval(s) (Edmunds and Shand, 2008; Senior, 2014).
At least two boreholes should be completed in the coal or shale formation of interest to be able
to collect groundwater samples and to measure groundwater levels (Ahern and Frazier, 1982;
Scott et al., 2013).
Higher priority should be given to boreholes, ideally, domestic boreholes, with known
construction data close to the wellpad, if the location of the production well is known (Eckhardt
and Sloto, 2012; Sloto, 2014).
Domestic boreholes or boreholes drilled close to domestic boreholes to the same depth as the
domestic borehole (if the domestic boreholes are not constructed properly for groundwater
188
sampling) should have higher priority, as the groundwater baseline should be receptor focussed
(Fross and Lyle, 2013).
operations) is known, boreholes should be selected in a radial pattern with at least one borehole
up-gradient of the wellpad, with the majority of the boreholes down-gradient in the direction of
groundwater flow, if the groundwater flow direction can be calculated, is known, or can be
reasonably inferred (WOGCC, 2014).
A large number of boreholes distributed throughout the study area at different depths are
suggested to be selected to assess whether unconventional gas activities have an impact on
groundwater quality and whether there is a connection between shallow and deep groundwater
(Gradient, 2013).
In the case of regional studies, where the location of the wellpad and storage facilities are not
known, boreholes completed in the different hydrostratigraphic groups over the entire study area
should be selected. Higher priority should be given to boreholes completed in or near geological
features which may cause a damming effect of contaminants, such as dolerite dykes, and lower
priority should be given to boreholes completed in preferential flow features such as faults
If the location of the wellpad is known, the majority of the boreholes selected should be in the
direction of groundwater flow or inferred groundwater flow, in the direction of potential receptors
(COGA, 2011; Ziemkiewicz et al., 2013).
The borehole should have a diameter sufficient for the preferred sampling method if more than
one borehole fits the same criteria as the above-listed suggestions.
Furthermore, it is recommended that at least one borehole completed into each hydrostratigraphic
unit down-gradient of the wellpad in the direction of potential receptors is selected for sampling.
As mentioned previously, when selecting boreholes for sampling, it is necessary to be aware of the
fate and transport and physiochemical properties of specific chemicals when establishing a
methodology for establishing a groundwater baseline for hydraulic fracturing and UCG operations, as
it would aid in selecting which chemicals to sample for at a specific borehole (at a specific depth),
based on which chemicals one would expect to encounter at a specific point, depending on the fate
and transport and physiochemical properties of specific chemicals.
It is, however, outside of the scope of this dissertation to recommend which chemicals to sample for
at a specific distance and depth from the wellpad.
189
It is, therefore, recommended that future studies should be aimed at determining at which distance
and depth to sample for specific chemical constituents based on their physiochemical properties for
hydraulic fracturing and UCG operations.
3.9.7 Selecting the sampling frequency

The publicly available literature on determining the minimum sampling intervals which would lead to
statistical independence or zero autocorrelation between consecutive samples are only related to
long-term monitoring plan optimisation. The optimal sampling frequency for monitoring is
determined by using geostatistics based on kriging, statistics based on trends, and autocorrelation
(Ling et al., 2004). No literature could be found on determining an ideal sampling frequency for
baseline sampling campaigns. Therefore, the suggested sampling frequencies presented in this section
are based on suggestions from the literature reviewed.
To assess the natural groundwater system in an area involves collecting successive groundwater
samples at different sites. This data can be used to help identify the natural variations, temporally and
spatially, of a groundwater body and help identify the geochemical processes that control the water
quality, and to distinguish the source of any changes in the groundwater (OBrien et al., 2013). By
successively collecting water quality samples, natural quantity ranges of specific chemical constituents
can be established for different hydrostratigraphic units.
It is essential to establish baseline ranges for different chemical constituents from the
hydrostratigraphic units in the study area, as these ranges can be used to indicate if contamination
due to unconventional gas activities occurred after unconventional gas activities have taken place
The key question is, however: How frequently is sampling required to establish reasonable,
trustworthy ranges for the different hydrostratigraphic units? This is an important question as there
are many factors which must be taken into account when selecting a sampling frequency, for example,
a deep confined aquifer requires a lower sampling frequency than a near-surface unconfined aquifer.
This is because water quality in the deep confined aquifer changes much slower than a near-surface
unconfined aquifer (Edmunds and Shand, 2008).
The sampling frequency is a function of the following:
Nature of the groundwate r body confined, semi-confined or unconfined

An unconfined aquifer has a higher rate of temporal changes in water quality than a confined
aquifer as it is open to the atmosphere, and therefore require higher sampling frequencies than a
confined aquifer (Edmunds and Shand, 2008; Heath, 1983).
190
Hydraulic conductivity is also higher in unconfined aquifers than confined aquifers, and therefore
require higher sampling frequencies than a confined aquifer, because the higher the hydraulic
conductivity, the more waterrock interaction/reactions, such as diffusion, decay, and adsorption
would occur (Singhal and Gupta, 2010; Steyl et al., 2012).
Type of media fractured or porous

The hydraulic conductivity of fractured media are much higher than the hydraulic conductivity of
porous unfractured media, and therefore require higher sampling frequencies (Edmunds and
Shand, 2008; Heath, 1983; Van Tonder et al., 2013).
Seasonal influences climate change, change in vegetation, and land use

Different areas have different seasonal rain patterns, and therefore influence the water level and
water quality of near-surface aquifers at different times throughout the year due to recharge,
which means that in order to establish ranges for different chemical constituents in the study area,
samples will need to be collected during different seasons (Edmunds and Shand, 2008; Johnston,
2007; OBrien et al., 2013; Senior, 2014).
During different seasons, the land may be used for farming, which means water levels may fall
due to abstraction from boreholes used for irrigation of crops. The water quality may also change
due to the use of pesticides (Senior, 2014).
Financial resources for sampling and laboratory analysis

Depending on the budget for the baseline sampling and analysis process, there may be constraints
on the sampling frequency; therefore, a sampling frequency has to be chosen by taking the project
budget into account (Edmunds and Shand, 2008).
The sampling frequencies presented in Table 3.26 are suggested or followed by different literature
reviewed. The literature reviewed focused on establishing groundwater baseline conditions for
unconventional gas projects and typical groundwater baseline establishment projects.
191
TABLE 3.26: SAMPLING FREQUENCIES SUGGESTED AND/OR PRACTICED IN THE LITERATURE REVIEWED
Confined Unconfined
Confined porous Unconfined
Reference Type of work fractured fractured
aquifer porous aquifer
aquifer aquifer
Edmunds and Book on natural Once every six Several times a Several times a
Shand (2008) groundwater years year year
quality
Singhal and Book on applied Once during Once during Once during Once during
Gupta (2010) geohydrology of rainy season and rainy season and rainy season and rainy season and
fractured rocks once during dry once during dry once during dry once during dry
season season season season
Brassington Book on Once a year Once a year Once a year Once a year
(2007) geohydrological
fieldwork
Sundaram et al. Book on Once every four Once every four Once every four Once every four
(2009) groundwater months months months months
sampling
Harter (2003) Book on Once a year Once a year Twice a year Twice a year
groundwater
sampling
Cal/EPA (2008) Manual on Once during Once during Once during Once during
representative rainy season and rainy season and rainy season and rainy season and
groundwater once during dry once during dry once during dry once during dry
sampling season for a season for a season for a season for a
minimum of one minimum of one minimum of one minimum of one
year year year year
Barcelona et al. Report on Quarterly for Quarterly for Quarterly for Quarterly for
(1989) groundwater more than two more than two more than two more than two
sampling years, to years, to years, to years, to
frequency determine determine determine determine
seasonal trends seasonal trends seasonal trends seasonal trends
and to minimise and to minimise and to minimise and to minimise
redundancy redundancy redundancy redundancy
Water Research Report on Twice a year Twice a year Twice a year Twice a year
Commission groundwater
[WRC], (2000) sampling
Senior (2014) Report on Monthly Monthly Monthly Monthly
groundwater sampling and sampling and sampling and sampling and
baseline analyses of 4 of analyses of 4 of analyses of 4 of analyses of 4 of
establishment the 20 boreholes the 20 boreholes the 20 boreholes the 20 boreholes
for for a year for a year for a year for a year
unconventional
gas projects
OBrien et al. Report on Minimum of Minimum of Minimum of Minimum of
(2013) groundwater three sampling three sampling three sampling three sampling
baseline runs, with one of runs, with one of runs, with one of runs, with one of
establishment the sampling the sampling the sampling the sampling
for runs at the end runs at the end runs at the end runs at the end
unconventional of summer (May) of summer (May) of summer (May) of summer (May)
gas projects and one and one and one and one
sampling run at sampling run at sampling run at sampling run at
the end of the end of the end of the end of
winter winter winter winter
(November) (November) (November) (November)
192
Research performed on the topic of groundwater sampling frequency by Barcelona et al. (1989) on
shallow sand and gravel aquifers, determined that by collecting samples four to six times per year
would result in an estimated data (information) loss of below 20% and would also minimise data
redundancy.
From the above information, the following sampling frequencies are suggested for the multi-porous
fractured aquifers of the Karoo Supergroup sedimentary succession, after completing the initial
sampling run during which all the chemical parameters listed in Table 3.10 are analysed for from each
of the boreholes selected for sampling in the study area:
3.9.7.1 Boreholes intersecting shallow (0 to 300 m) aquifers
For boreholes intersecting shallow (0300 m) fractured aquifers, a sampling frequency of once every
three months for two years is suggested.
Every three months all the boreholes should be analysed for the major ions, trace metals, silica and
organics listed in Table 3.10. The purpose of sampling and analysing the boreholes every three months
is to determine the seasonal variability of the shallow groundwater resources. Furthermore, twice a
year all the boreholes should be analysed for all the chemical parameters listed in Table 3.10. This is
done to decrease sampling and analysis cost.
Table 3.27 illustrates the sampling and analysis frequency suggested for shallow (0300 m) boreholes
according to the different seasons encountered in South Africa throughout a calendar year in a typical
summer rainfall region.
TABLE 3.27: SUGGESTED SAMPLING AND ANALYSIS FREQUENCY FOR SHALLOW (0 TO 300 m) BOREHOLES
Major ions, trace metals, Additional sampling for all
Sample and analyse for All chemical parameters
silica, organics the chemical parameters
Which boreholes All the boreholes All the boreholes Quarter of the boreholes
December
Summer January
February
March
Autumn April
May
June
Winter July
August
September
Spring October
November
193
3.9.7.2 Boreholes intersecting deep (300 to >1 000 m) aquifers
For boreholes intersecting deep (300>1 000 m) fractured aquifers, a sampling frequency of once
every six months for two years is suggested.
Every six months all the boreholes should be analysed for all the chemical parameters listed in Table
3.10. The boreholes should be sampled during February and August. These months represent the
approximate end of summer and winter seasonal periods in South Africa (WeatherSA, 2016). The
purpose of collecting samples at the end of each season is to determine the seasonal variability of the
groundwater. Table 3.28 presents the sampling and analysis frequency suggested for deep (300
>1 000 m) boreholes according to the different seasons encountered in South Africa throughout a
calendar year in a typical summer rainfall region.
TABLE 3.28: SUGGESTED SAMPLING AND ANALYSIS FREQUENCY FOR DEEP (300 TO >1 000 m) BOREHOLES
Additional sampling for all the chemical
Sample and analyse for All chemical parameters
parameters
Which boreholes All the boreholes Quarter of the boreholes
December
Summer January
February
March
Autumn April
May
June
Winter July
August
September
Spring October
November
3.9.7.3 Additional sampling
Additional sampling and analysis is required each month for two years from a quarter of the boreholes
(shallow and deep) selected for sampling and analysis. The boreholes selected to be sampled each
month should ideally contain dissolved methane concentration in excess of 1 mg/l (which can only be
determined after the initial sampling run), ideally be installed into different aquifers in the direction
of groundwater flow, if the location of the wellpad(s) is/are known, and spread out over the study
area if the location of the wellpad(s) is/are not known. The boreholes selected for additional sampling
will provide essential data on the seasonal variability in groundwater quality. The data can be used to
194
develop a good understanding of the natural groundwater system in the study area. Furthermore, the
data can be used to determine the representativeness of each sample collected (Senior, 2014).
Only boreholes which contain methane in excess of 1 mg/l should be tested for D CH4 and 13 CCH4 . This
is done to determine the origin of the methane.
If the additional sampling frequencies would prove too costly, the minimum suggested sampling
frequency would be each second month for two years. Implementing a limit on the number of samples
that should be collected during the groundwater baseline establishment programme could prevent
the programme from becoming too costly. The disadvantage of placing a limit on the number of wells
sampled is that the limit would make the testing programme less comprehensive.
3.9.7.4 Conclusion
Although higher sampling frequencies (each month for two years) from each available borehole would
result in more complex spatial and temporal characteristics, it would increase the cost of sampling
and laboratory analysis to the point that it would be impractical.
It is believed that the suggested sampling and analysis frequency for shallow and deep boreholes
would provide reasonable quantity ranges for the chemical parameters listed in Table 3.10, for each
hydrostratigraphic unit in the study area. It is believed that by implementing the suggested sampling
frequencies a good understanding of the natural groundwater system, with time in the study area,
would be achieved without collecting redundant information and without being too costly.
3.9.8 Establishing quality assurance and quality control measures

To ensure data integrity the following practices should be followed:
1. The field sampling practices should comply with the sampling and analysis plan.
2. The samples should be analysed by an accredited analytical laboratories which follow approved
standard analytical methods.
3. Field quality assurance samples should be collected.
Field quality control samples should be collected as follows:
Field duplicate samples are used to determine the precision of the laboratory analysis (Fetter
and Willard, 2001). For every twenty groundwater samples collected, one complete set of
duplicate samples should be collected immediately following the original sample collection, using
identical sampling methods. The duplicate sample should be analysed for the same parameters as
the original sample.
195
Data quality objective: The duplicate sample results should be evaluated using the relative percent
difference (RPD) between the original sample result and the duplicate, and is calculated as:
| |
= 100
0.5( + )
Where:
RPD = Relative percentage difference
|S D| = Absolute value of SD
S = Original sample result
D = Duplicate result
The data quality objective is 20% RPD will be used for the original and duplicate sample values.
Field equipment blanks to determine the degree of equipment decontamination (Nielsen and
Nielsen, 2006). For every ten groundwater samples collected, one equipment blank should be
collected if decontaminated sampling equipment is used. The sample should be collected
immediately following equipment decontamination, by sampling distilled deionised water that
has been run through or over the equipment. Equipment blanks should be analysed for major
cations and BTEXs.
Data quality objective: The equipment blanks should have concentrations below the method
detection limits.
Field blanks should only be collected if the sampler believes that the conditions on-site may
cause cross-contamination of the sample by VOCs or methane (for example, the well to be
sampled is situated adjacent to a fuelling area). The field blanks should be analysed for dissolved
gases (methane, ethane and propane) and BTEXs.
Data quality objective: The field blanks should have concentrations below the method detection
limits.
Laboratory quality assurance samples to determine laboratory accuracy and precision (Nielsen
and Nielsen, 2006). Quality assurance samples such as matrix spike and duplicates should be
prepared in the laboratory and analysed as specified by the specific method. The results must be
reported along with the original sample results on the laboratory report.
4. Data review should be performed after all the data has been received from the laboratory. The
data quality reviews should be documented on a data quality review sheet and stored in a project
file, together with the field sampling data sheet and the laboratory report.
196
The purpose of the data quality review sheet is to confirm that all the necessary data has been
collected (COGA, 2011; Nielsen and Nielsen, 2006).
3.9.9 Selecting a laboratory(s)

Before selecting a laboratory, it is recommended to first decide which sampling devices and methods
would provide the most representative results based on the specific site/field conditions.
Each laboratory uses specific analytical techniques which require recommended sampling devices and
sampling procedures, preservation or field treatments (COGA, 2011). Therefore, the ideal laboratory
should be able to analyse for the samples based on the samplers preferred sampling method. If not
possible, the preferred sampling device and procedure should be communicated to the laboratory to
resolve the issue and determine which sampling device and procedure can be used that suites both
the sampler and the laboratory.
3.9.10 Conducting the initial and subsequent sampling events

After selecting which physiochemical parameters to measure; selecting which chemical parameters to
analyse for; selecting which sampling device and methods to use; selecting the sampling frequency;
establishing quality assurance and quality control measures; and selecting a laboratory(s) for chemical
analysis the initial and subsequent sampling events can be conducted.
3.9.10.1 Generalised flow diagram of groundwater sampling steps
Figure 3.8 presents the protocol of the groundwater sampling sequence in the field. From the figure,
it can be seen that there are two sampling branches filtered and unfiltered which denotes which
samples should be field filtered in order to determine the dissolved constituents and which samples
should not be filtered. The sampling sequence progresses from the constituents which are the most
sensitive to handling (VOCs, where care should be taken by the sampler to not hinder the sampled
water and ultimately impact the chemical and physical properties of the sample) to the constituents
which are the least sensitive to handling (major ions). Furthermore, borehole purging parameters and
alkalinity should be determined in the field.
When conducting the sampling campaign, it is important to sample from the boreholes which are
expected to be the least contaminated to the boreholes which are expected to be the most
contaminated (for example, shallow boreholes to deep boreholes, and/or boreholes with high electric
conductivities to boreholes with low electric conductivities). This is done to prevent cross-
contamination of samples by the sampling equipment, especially if the same grab sampling equipment
such as bailers and thief samplers are used in multiple boreholes, even if the equipment has been
197
decontaminated between boreholes. It is therefore recommended to use new sampling devices for
each borehole if it is feasible to do so. Cross-contamination by the sampling device is, however, not a
problem in boreholes into which dedicated bladder and/or piston pumps are installed for sampling.
Figure 3.8: Generalised flow diagram of groundwater sampling
3.9.10.1.1 Installation of dedicated pumps and borehole purging
After selecting the boreholes to be sampled, the dedicated bladder or piston pumps need to be
installed at specific depths in order to collect groundwater samples from specific hydrostratigraphic
units. The installation can be done by a trained/experienced hydrologist or hired contractors.
198
If grab sampling devices will be used (bailers, thief or syringe samplers), the borehole should first be
sufficiently purged before collecting the samples.
3.9.10.1.2 Borehole purging for sample collection
Purging a borehole before sampling is essential to get representative samples to assess

hydrogeochemical processes or groundwater contamination issues. This is because the chemical
composition of stagnant water in an unused borehole is modified with time to the extent that a sample
taken from the stagnant water may be unrepresentative of the formation water. Therefore, purging
is required to remove stagnant water from the borehole to be able to sample fresh groundwater
drawn from the aquifer. Refer to Weaver et al. (2011) for processes that modify the chemistry of
stagnant water.
Fundamentally purging involves removing sufficient volumes of water from the borehole until the field
chemistry parameters stabilise, and samples can be collected. The most significant aspect of purging
a borehole is being consistent in operation between different boreholes, and during different sampling
runs, to meet accuracy and precision goals.
The volume of water that needs to be removed is generally three to five times the volume of the
standing water in the borehole before pumping takes place (this does not mean that the borehole
should be pumped dry). According to Weaver et al. (2007) boreholes should not be pumped dry (or
below the main water strike), because erroneous field readings will occur due to the influx of
formation particles; increase in turbidity; oxygen is introduced into the system; and gases and volatiles
are lost to the atmosphere (which might be dangerous to the field personnel). Therefore, it is
necessary to examine the borehole record sheet before pumping is started.
Note that three to five times the water volume of the well is merely a guideline and recommendation,
and purging should be done until chemical parameters have stabilised.
The following information needs to be collected and calculated when purging a borehole to collect a
representative sample of the borehole:
Field chemistry parameters: Temperature (C), pH, EC (mS/m), DO (mg/l) or Eh (volts).

Purge information: Purge time (per minute), purge volume (per litre), pumping rate/flow rate/
yield (l/s).
Borehole information: Borehole diameter (per metre), water level static (per metre), borehole
depth (per metre m), standing volume of water (per litre).
Additional information that need to be taken in the sampling sheet: Location, coordinates,
elevation, date, time, weather, and geological setting.
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P u r g i n g a h i g h - yi el d i n g b o r eh o l e w i t h n o p e rm a n en t p u m p i n g e q u i p me n t
Before any pumping takes place, the following measurements need to be taken: water level, borehole
depth, and collar diameter. The pump should be cleaned with potable water to remove dirt and debris
prior to purging (COGA, 2011).
It is essential to determine the yield of the borehole because it determines whether purging or low-
flow sampling techniques are required to assess hydrogeochemical processes or groundwater
contamination issues. If the borehole is high-yielding (5 l/s or higher), purging can be done (low-
yielding boreholes of 1 l/s or less require low-flow sampling techniques).
To determine if a borehole is low- or high-yielding (if it is not already known from the geohydrological
field investigation) a slug test has to be performed on the borehole that needs to be sampled. Refer
to Vivier et al. (1995) for more information on how to predict borehole yields using slug tests.
If it was determined that the borehole is high yielding (5 l/s or higher) a submersible or bladder pump
can be used to purge an open hole borehole, and as already mentioned, it is necessary to examine the
borehole record sheet to determine the depth of the main water source 14 .
To successfully purge a borehole, it is recommended that three times the volume of the water in the
borehole be pumped out to purge the borehole of any stagnant water to be able to collect a
representative groundwater sample.
After the determining the pumping time required to remove three volumes of water from the
borehole and the approximate yield of the borehole using a slug test has been determined, the pump
can be installed. The pump should be installed close to the static water level, and above the main
water strike.
P u r g i n g a b o r e h o l e w i t h a p e r m a n e n t p u m p i n s ta l l ed
depth, and collar diameter, and it should be recorded when the borehole was previously pumped. If
it is continuously used (for example, for irrigation) there is no need to purge the borehole. A sample
can be collected from a discharge point; however, if the borehole is not continuously pumped, the
pump should be turned on and run for the time calculated to remove three casing volumes, and the
sample collected (Sundaram et al., 2009), or use the purging procedure by COGA (2011) discussed
below.
14
A crude method of determining the sustainable yield of a borehole is to multiply the blow yield of the main water strike,
which should usually be recorded during drilling, with 0.4, for example, blow yield = 10 l/s, therefore sustainable yield =
4 l/s, which can be used as the pump rate during purging.
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Before purging the well, the owner of the borehole has to be contacted to acquire information on the
yield of the borehole. If the owner does not know the yield it can be calculated as follows if the
borehole has a pump installed:
Start pumping.
Use a stopwatch to measure the time it takes for the discharged water to fill a 50 l bucket (or 20 l
bucket), for example, 10 seconds to fill a 50 l bucket = 50 l/10s, therefore yield = 5 l/s.
If it is determined that the borehole yield is high, the borehole can be purged. Refer to COGA (2011)
and Weaver et al. (2007) for more information on purging a borehole with a permanent pump
installed.
S a m p l e c o l l e cti o n o f p u r ge d b o re h o l es
During sampling, the individuals collecting the samples should wear disposable polyethylene gloves to
prevent cross-contamination of the samples. New gloves should be worn at each individual sampling
location (COGA, 2011). Before sampling, the following water quality parameters have to be collected:
temperature (C), pH, EC (mS/m), DO (mg/l) or Eh (volts).
A complete set of samples should be collected from each borehole. For reliable instructions on
collecting filtered, unfiltered and dissolved gas samples for chemical and isotope analysis, refer to
Weaver et al. (2007), who provided consistent groundwater sampling techniques that will ensure that
all the groundwater samples collected are representative of the in situ groundwater quality.
There are different procedures for collecting samples. It is critical to choose a reliable sampling
procedure and to use it at every new sampling location and sample run to ensure comparable results.
C o l l e c t i n g a s a m p l e f r o m a l o w - y i e l d b o r eh o l e b y p u rgi n g o r l o w - f l o w
meth o d
Low-flow sampling can be used for either high- or low-yielding boreholes. Low-flow sampling has the
following advantages over normal (drawdown) purging:
It minimises mixing between overlying stagnant water and water within the screened interval (of
main water discharged zone-fractures).
Less operator variability, as this method is fairly simple to employ, which means better sample
consistency between different boreholes, and different sampling runs.
Reduced drawdown, which means that the chance of lowering the water level below the main
water discharge zone is significantly minimised.
Decreases purging volume.
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The only disadvantages of low-flow sampling are the greater setup times (if dedicated sampling
equipment is not used), increased training needs, and higher costs (Puls and Barcelona, 1996).
depth, and collar diameter. Next, the yield of the borehole should be determined. If the borehole has
a low yield (less than 1 l/s), one of two methods can be followed to collect a sample of the
groundwater.
Refer to COGA (2011) for more information on purging a low-yielding borehole with no permanent
pump installed.
L o w - f l o w s a m p l i n g/ p u rgi n g m e t h o d
Low-flow sampling is used in low-yielding boreholes to acquire a representative sample of a specific

formation by placing a pump (for example, a bladder pump), with a flow rate of 0.10.5 l/min, in the
middle or just above the middle of the screened interval of the borehole. This type of purging
minimises mixing of the overlying stagnant water with the screened interval water and maintain
minimal drawdown in the borehole. The pump can be placed on top of the water column for an
unconfined aquifer, but placement of the pump near the screened interval is acceptable for any type
of aquifer.
If dedicated sampling devices (pumps left in wells) can be afforded for sampling, it is highly
recommended to use them over any other sampling device, because these devices decrease mixing of
stagnant water and bottom suspended sediments with the formation water that is required for
sampling (Puls and Barcelona, 1996).
When lowering the pump, water level meter, water quality meters and sampling device into the
borehole, try to minimise disturbances to the stagnant water column, by lowering the devices slowly
and gently down into the borehole.
Low-flow sampling in fractured rock formations requires packers to isolate the sampling zone before
purging of the borehole takes place. It is of vital importance to first identify water-producing fractures
before sampling takes place. These fractures can be identified by using a Solinst 107 TLC Meter
(Temperature, Water Level and Conductivity) and geophysical tools for borehole profiling, and
borehole drill logs which have records of water strikes at different depths.
According to Puls and Barcelona (1996), to acquire the most representative sample of the fractured
formation, passive multi-layer sampling devices should be installed in-between packers. Dedicated
sampling devices installed at different depths in-between packers are also acceptable.
Refer to Puls and Barcelona (1996) for more information on the low-flow sampling procedure.
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L o w - f l o w s a m p l e c o l l ec ti o n
Gloves should be worn by all field operatives participating in sampling to prevent cross-contamination
of the collected samples.
Depending on the container type used for sampling, the pump tube can be used to collect the samples.
If the container contains any preservatives, the water from the tube should be discharged into a clean
plastic bucket, the bucket washed out with the tube water twice, then filled and used to carefully fill
the container, containing the preservatives 95% full. The preservatives used depend on the analysis
that will be performed on the sample (Puls and Barcelona, 1996).
Generally when sampling volatiles, such as solvents and fuel constituents, and gas sensitive
parameters such as Fe2+, CH4 , alkalinity, H 2 S/HS, should be sampled first, and filtered samples
collected last. Protective clothing should be worn during both purging and sampling (Puls and
Barcelona, 1996).
T o p u r g e o r n o t t o p u rge
In an investigation by Gomo and Vermeulen (2015) on the comparison of water quality differences
between 15 purged and non-purged monitoring wells in typical Karoo aquifers, it was found that there
was no significant statistical difference between inorganic chemistry and saturation indices between
purged and non-purged groundwater samples collected with an inertial lift foot-valve sampler at the
groundwater flow zone. It was concluded that it is possible in some geohydrological conditions that
non-purged groundwater samples are just as representative as the purged samples.
Furthermore, work done by van Tonder et al. (2002) suggested that during pumping from a typical
Karoo aquifer, the initial water will be from fractures during linear flow, and later from the matrix as
bi-linear flow (when the stored water from the fracture has been pumped out), which can lead to
mixing of groundwater before sampling. This suggests that purging of the borehole in fractured rock
aquifers might not be entirely necessary, and in some cases may even lead to the collection of water
samples from different hydrostratigraphic units. Therefore, when sampling to establishing a
groundwater baseline in fractured rock aquifers of the Karoo, during the first sample run, samples may
be collected before and after purging and the chemical data compared; if the chemical compound
concentrations are found to be similar, non-purged samples may be collected during the following
sample runs to reduce operational cost.
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3.9.10.1.3 Preservation of samples
After the samples have been collected, the samples must be preserved to protect the chemical and
physical integrity of the sample. The suggested method for preservation of the sample is to use sample
bottles that already contain parameter-specific preservatives. This method saves time, the sampling
team do not have to handle preservatives, and no errors associated with adding the correct volume
of preservatives can be made by field personnel (Nielsen and Nielsen, 2006).
After collecting the sample in the sample container, the bottle should be inverted (but not shaken)
with the sample cap secured to mix the sample and the preservative.
3.9.10.1.4 Sample handling and shipment
The sample containers should be labelled using a lead-free permanent marker. The containers should
contain the following information: name of the sample, date and time collected, requested analysis,
sampler initials, other information, if needed, such as sample depth, project name or number.
After sampling, the samples should be placed on ice in a pre-cooled icebox or cooler. The cooler should
be kept at a temperature below 4 C during storage and shipment to the laboratory. The containers
should be packed in such a way to prevent damage to the containers and to maintain the required
temperature during shipment.
3.9.10.1.5 Equipment decontamination
Disposable sampling equipment should be used whenever possible to prevent cross-contamination of

samples. The non-disposable equipment (for example, water level meters, sampling pumps with non-
disposable tubing, and water collection buckets) that come into contact with the samples must
undergo decontamination before being used and also in-between samples by using the following
procedure:
Dry brush the equipment followed by tap water rinse (where possible).
Wash the equipment with a laboratory grade detergent solution.
Rinse the equipment with tap water followed by deionised water.
Leave the equipment to air-dry.
The pumps and non-disposable discharge tubing should be flushed with a decontamination solution
to decontaminate the equipment.
Before arriving at the sampling location, decontamination should be performed. The decontaminated
equipment should be stored in sealed containers such as plastic bags (zip-lock plastic bags) to protect
the equipment from airborne dust contamination prior to use.
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3.9.10.1.6 Laboratory validation
After the samples have been analysed and the results have been generated, the results must be
validated. This is usually done by the laboratory section heads. Once the results have been validated,
the laboratory head should sign the analytical data before the results are forwarded to the sampler
(Nielsen and Nielsen, 2006).
After receiving the analytical results from the laboratory(s), the results need to be independently
validated by an experienced quality assurance chemist. The purpose of the independent review is to
ensure that the results are correct (Nielsen and Nielsen, 2006). One of the procedures which the
independent quality assurance chemist can utilise is electroneutrality (cationanion balance) as a
quality control check by calculating the cationanion balance. Errors between 5% and +5% are
considered acceptable (Edmunds and Shand, 2008).
3.10 ESTABLISHING A GROUNDWATER BASELINE
After validating the results, the results can be presented graphically on different plots and maps to
assess the water data, to identify chemical relationships, and to predict chemical changes in space and
time (after completing the groundwater baseline establishment). By presenting the data graphically
on cross-sections and maps, enables one to integrate all the chemical and hydrogeologic conditions,
which is useful to interpret flow paths, groundwater movement and quality controls (Nielsen and
Nielsen, 2006).
Water quality data can be displayed on a number of diagrams such as a Stiff diagram, contour maps,
histograms, time series diagram, Schoeller diagram and Piper diagram. For more examples on
presenting water quality data, refer to Nielsen and Nielsen (2006) and Hem (1985).
After plotting the water quality on different diagrams, preparation for the subsequent sampling events
can be made. Furthermore, after completing the subsequent sampling events and by following the
exact same sampling procedures as during the initial sampling event, the water quality and quantity
database can be updated, new diagrams can be constructed, of which the time series diagram is the
most important for establishing a groundwater baseline for unconventional gas projects.
The time series data for each hydrostratigraphic unit should be used to establish quantity ranges
(maximum-minimum) for the different chemical parameters analysed for during the groundwater
sampling events, including the water levels measured. These ranges, maximum and minimum values,
represent the baseline for the different parameters for each hydrostratigraphic unit in the study area
from the surface down to the production zone. These ranges will be used during monitoring, after
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unconventional gas activities have commenced, to determine if the activities have any quantitative
effects on the groundwater system in the study area.
Furthermore, after completing the subsequent sampling events, the conceptual and numerical models
can be updated and used as predictive tools for groundwater impact assessment due to
unconventional gas activities.
3.11 CONCLUSION
In this chapter a possible groundwater baseline methodology for hydraulic fracturing and UCG projects
in South Africa was outlined based on best practices and recommendations made in similar studies
and is presented in the form a flow diagram (see Figure 3.9). The different phases of establishing a
groundwater baseline were discussed and answers were provided to questions that have not been
fully answered in the existing literature on establishing a groundwater baseline for unconventional
gas projects.
In the description of the methodology section the question, during which phase of the unconventional
gas project should the baseline be established, was answered. The desk study, as well as the geological
and geohydrological sections, answered the question on what information should be collected before
conducting a sampling event. In the areal extent of the preliminary baseline study section, answers
were provided on what size the study area should be. The drilling new boreholes section answered
the question on whether drilling dedicated boreholes is required to collect representative
groundwater samples.
The initial and subsequent sampling events section answered the questions as to the parameters that
need to be sampled; the water quality standards for these parameters; which sampling devices and
methods to use to collect representative groundwater samples; how to select boreholes for sampling
and how frequently groundwater samples should be collected.
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Figure 3.9: Proposed groundwater baseline methodology for unconventional gas projects in South Africa
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Chapter 4
CASE STUDIES
4.1 INTRODUCTION
In this section the investigation sequence, practices, and results of three different case studies on
groundwater baseline establishment for unconventional gas projects in South Africa are reviewed and
summarised.
After reviewing the case studies, suggestions are made on how the studies could have been improved.
The suggestions were made by:
determining which activities were conducted and which activities were not conducted, and how
not conducting the activities affected the results; and
determining how different activities were planned, and also the procedures, methods, and devices
used during each activity, specifically focussing on groundwater sampling and how these practices
affected the results.
The suggestions are arranged according to the established baseline methodology sequence. This is
done in order to categorise the suggestions and also to indicate which activities have been conducted
and which activities have not been conducted.
After providing suggestions on how the case studies could have been improved, the practices and the
results and findings of the case studies are used to determine if the established baseline methodology
could have been improved or refined.
4.2 CASE STUDY ONE
4.2.1 Case study description
An environmental consultancy company (herein after referred to as Contractor A) was appointed by

a mining company (herein after referred to as Company X) to complete a geohydrological
investigation at The Site, after Company X intended to develop a coal resource at The Site, either as
a UCG project or as a conventional underground mine in South Africa. The Site is situated in one of
the Karoo sub-basins. The purpose of the geohydrological assessment of the proposed UCG or
conventional coal mining project was to gain a better understanding of any potential changes to the
groundwater system(s) that may be associated with the project, and also to manage these potential
changes. Contractor A was appointed to complete the required groundwater studies which included:
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Groundwater baseline study.
Construct calibrated flow and transport models.
Conduct a groundwater risk assessment.
The company name, contractor names and site name may not be disclosed as it is regarded as
confidential business information. It should also be noted that the author of the dissertation was part
of the groundwater baseline data collection process, report writing, and conceptual model design of
the current case study. The author and an associate collected all of the groundwater field data during
the hydrocensus and the specialised follow-up sampling campaign.
4.2.2 Objectives of the project

The main objectives of the project were to:
undertake a groundwater baseline study;

develop a groundwater monitoring network and programme;
determine the potential contaminants of concern and also their concentrations which were
anticipated to be present within the area of operation (i.e. source term characterisation);
predict the potential impacts to groundwater due to UCG and conventional coal mining projects;
use numerical flow and transport groundwater models for impact assessment; and
conduct a risk assessment using the outputs of the numerical model.
Therefore, the scope of the work was focused on the construction of a conceptual groundwater model
based on the available information and the field investigations undertaken.
Of these objectives, only the first three objectives were of interest for this dissertation as they could
be used to modify and update the present suggested groundwater baseline establishment
methodology for unconventional gas projects. The other objectives listed had to do with impact
prediction, impact assessment and risk assessments, which fell outside the scope of this dissertation.
4.2.3 Investigation sequence

Figure 4.1 is a flow diagram of the different activities that were conducted during the geohydrological
investigation by Contractor A in order to establish a groundwater baseline for the site, together with
the purpose(s) of each activity. The green coloured boxes indicate the activities and the yellow boxes
indicate the different purposes of each activity.
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Figure 4.1: Flow diagram of the sequence in which activities took place
In order to conduct a geohydrological investigation, Contractor A conducted a desk study, a first -order
geochemical assessment, a hydrocensus, a specialised follow-up sampling campaign, hydraulic packer
testing, and constructed a conceptual model.
This sections that follow will discuss each activity, focusing on the activities that are more significant
to groundwater baseline establishment.
4.2.3.1 Desk study
The purpose of the desk study was to determine what information of the site area was already known
or available. During the desk study, it was determined that the following previous projects/activities
were conducted at the site prior to the geohydrological investigation conducted by Contractor A (see
Table 4.1). The table includes the specific activities that were conducted, the date which a specific
contractor (Contractor B to F) conducted the activity(s) and the purpose of the activities.
Figure 4.2 is a flow diagram of the different activities that were conducted by other contractors prior
to the activities conducted by Contractor A, together with the purposes of each activity. Only the
yellow coloured boxes are purposes of the specific activity that are of interest for groundwater
baseline establishment; the blue coloured boxes are related to either resource estimation, mining, or
processing of the coal.
After the desk study was completed the following data gaps were identified based on the results of
the different investigations:
1. Lack of understanding of the geological structures which influence the geohydrology,

such as the orientation and nature of faulting.
2. Lack of geohydrological properties of the major structures on-site.
3. Only limited information was gathered on the geohydrological properties of the
different formations.
4. Baseline water quality had not been established for specific aquifer systems.
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TABLE 4.1: SUMMARY OF ACTIVITIES COMPLETED BEFORE THE GEOHYDROLOGICAL INVESTIGATION BY CONTRACTOR A
Type of
What Where When Main objective Completed by
project/activity
Desktop study Desktop screening study Office 01 January 2012 To determine if the coal resource, given a Contractor B
partly-known geological and geohydrological
setting, could be suitable for a commercial
UCG project.
Geophysics Ground magnetic (MAG) and The potential UCG site March 2013 To delineate possible geological structures in Company X
electromagnetic (EM) surveys were the area and to site boreholes for Geophysicists
done. groundwater drilling target purposes.
Exploration Eight exploration boreholes were drilled, In the north-eastern corner of the 07 March 2013 to 21 June To complete a 500500 m drilling grid over Contractor B
drilling logged and sampled. farm on which UCG will potentially 2013 a 380 ha area selected in the north-
be conducted. eastern corner of the site.
To extract T6-146 (123 mm) drill core
samples from two coal horizons for
ultimate and proximate coal analysis.
Drilling results were used to assist in the
compilation of a structural geology report.
Drilling and analysis results were used to
update the conceptual geological model.
The results were used to evaluate the
potential for UCG development on the
site.
Geotechnical Drilling of three geotechnical boreholes . Two close to each other in the 08 April 2013 to 06 To collect core samples for rock strength Company X,
drilling target area, and the other one in September 2013 analysis. Contractor B and
close proximity to a fault. To geologically log the boreholes. Contractor F
To verify the formation and coal seam
depth.
To be able to conduct downhole
geophysics.
To identify geological structures.
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Type of
project/activity
Groundwater Collection of groundwater levels with From all of the exploration 09 May 2013 to To understand and interpret groundwater Contractor B
levels the use of groundwater level monitoring boreholes. 22 September 2013 levels before drilling and during the aquifer
probes (from some of the exploration testing programme.
boreholes at one-hour intervals since
May 2013) and water level dip meters
(from the other exploration boreholes
between June 2013 and July 2013).
Geohydrological Drilling of four geohydrological At locations where geological 19 June 2013 to To intersect geological structures such as Contractor B
drilling boreholes and conducting specific structures might have been 13 July 2013 faults, and to determine the hydraulic
aquifer tests such as constant discharge present. Selected by using the parameters of the water-bearing horizons
and packer testing. March 2013 geophysical results and structures intersected by the borehole.
together with a 1:250 000
geological map to identify these
structures.
Slug test Slug testing was conducted on thirteen On boreholes distributed across 01 June 2013 to To supplement the packer testing data and Contractor B
exploration and/or hydrogeology the site. 01 July 2013 provide an indication of the hydraulic
boreholes. conductivity of the drilled exploration and
geohydrology boreholes. During the drilling
the water strike depths and airlift yields
were recorded.
Packer testing Packer testing on four hydrogeological Packer testing on six different 07 August 2013 and To determine the hydraulic conductivity in Contractor C
(Lugeon tests) boreholes, two exploration boreholes boreholes in three different 18 September 2013 the different aquifers at depth.
and one geotechnical borehole. lithological sections (in each
borehole). The tests were
conducted at contacts between
different formations and at
interbedded coal seams.
Aquifer testing Different aquifer tests on four Step test, constant rate test, September 2013 To obtain aquifer parameters (for example, Contractor C
hydrogeological boreholes and two recovery test and a constant transmissivity).
exploration boreholes. discharge test.
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Type of
project/activity
Downhole fluid Downhole fluid profiling on the six Dissolved Oxygen (% saturated), September 2013 Readings before and after the aquifer test Contractor C
profiling before boreholes used for aquifer testing. electrical conductivity (EC) can be compared to determine the
and after (uS/cm), pH and temperature (C) behaviour of groundwater at the site. The
aquifer test were measured before and after logs provided the water strikes (where
the aquifer test, to a depth of present) of the various boreholes and were
300 mbgl, in six boreholes, by also incorporated into the interpretations.
lowering a multi-parameter probe These profiles can be used to determine
down the borehole. where increased groundwater flow may
occur (structures which control groundwater
flow, such as fractures).
Hydrochemical Collection of groundwater samples From the boreholes used for September 2013 To determine the groundwater chemistry. Contractor C
sampling during the aquifer test at each borehole, aquifer testing and two other The analysis included: major ions, ICP metal
and also at two other boreholes requested boreholes. scan, pH, TDS, alkalinity, EC, total hardness,
requested for sampling by Company X. VOC, PAHs and TPHs.
Downhole The following downhole geophysical In eight exploration boreholes, September 2013 The results were used to correct lithological Contractor D
geophysics surveys were conducted: composite four geohydrological percussion logs, validate borehole depths,
logs, density, calliper, gamma, sonic, boreholes and three geotechnical determine/validate lithological unit depths
resistivity, neutron, verticality and boreholes. and thicknesses, and also to orientate
vertical seismic. structures.
Geotechnical Geotechnical core logging of recovered Geotechnical core logging on the September 2013 To determine the location, length, type, Contractor B
core logging cores from drilled boreholes. cores of the three geotechnical continuity, dip/angle, consistency, surface
boreholes. shape of joints and structures.
To determine formation type, the depth,
and thickness of a formation and rock
quality designation.
Aquifer testing Step rate test on one geotechnical In one borehole at four different November 2013 To obtain aquifer parameters. Contractor E
borehole. zones, isolated by packers.
Packer testing Packer testing on five different Four of the boreholes which were December 2013 To determine the hydraulic conductivity in Contractor E
(Lugeon tests) boreholes. previously packer tested were re- the different aquifers at various depths.
tested.
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Figure 4.2: Activities that were conducted prior to the geohydrological investigation by Contractor A
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4.2.3.2 First-order geochemistry assessment
After the desk study was completed, 34 rock samples were collected during the period 18 to 20 March
2014, from all the rock units that would potentially be exposed during mining and UCG at the site,
whereafter a first-order geochemical assessment was done on these samples.
4.2.3.2.1 Geochemical sampling
The purpose of the sampling was to assess the likely influence of the materials on the quality of
drainage from the UCG processes by geochemically analysing the samples. The following sampling
methodology was followed during sampling:
By using a scoop, two composite samples (one from the hanging wall coal zone and one from the
footwall zone) were collected from three coal zones in a nearby open pit mine, from piles of
blasted coal (as core samples were not available).
A sample from a coal zone underlying the coal zone considered for UCG was collected from three
geotechnical borehole cores.
Samples were collected from three geotechnical boreholes at regular intervals of 20 m up to 40 m
above the zone considered for UCG processes, from the formation directly overlying the zone.
These samples were considered to be representative of the overburden that was likely to be
affected by the UCG processes in the target coal zone. The samples were mixed to make two
composite samples of the overburden.
Sub-samples were collected from each lithological unit above the unit that was likely to be
affected by UCG processes in the target coal zone in the event that conventional mining is
considered instead of UCG.
The following guidelines were followed in developing the above sampling methodology:
In order to determine the statistical and spatial distributions of relevant geochemical parameters
in applicable strata, sufficient samples should be collected and analysed.
The available sample material determines the number of samples and sample size material and is
guided by site-specific information and use of statistical guidance.
Sampling depends on the required confidence level.
The assumed distance from the target coal zone at which formations would be affected by the
UCG process.
It was agreed that a total of 34 samples would have been collected, including duplicate samples for
quality control purposes.
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4.2.3.2.2 Laboratory geochemical analyses
The samples were then sent to a laboratory which is accredited by the South African National
Accreditation System (SANAS) for sample preparation and static geochemical tests, as required for
geochemical characterisation. The analysis included the following:
X-ray diffraction method to determine the mineralogical composition of the materials and
identifying minerals that might have a potential of generating acidity and neutralisation potential.
Multi-acid digestion, followed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) for
trace element determination.
Acid-base accounting (ABA) to determine the acid or neutralisation potential of the coal samples
and carbonaceous overburden and interburden samples from the different lithological units.
Standard net acid generation (NAG) and leach test on coal, interburden, and overburden samples,
to determine the potential drainage quality from UCG operations (and from the underground
conventional mine).
Deionised water leach tests to determine elemental mobility.
4.2.3.3 Hydrocensus and specialised follow-up sampling campaign
After the desk study was completed and the first-order geochemical assessment conducted, a total of
two field investigations were conducted, namely a hydrocensus and a specialised follow-up sampling
campaign. The hydrocensus and specialised follow-up sampling campaign were conducted in a 2 km
radius around the site. The hydrocensus was conducted from 31 March 2014 to 2 April 2014 in the
immediate and surrounding area, and the specialised follow-up sampling campaign from 31 July 2014
to 5 August 2014, also in the immediate and surrounding area.
The purpose of the hydrocensus was to establish a geohydrological and hydrochemical baseline for
the proposed UCG project at the project area, and the specialised follow-up sampling investigation
was conducted to confirm the baseline water chemistry results and also to investigate the occurrence
of different aquifer systems. The baseline was used to identify if any pollutants were presents prior to
the UCG operations.
4.2.3.3.1 Hydrocensus
During the hydrocensus all the existing boreholes and water bodies within a 2 km radius of the site
were visited, information collected, and samples collected at specific sites, and analysed for specific
parameters to establish the baseline water quality for the study area. From these sites the following
information was collected and noted on hydrocensus forms (where available or applicable): borehole
number (if any), farm name, coordinates, Global Positioning System (GPS) elevation, description of
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the topography, borehole owner and contact details, borehole depth, diameter, casing type, water
level, yield (reported), measuring height, water sample collected and time, infield water quality
parameters (including pH, EC, temperature, DO, TDS), pump type, driven by whom, pump depth,
discharge, pumping period, diameter of discharge pipe, condition of facility, use of borehole, how
many dependants, and any additional comments.
The groundwater baseline for the study area was established by calculating the baseline range for
each analysed parameter from each borehole sampled during the hydrocensus. For example, the
baseline range for magnesium for the study area was calculated by calculating the average and
standard deviation magnesium concentration for all the boreholes sampled and analysed for
magnesium and then subtracting the standard deviation concentration from the average
concentration to get the lower magnesium baseline concentration for the study area. To calculate the
upper magnesium baseline concentration, the standard deviation concentration was added to the
average. Therefore, the range = (average standard deviation; average; average + standard deviation)
= (lower range; average; upper range). This was done for each analysed parameter in order to establish
the groundwater baseline range for all the chemical parameters analysed for.
4.2.3.3.2 Specialised follow-up sampling campaign
During the specialised follow-up sampling campaign, PDBs were installed into five boreholes, and
some of the hydrocensus boreholes within a 2 km radius of the site were visited and sampled again to
confirm the baseline water chemistry results and also to investigate the occurrence of different
aquifer systems.
The same information was collected from these boreholes as during the hydrocensus, and noted on
hydrocensus forms.
4.2.3.4 Selected boreholes for sampling
It was decided that to establish a groundwater baseline for the area, the nearest surrounding
boreholes and surface water bodies needed to be sampled from surrounding farm properties in a
radius of 2 km around the site.
Sites (boreholes) that tested positive for methane during the hydrocensus were selected to be
sampled again during the specialised follow-up sampling campaign. Furthermore, five boreholes were
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selected into which PDBs were installed at different depths. These boreholes were selected because
they fit the following criteria:
They were drilled to depths as deep as 380 mbgl.

Their entire lithological logs were available.
They were located near faults.
They contained each lithological unit, including the UCG target coal zone.
There were a variety of tests conducted on these boreholes such as:
Packer tests conducted by Contractor C: The packer test results for the different formations
(together with the lithological logs) could be used to identify areas of high hydraulic
conductivity (areas where increased flow is present).
Detailed downhole fluid profiling using a multi-parameter probe conducted by Contractor C

before and after aquifer tests. These tests included dissolved oxygen (% saturation), electrical
conductivity (EC) (uS/cm), pH and temperature (C).
By comparing the downhole fluid profiles before and after aquifer tests, the profiles could be used to
identify where fractures might be present, which is regarded as an ideal location to install a PDB to
capture any VOCs which might diffuse from the formation.
The selected depths into which the PDBs were installed, were based on the packer test results and the
results from the downhole fluid profiling. The following is a list of reasons why a specific depth in a
borehole was chosen at which a PDB needed to be installed:
Based on packer test results the formation had a high hydraulic conductivity, indicating that the
formation was a good aquifer.
There was a significant difference in EC and/or pH values before and after the aquifer tests,
indicating a potential fracture zone.
PDBs were also installed into different formations to achieve a good coverage of the groundwater
chemistry variability in the different formations.
The purpose of installing the PDBs at different depths in the boreholes was to analyse the water from
the PDBs for organics to establish the variability of groundwater chemistry amongst the different
geological formations at the project site and to determine where different aquifer systems were
present.
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4.2.3.5 Selected parameters for sampling
The parameters that were analysed for during the hydrocensus and specialised sampling event
included: physical constituents such as pH and EC, macro, micro and organic constituents (including
VOCs, SVOCs, PAHs, extractable petroleum hydrocarbons (EPHs), phenols and organic pesticides).
The PDBs were analysed for the contamination scan, and the grab samples from the boreholes into
which the PDBs were installed were analysed for macro constituents.
For the full list of parameters analysed for, refer to Appendix D, Table D 1.
4.2.3.5.1 Rationale for sampling and analysing for the selected chemical parameters
Company A stated that because of their involvement in other UCG studies, the company had
developed a suite of organic chemical analyses specifically for UCG baseline establishment.
4.2.3.5.2 Sampling device(s), procedures and methods
S a m p l i n g d e vi ce ( s )
During the hydrocensus and specialised groundwater sampling events, disposable polyethylene
bailers were used to collect groundwater samples from the boreholes. Most of the boreholes were
suitable to sample with a bailer as they were either open (no equipment installed) or had a diameter
sufficient to allow a bailer to be lowered down the borehole and collect the water sample without the
bailer becoming entangled with the wiring of the installed pumps.
When the boreholes had pumps installed which could not be moved or did not have sufficient
openings to allow a bailer to be used, the owners, or a worker, activated the installed pump which
allowed water to be sampled from a nearby discharge hose.
During the specialised groundwater sampling event, PDBs were installed into five different boreholes;
two in each borehole at different depths where horizontal flow of water was expected.
S a m p l i n g p r o ce d u re s a n d m e t h o d s
Before collecting a water sample into the sample bottles, the borehole water levels were measured
using a Solinst (Model 101) water level meter. After measuring the water level, in-field water quality
measurements were taken from water collected with a bailer or from the pump discharge hose into a
500 ml plastic bucket. Measurements included: turbidity, dissolved oxygen, conductivity, TDS,
resistivity, salinity, pH, oxidation-reduction potential (ORP), and temperature. During the hydrocensus
these measurements were taken with the Hanna HI98129 pH/Conductivity/TDS Tester, and during the
specialised groundwater sampling event the Aquaread Aquameter with AP-800 Aquaprobe was used.
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Sampling using a bailer or pump discharge hose
After the in-field water quality measurements were taken, the water samples were collected by
discharging the water from the bailer (through the nozzle), or directly from the installed pump
discharge hose, into a 500 ml plastic bucket from where it was poured into the different sample
bottles, one containing 2 ml of 1% nitric acid (filtered on-site by using filters attached to the nozzle of
the syringes to prevent solids from being discharged into the sample bottle) and one containing 2 ml
of 1% sulphuric acid (not filtered).
Sampling using a passive diffusive bag

During the specialised sampling event, PDBs were installed into five boreholes; two in each borehole
at different depths where horizontal flow of water was expected to take place. Before installing the
PDBs at different depths in a borehole, the tubes were filled with deionised water at each installation
borehole by pouring the water into the bottom end of the PDB tube by removing the plug, inserting
the funnel into the opening and pouring the deionised water into the PDB. A PDB is used to passively
obtain concentrations of a variety of VOCs.
The bags were left in the boreholes for a week during which time the VOCs in the groundwater diffused
across the bag material until constituent concentrations within the bag reached equilibrium with
concentrations in the surrounding groundwater. The bags were retrieved after the week had passed.
The water was immediately transferred from the PDBs into the sample bottles and sent to an
internationally accredited laboratory.
Sample bottles
During the hydrocensus the following sample bottles were filled at each of the sampled sites:
Two plastic sample bottles (25 ml); one with 2 ml of 1% sulphuric acid, and the other containing
2 ml of 1% nitric acid.
One plastic sample bottle (100 ml).
One glass sample bottle (100 ml).
Two glass vials (50 ml).
During the specialised sampling event, the following sample bottles were filled at each of the sample
sites:
Two glass vials (50 ml).
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One glass sample bottle (100 ml).
Additionally grab samples were collected during the specialised sampling event from each of the
boreholes into which PDBs were installed. The following sample bottles were collected from these
boreholes.
The 25 ml plastic sample bottles were analysed for major ions; the 100 ml plastic and glass sample
bottles were analysed for trace metals and dissolved gases, respectively, and the 50 ml glass vials were
analysed for VOCs.
All of the samples bottles were handled while wearing latex gloves during sampling to prevent cross-
contamination between sites.
The information that needed to be written on each sample bottle with a non-lead permanent marker
(to prevent contamination) were:
Client name.
Project name.
Sample identification number.
Depth.
Date.
The samples were then placed in a Ziploc packet and placed in a cooler box which contained ice and
gel ice packs to keep the samples cool at <4 C, to prevent evaporation and chemical reactions from
taking place. After collecting, a sample measuring tape was used to measure the collar height and
diameter of the borehole casing. A GPS was then used to mark the point and take a geo-referenced
photo of the sampled borehole or surface water body.
4.2.3.5.3 Sampling frequency
Only two sampling events were conducted, of which the first was a hydrocensus during March 2014
(just after the wet season in summer), and the second a specialised follow-up sampling campaign
during August 2014 (just after the dry season in winter). This was done to assess the seasonal variation
of the chemical data.
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4.2.3.5.4 Quality assurance and quality control measures
By using daily calibrated equipment, the field-measured pH and EC values for all the samples were
compared to the laboratory pH and EC values. Also, during the hydrocensus, duplicate samples were
collected at each 20th consecutive sampling location, using identical sampling methods, and analysed
for the same parameters as the original sample to assess the precision of the laboratory analysis.
4.2.3.5.5 Selected laboratory
An internationally accredited laboratory was used to analyse the water samples collected during both
groundwater sampling events.
4.2.3.6 Hydraulic packer testing
Contractor A received packer test data (stepped pressure test; constant pressure and shut-in test) for
three boreholes located on the site; each with several packer test zones selected by Company X. The
packer tests were conducted by utilising the double packer configuration system and by using a
Standard Wireline Packer System (SWiPS) equipped with a straddle packer system. The three sets of
data were analysed, where relevant, to determine formation transmissivity, fracture pressure, and
gradient.
4.2.3.7 Result interpretation
4.2.3.7.1 Hydrocensus and specialised follow-up sampling
After receiving the data from either the first or second groundwater sampling events, all the sampling
data for the specific field events were qualitatively and quantitatively assessed by using the stacked
geochemistry plot, pie chart site distribution map for major ions at different sites, piper plot, and by
comparing the water quality to the South African Water Quality Guidelines for domestic uses (RSA
DWAF, 1996).
4.2.3.7.2 Hydraulic packer test
The received packer test data was analysed and interpreted using Contractor As own developed
software designed to analyse different types of geohydrological tests.
4.2.4 Results
The following is a description of the major findings of the investigation. It should be noted that the
results of the different geochemical assessments and chemical analysis data from the two
groundwater sampling events are classified information and are not disclosed in this dissertation.
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4.2.4.1 First-order geochemical assessments results
From the static geochemical analysis of the rock/core samples collected, the following key findings
were made:
It was reported that X-ray diffraction proved useful in determining the mineralogical composition
of the materials and identifying minerals that have a potential of generating acidity and
neutralisation potential.
It was reported that whole rock geochemistry proved useful in determining the extent of
elemental enrichment in the different samples collected.
It was reported that ABA proved useful in determining the acid or neutralisation potential of the
coal samples and carbonaceous overburden and interburden samples from the different
lithological units.
It was reported that the NAG tests proved useful in determining the potential drainage quality
from UCG operations.
4.2.4.2 Hydrocensus
A total of 49 sites were located, of which 41 sites were boreholes; 3 sites were drinking troughs
for cattle; 2 sites were dams; 1 sits was a river; 1 site was a surface water body (sewerage water
runoff); and 1 site was a water storage tank. Of these 49 sites, a total of 34 samples were collected
for chemical analysis, including boreholes, drinking troughs, dams, a river, a sewerage water
runoff and a water storage tank.
Some of the boreholes had depths exceeding 150 m, which indicated that they might have been
drilled through the coal zone of interest for UCG. These deep boreholes might have cause mixing
of deep saline groundwater from the coal seam with the fresh shallow aquifer water when
pumped.
The measured groundwater levels from 24 boreholes were used to determine the regional and
local groundwater flow regime and movement of groundwater within the strata.
The groundwater levels were compared with surface elevation and a good correlation was found.
Therefore, it was assumed that the groundwater flow direction follows the topography of the
area.
From the water level data, a shallower and deeper aquifer system could be inferred by comparing
the water level from the different boreholes drilled to different depths to one another.
The water chemistry data plotted on the piper plot indicated that dynamic groundwater flow was
present in the aquifer and that groundwater had not recently been recharged.
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4.2.4.3 Specialised follow-up sampling campaign
The PDB samples were used to determine that low concentrations of PAHs found in river water
could not be linked to the coal-bearing horizons.
It was found that methane and ethane were present in the groundwater on and off-site and
should, therefore, be routinely monitored before and after UCG operations.
4.2.4.4 Hydraulic packer testing
The data from the shut-in phase of the constant pressure tests was regarded as the best data.
Results obtained for the constant pressure test were regarded as more accurate than those of the
stepped pressure tests.
The three sets of data showed variable characters and interpretation viability for transmissivity,
fracture pressure, and gradient.
4.2.4.5 Site conceptual model
The results from the different investigations conducted by Contractor A, and the results from the
previous investigations by other contractors, were used by Contractor A to construct a site conceptual
model of the site and the nearby adjacent farms containing the following information (see Appendix
E):
The geology of the site, including:

The different formations, groups and supergroup.
The thickness of the different formation lithologies.
The location of major fault lines located on- and off-site.
Displacement direction of the major fault zone in the area.
The geohydrology of the site, including:
The transmissivity of the different geological groups.
An indication of the type of groundwater geologic formations (such as aquifer, aquitard or
aquiclude) together with an indication of water strikes or seepage in the formation.
The hydrology of the site, including:

Groundwater flow direction.
Groundwater level distribution map.
Generalised shallow groundwater level in the area.
Other
Satellite image of the area.
Property boundaries.
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4.2.5 Case study conclusion
A groundwater baseline for the potential UCG site was established, which identified whether
pollutants were present prior to the UCG operations. The established baseline consisted of natural
background groundwater values, which might be used for future groundwater monitoring purposes
to determine if the potential UCG project had any impact on the groundwater system qualitatively or
quantitatively.
4.3 SUGGESTIONS FOR CASE STUDY ONE

Based on the suggested methodology for establishing a groundwater baseline for unconventional gas
projects presented in this dissertation, the following additions are proposed for Case Study One, based
on the investigation design and the activities that were conducted:
With respect to the Desk study, no suggestions could be formulated on how the desk study could have
been improved.
With regard to defining an Areal extent for the preliminary baseline study, the following suggestion
is made:
The hydrocensus and specialised sampling events were conducted within a 2 km radius of the site.
The study is a local scale baseline assessment as the relative location where gas production may
potentially occur, is known. When calculating the appropriate size for the local baseline study, the
most vital aspect to consider is the size of contamination one would expect from the
unconventional gas project. In a study by Van Tonder et al. (2013), it was determined that if
hydraulic fracturing fluid was released into groundwater through preferential flow paths, the
contaminant could travel, under the worst-case scenario, 6 km in less than two months down-
gradient of the gas well. As the fluids and gases may migrate from the UCG production zone
through similar pathways as in hydraulic fracturing operations, it is suggested that the
groundwater baseline should have been established within a 5 km radius from the possible
wellpad area, or 5 km from the furthest point in the expected production zone (if known), to be
able to measure the potential contamination migration extent.
The same allocated budget for sampling could have been used, but instead, the samples could
have been collected in a radial pattern around the site within 5 km from site, with the majority of
the samples collected downstream of the site in the direction of groundwater flow at boreholes
used for domestic and irrigation purposes as it is suggested that the baseline should be receptor
focussed.
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During the planning stage of the Geological and geohydrological investigations, the following
additional activity is proposed:
Surface geophysics were conducted in the study area and downhole geophysics were conducted
on three geotechnical boreholes to identify and delineate geological structures which may act as
preferential flow features for migrating dissolved phase contaminants from the UCG production
zone. Two of the borehole drill locations were chosen to be within the sweet spot area and one
was drilled close to a fault, which was indicated on a two-dimensional seismic line graph.
Remote sensing is an inexpensive useful tool which may be used to identify lineaments and
fracture zones along which groundwater may flow before undertaking any field tests. If remote
sensing was conducted before conducting the surface geophysics, areas where abundant fracture
zones and lineaments occurred, could have been isolated and targeted for the surface geophysical
survey. The surface geophysical survey could then have been used to confirm if the preferential
flow features existed. The features could then have been targeted during drilling of the
geotechnical boreholes to determine the depth, shape, and orientation of these features with the
help of downhole geophysics. Furthermore, the results of the remote sensing and geophysical
surveys may then have been used in selecting existing boreholes and drilling new boreholes on
which to conduct aquifer tests to obtain aquifer parameters.
Remote sensing may also have aided in determining where increased groundwater flow occurred
in the boreholes used for downhole fluid profiling, supplementing the findings of the downhole
fluid profiling. A15
During the Geological investigation, the following additional activities are suggested:
Packer tests and downhole fluid profiling tests were conducted at various boreholes to determine
where increased groundwater flow occurred, such as fractures, or possibly between contacts of
two different formations. This information was used when selecting depth at which to install PDBs
to capture any VOCs which might have diffused from the formation or fracture. It is therefore
suggested that additional borehole logging tools, such as the downhole camera borehole logging
method, should have been used in conjunction with packer tests and downhole fluid profiling in
order to more effectively identify areas where increased groundwater flow occurred before
selecting depths at which to install the PDBs.
During the Geohydrological investigation, the following additional activities are suggested:
15
The letter in superscript, bold format, at the end of the paragraphs listed as A to O are referenced again in
the following case study as additional suggestions.
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During the different activities, the presence and condition (depth, water stage, dimensions, and
orientation) of geohydrological boundaries in the study area, such as rivers, dams and lakes, were
not inspected. This information is necessary when planning an aquifer test, and is also required
for improving the accuracy of the numerical model. It is therefore suggested that remote sensing
should have been conducted during the planning of the geohydrological investigation, and field
measurements should have been taken during the geohydrological field investigation. B
During the different activities, the location, rate, duration, and time (spatial and temporal
variability) of groundwater recharge and discharge were not determined. This information should
have been collected as it is required for calculating the water balance of the groundwater system
on- and off-site. It is also necessary for numerical modelling purposes, such as determining the
potential impact that UCG operations would have on the groundwater levels in the area, and also
aided in potential UCG contamination migration predictions. C
During the geohydrological investigations it is suggested that that tracer injection tests should
have been conducted. By conducting tracer tests would have aided in:
determining the groundwater flow rate and boundary conditions in the different aquifers;
determining the interconnectivity between the fractures and faults in the study area;
determining the fracture and matrix flow mechanisms; and
estimating fracture yields, hydraulic conductivity, seepage velocity, effective thickness and
kinematic porosity.
This information would all improve the accuracy of the numerical model and increase the
understanding of the flow mechanisms in the aquifers. Additionally, it is critical to know if
interconnections between different aquifer systems exist and also the vertical component of flow
in fractured aquifers. This could have been determined by conducting a pumping test and a tracer
test at the same time. D
With regard to Updating the preliminary conceptual site model and performing a gap analysis , the
following suggestion is made:
After different activities were conducted, the conceptual site model was not updated with the
new information. An updated model would have led to a better understanding of the processes
which control the groundwater chemistry, and also the different geological features which control
groundwater flow. By developing a better understanding of the site, it could have been
determined where information gaps existed and aided in determining what additional
investigations had to be conducted to fill these data gaps. E
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With regards to Drilling new boreholes to gain additional information, the following suggestion is
made:
The drilled geohydrological boreholes which were used for aquifer testing, hydrochemical
sampling, and downhole fluid profiling by Contractor C in September 2013, were all located near
fault zones (preferential flow features) across the site area. By drilling the boreholes near fault
zones would aid in determining if, and in which direction, a contamination plume is migrating on-
site. It is, however, suggested that the majority of the geohydrological boreholes should have been
drilled in a radial pattern near fault zones closer to the in-use domestic and irrigation boreholes
of adjacent properties in the direction of groundwater flow, as it is suggested that the
groundwater sampling programme should be receptor-focused. Also, higher modelling accuracy
is required near the receptors when predicting the potential contamination plume migration of
the UCG project.
During Planning for the initial and subsequent sampling events, it is suggested that the following
should have been done:
The hydrocensus groundwater samples were collected during the summer of 2014 and the
specialised follow-up groundwater sampling was conducted in the winter of 2014. As the samples
were collected only in one year during two seasons, it would be difficult to determine if the
differences in chemical concentrations were due to seasonal variation or laboratory bias.
Therefore, as suggested in this dissertation, a sampling frequency of once every three months for
two years is suggested. By following the suggested sampling frequency the seasonal variations
would have been evaluated accurately and it would have provided reasonable concentration
ranges for the chemical parameters suggested to be analysed for.
During the hydrocensus and specialised sampling event, no field alkalinity measurements were
taken from the sampled boreholes. Field alkalinity measurements are needed for waterrock
saturation calculations and to indicate if faulty or inaccurate equipment is used to measure the
pH of the sample. Also, in the study by Murray et al. (2015), it was found that alkalinity can be
used to differentiate between shallow and deep groundwater. It can, therefore, be analysed for
during the groundwater baseline establishment and monitoring phases to determine if mixing
between different aquifers occur. It is therefore suggested that field alkalinity measurements
need to be collected with the use of the titration method. F
During the hydrocensus, field measurements were taken with the Hanna HI98129
pH/Conductivity/TDS Tester, and during the specialised groundwater sampling event an Aquaread
Aquameter with an AP-800 Aquaprobe was used to collect field measurements of turbidity,
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dissolved oxygen, electrical conductivity, TDS, resistivity, salinity, pH, ORP, and temperature in an
open container. DO and ORP should not be measured in an open container where there is an air
water interface as the readings will be affected by exposure to atmospheric air which would lead
to inaccurate readings. It is therefore suggested that a flow-through cell should have been used
to collect representative readings for ORP, DO, and also for all the other field measurements
collected.
Furthermore, if it is not feasible to use a flow-through cell to collect representative field

measurements, it is suggested that the device which is able to measure most (if not all) of the
suggested field parameters accurately, should have been used during each sampling event. This
would have allowed for comparable field measurements and aided in interpreting the data. G
During the hydrocensus and specialised groundwater sampling events, disposable polyethylene
bailers (bottom fill, single bottom check valve) were occasionally used to collect groundwater
samples from the boreholes to be analysed for macro, micro, and organic constituents. Bailers
were used because they are portable, inexpensive, able to collect samples at great depths and
easy to use.
Bailers should, however, not be used when attempting to collect representative groundwater
samples as aeration of the sample may occur (Wilde et al., 2005). Also, bailers should not be used
when attempting to collect representative samples for organic constituents as loss of volatile
organic constituents may occur during sample transfer from the bailer nozzle into the sample
bottles. Further, during sample collection, bailers cause pressure reduction, which is undesirable
when attempting to collect representative samples for organic analysis (Weaver et al., 2007). It is
therefore suggested that syringe samplers should be used as these samplers are relatively
inexpensive and can be used to collect representative groundwater samples for most chemical
parameters. H
Bailers were occasionally used to collect groundwater samples during the hydrocensus and
specialised groundwater sampling events. When establishing a groundwater baseline, the tools
and procedures used must minimise subsurface and sample disturbance, from collecting the
samples to analysing the samples. When using a bailer to collect groundwater samples, significant
mixing of the water column occurs which results in deleterious effects on the collected water
sample, therefore lowering the accuracy and representativeness of the sample (Powell and Puls,
1993). It is therefore recommended that dedicated positive displacement bladder pumps,
dedicated piston pumps and/or syringe samplers should have been used to prevent or minimise
mixing of the water column in order to collect representative samples. I
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During the hydrocensus and specialised groundwater sampling events, existing pumps were also
occasionally used to collect groundwater samples from boreholes at discharge pipes if permanent
and active pumps were installed. These boreholes are, however, not ideal for collecting
groundwater samples as the pumps may have long-lasting effects on the chemistry of water
entering the borehole from the aquifer(s) (Lapham et al., 1997) and are therefore not
recommended for collecting representative groundwater samples. It is therefore recommended
that if an abandoned borehole with no equipment installed, is present in close proximity of the
borehole with a pump installed, that the abandoned borehole should rather be sampled, assuming
the abandoned borehole taps the same aquifer. Alternatively, a dedicated borehole should be
installed if and abandoned borehole is not present, and/or does not tap the aquifer of interest. J
During sampling, the groundwater samples were collected directly from the bailers, PDBs, and
discharge pipes into the sample bottles. According to the referenced material in Section 3.9.5.2
on collecting groundwater samples, representative samples would not have been collected due
to aeration of the samples. Therefore, in order to collect representative samples, it is proposed
that the sampling procedures and methods suggested in this dissertation be followed in order to
collect representative groundwater samples. K
During the hydrocensus and specialised sampling events, the collected samples were not analysed
for dissolved stable isotopes, radioactive isotopes, and petroleum hydrocarbons. The following
provides rationales for analysing for dissolved stable isotopes, radioactive isotopes, and
petroleum hydrocarbons. L

By not sampling and analysing for 18 OH2O and DH2O, deep groundwater cannot be
differentiated from shallow groundwater, and therefore, not be used to determine if deep
groundwater migrated into shallow groundwater due to UCG activities.
By not sampling and analysing for 13 CCH4 and D CH4 ; and 13 CC2H6 and D C2H6 , the source of
methane and ethane cannot be determined. Therefore, if increased concentration of methane
and ethane are encountered after UCG activities, the source of the gases cannot be
determined and attributed to the UCG activities.
Radionuclides may occur at elevated concentrations in both shale and coal formations and
produced water. Radioactive constituents are carcinogenic and may cause serious health
issues if present at concentrations exceeding any health-based screening levels for humans,
230
and are therefore recommended to be sampled and analysed for during groundwater baseline
establishment.
Total petroleum hydrocarbons

By analysing for gasoline range (C6C10) organics and diesel range (C10C28) organics, would
have provided measurement for the light and intermediate end hydrocarbons, which would
have included additional SVOCs, VOCs, oil and grease, and petroleum compounds which were
not sampled and analysed for and may be used during farming activities.
For the Initial and subsequent sampling events the following suggestions are made:
Before groundwater samples were collected from boreholes, the stagnant water in the boreholes
were not purged from the borehole. Purging is required to remove stagnant water from the
borehole to be able to sample representative groundwater drawn from the aquifer. It is suggested
that the purging procedure suggested in this dissertation should have been followed in order to
collect representative samples. The samplers should have determined whether the boreholes
were high or low-yielding. If it was determined that a borehole was high-yielding a submersible or
bladder pump should have been used to remove three times the volume of the water in the
borehole to successfully purge the borehole. If it was determined that a borehole was low-
yielding, low-flow sampling should have been used to collect representative samples. If it was,
however, not possible to purge the borehole successfully (due to no pump available or large
borehole volume) it is suggested that the top stagnant water column should have been removed
by using a bailer and then using a clean bailer to collect the groundwater samples for analysis. M
Even though it might not have a noticeable effect on the analytical laboratory results, during both
groundwater sampling events the same nylon rope was tied to the disposable bailer in order to
collect the groundwater sample from the boreholes. Organic contaminants from a borehole
containing high concentrations of organic contaminants may adsorb onto the rope, and diffuse
into the water of a borehole which has low concentrations of organic contaminants. This may lead
to the cross-contamination of groundwater samples if the same rope is used repeatedly in
different boreholes. It is therefore suggested that different nylon ropes should have been used for
each individual borehole, or decontaminated before use.
During the Groundwater baseline established for the study area, the following suggestion is made:
The groundwater baseline for the study area was established by calculating the baseline range for
each parameter analysed for from each borehole sampled during the hydrocensus. It is suggested
that, instead of calculating concentration ranges for specific parameters for the study area as a
whole, concentration ranges should have been established for deep, intermediate and shallow
231
aquifer systems. By establishing concentration ranges for specific parameters analysed for deep,
intermediate and shallow aquifers, would aid in determining more accurately whether potential
groundwater contamination occurred due to UCG activities. It would also help in determining at
which depth potential contamination occurred, and in determining how potential contamination
plume is spreading in the groundwater systems, through regular monitoring of the groundwater
system. N
Additional suggestions:
The following investigations were not conducted on the farm properties adjacent to the site area
(which fall within the study area):
Desk study.
Geological investigation, which includes:
Surface geophysics.
Borehole inspection.
Borehole logging.
Geohydrological investigations, which includes:
Geohydrological field investigation.
Aquifer tests.
Therefore, the following information on these farm properties were not known:
The formation into which the boreholes are installed. Therefore, it was not certain what the
source or sources were of the sampled water that were collected for analysis and field
measurements; and what aquifer or aquifer hydraulic heads were measured. This means that
calculated direction of groundwater flow would not have been accurate.
The lithology, depth, thickness, extent, orientation, homogeneity, and heterogeneity of the
aquifer systems/formations off-site. Therefore, the constructed conceptual model was not
accurate as the surrounding property geology was based on the known site geology; consequently,
the numerical model would also not be accurate.
The position, orientation (strike and dip), geometry and the type of preferential flow paths and
barriers. Therefore, it is not known which geological features/structures would control the
migration of a potential contamination plume off-site. Also, the numerical model would be less
accurate when being used as a predictive tool for potential contamination migration off-site.
Hydraulic properties of preferential flow features off-site. This means that the numerical model
would be less accurate when being used as a predictive tool for potential contamination migration
off-site.
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Hydraulic interconnectivity between the deep groundwater and shallow aquifers off-site. This
means that the numerical model would be less accurate when being used as a predictive tool for
potential contamination migration between different formations off-site.
Although the geological and geohydrological information for the adjacent properties can be
reasonably interpolated with the use of different interpolation techniques such as kriging, the exact
position, orientation and geometry of specific geological structures, as well as borehole construction
and installation, cannot be interpolated.
Therefore, during the hydrocensus and specialised sampling events on the adjacent farm properties,
samples were collected from boreholes with unknown construction and unknown sources, or a
mixture of different sources.
This, in turn, means that the established baseline quantity ranges were a mixture between different
groundwater sources. This would only prove useful in determining if significant UCG contamination
were to occur during monitoring. By establishing a groundwater baseline for different parameters
analysed for the entire study area from boreholes with unknown water sources, instead of establishing
a groundwater baseline for each hydrostratigraphic unit (or for shallow intermediate and deep
aquifers) from dedicated boreholes with known water sources, has the following disadvantages if
contamination due to UCG were to occur:
The depth, thickness, and extent of the contamination plume migration would not be known.
Vertical migration between different aquifers would not be known.
The aquifer(s) or preferential flow feature(s) through which the contamination would have to
migrate, would not be known.
The exact location of the contamination source would not be easily determined.
Therefore, it is suggested that before the boreholes were sampled, the borehole construction should
have been determined to identify the source(s) of the groundwater in the borehole. If it was
determined that the boreholes received water from different aquifers, the different sources could be
sampled with dedicated positive displacement bladder pumps or syringe samplers. Ideally, dedicated
boreholes completed in different hydrostratigraphic units with the borehole casing and construction
preventing groundwater mixing between different units, should have been used to be able to collect
representative samples from each unit and to be able to establish a groundwater baseline for each
hydrostratigraphic unit (or for shallow, intermediate, and deep groundwater) and allowed for easier
interpretation and comparison of analytical data. O
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4.4 CASE STUDY TWO
As part of an Environmental Impact Assessment (EIA) and Environmental Management Programme

(EMP), an environmental consultancy company in South Africa (herein after referred to as Contractor
A) was appointed by a coal resource development company (herein after referred to as Company X)
to complete a geohydrological investigation for a proposed UCG project site which is located in the
MKB of South Africa. In order to conduct a groundwater impact assessment, a groundwater baseline
was established for the site area.
The company name, contractor name, and site name may not be disclosed as it is regarded as
confidential business information. However, it is important to note that the Contractor A referred to
in Case Study One is the same environmental consultancy referred to as Contractor A in the current
case study. Therefore, there are many similarities in the devices, procedures, and methods used
during sampling.

The main aim of the geohydrological investigation was to investigate and determine the pre-UCG
geohydrological conditions present at the site, to inform the EIA and EMP processes.

Figure 4.3 is a flow diagram of the different activities that were conducted during the geohydrological
investigation by Contractor A to establish a groundwater baseline for the site, together with the
purpose(s) of each activity. The green coloured boxes indicate the activities and the yellow boxes
indicate the different purposes of each activity.
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With the purpose of undertaking a geohydrological investigation, Contractor A conducted a
hydrocensus, drilled exploration boreholes, conducted hydraulic tests on some of the drilled
exploration boreholes, constructed a conceptual site model, developed a numerical model, and
conducted a specialised follow-up sampling campaign.
This sections that follow will discuss each activity, focusing on the activities that are of most
importance for groundwater baseline establishment.
4.4.3.1 Hydrocensus
A hydrocensus was conducted in June 2013 as part of the scoping phase on the proposed UCG site
and the larger area on adjacent farms surrounding the proposed UCG site. Borehole information was
collected from the UCG site and from the adjacent farms. The purpose of the hydrocensus was to
provide the groundwater baseline conditions for the site area and to inform the EIA and EMP
processes.
During the hydrocensus, existing boreholes within 6 km of the project site were visited. Only thirteen
boreholes were located, of which six were sampled. Most of the boreholes sampled were reportedly
used for either domestic or irrigation purposes which might potentially be the reason why these
boreholes were sampled.
From these sites the following information was collected: GPS coordinates of the located boreholes,
borehole and landowner contact details, type of equipment installed, and the use of the borehole,
reported or measured yields, borehole depth (reported or measured), static water level, in-filed water
quality parameters (including pH, EC, temperature, DO, ORP, turbidity and TDS), and samples for
chemical analysis.
The field geochemical parameter readings were taken from the sampled boreholes and compared to
the SAWQG (RSA DWAF, 1996) to determine the suitability of the water for domestic use.
4.4.3.2 Specialised follow-up sampling campaign
A specialised follow-up sampling campaign was conducted during February 2014. During the
specialised follow-up sampling campaign, PDBs were installed into two boreholes at different depths
to investigate the occurrence of different aquifer systems, and grab samples were collected from each
borehole for inorganic analysis. Grab samples were also collected from the six sampled hydrocensus
boreholes to confirm the baseline water chemistry results.
Similar information was collected from these boreholes as during the hydrocensus, and noted on
hydrocensus forms.
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4.4.3.3 Selected boreholes for sampling
Six of the thirteen boreholes located during the hydrocensus were sampled. It was stated that the six
sampled boreholes were key boreholes. It is not clear why these boreholes were considered key
boreholes.
All the hydrocensus boreholes were resampled during the follow-up sampling campaign. It is believed
that these boreholes were resampled to be able to compare the chemical data from the wet and dry
seasons and to confirm the hydrocensus results. Additionally, PDBs were installed into two of the
exploration boreholes located on or near the proposed gasifier area. It is believed that these boreholes
were chosen because they contained the entire stratigraphy down to the coal members considered
for UCG.
4.4.3.4 Selected parameters for sampling
The collected samples were analysed for pH, EC, TDS, standard cations and anions, trace metals and a
comprehensive list of organic parameters. It is stated that the organic analysis included more than 200
organic compounds that are common contaminants in groundwater. Further, it is stated that by
performing a comprehensive analysis, all possible contaminants which may have been present prior
to UCG activities could have been included in the baseline description.
The hydrocensus boreholes were re-analysed for the same inorganic parameters as during the
hydrocensus, and also an additional list of organic compounds. The PDB samples were analysed for
pH, EC, alkalinity, standard cations and anions, trace metals, PAHs, dissolved, methane, ethane,
ethene and petroleum ranged hydrocarbons.
4.4.3.5 Rationale for sampling and analysing for the selected chemical parameters
The collected samples from the six boreholes were all analysed for pH, EC, TDS standard anions and
cations, trace metals as well as a comprehensive list of 200 organic compounds that are reported to
be common groundwater contaminants.
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The comprehensive list of organic compounds was analysed to determine which organic compounds
were present before any UCG activities, and also to define the baseline conditions.
The anions and cations were used to determine the groundwater type, to identify samples that have
similar compositions and/or to distinguish different water facies. The anions and cations, together
with the trace metals, were analysed to determine if any of the parameters posed any serious health
risk to users and to establish baseline conditions. The list of organic and inorganic compounds sampled
and analysed for during the hydrocensus are listed in Appendix D, Table D 1.
It is believed that the same chemical constituents were selected to be analysed from the samples
collected from the hydrocensus boreholes for comparative purposes, and to determine temporal
concentration variability for the chemicals analysed for.
No rationale was provided for selecting the specific chemical constituents to be analysed from the
collected PDB samples. The list of organic and inorganic compounds sampled and analysed for during
the specialised follow-up sampling campaign are listed in Appendix D, Table D 1.
The sampling device(s), procedures and methods used during the hydrocensus and specialised
sampling event was similar to the sampling device(s), procedures, and methods used for the
hydrocensus in Case Study One. This is because Contractor A refers to the same environmental
consultancy company.
4.4.3.5.4 Selected sampling frequency
Two groundwater sampling events were undertaken. The hydrocensus was conducted during June
2013, which represent the baseline conditions for the dry season, and the specialised follow-up
sampling campaign was conducted during February 2014, which represented the baseline conditions
for the wet season.
4.4.3.5.5 Quality assurance and quality control measures
No quality assurance or quality control measures were taken.
4.4.3.6 Exploration borehole drilling
Nine exploration boreholes were core drilled on or near the proposed gasifier area to be able to
conduct downhole geophysical logging and hydraulic tests on two of the newly drilled core holes. The
core of one of the exploration boreholes was used to construct the lithological log for the site. The log
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was used to construct the conceptual model of the site which represented the basis of the numerical
model.
4.4.3.7 Downhole geophysics
As soon as two core holes were completed, the core holes were logged using downhole geophysical
techniques including density logger and calliper wireline logging. The purpose was to determine at
which intervals to conduct packer testing.
4.4.3.8 Hydraulic testing
Packer and pumping tests were conducted on two of the newly drilled exploration boreholes (one on
the north-western side of the proposed gasifier and one on the south-eastern side of the proposed
gasifier) at selected intervals to determine the hydraulic parameters of geohydrological units which
would be used as inputs into the numerical model.
Packer testing was done using the double packers (straddle) technique to isolate specific horizons to
determine the hydraulic parameters of a specific geohydrological unit. The intervals were selected
based on the core and wireline logs. The intervals selected were either over coal seams or formations
overlying and underlying the coal seams. The pumping tests were conducted at selected intervals
based on the packer test results.
4.4.3.9 Conceptual model
The collected geological and geohydrological information was used to create a conceptual site model.
The created geohydrological conceptual model for the site was based on the core logs collected and
the packer test results from one of the exploration boreholes. The conceptual model represented the
basis of the numerical model. The lithological units were translated into geohydrological units based
on their hydraulic characteristics.
4.4.3.10 Numerical model

A preliminary numerical model was developed based on the constructed conceptual model. The
numerical model was constructed by using the finite element code of FEFLOW16 (a software program
by DHI-WASY). The purpose of the model was to determine the impact of UCG on the groundwater
system. Boundary conditions were added to the model and the model was discretised horizontally and
vertically to allow characterisation of groundwater flow. The recharge value for the model was
calculated as being 2% of the average annual rainfall for 91 years.
16
Finite Element subsurface FLOW system.
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Piper and Stiff diagrams were used to interpret the hydrocensus chemical analysis data and to
characterise the groundwater. The results were also compared to the SAWQG (RSA DWAF, 1996) for
domestic use to assess if any of the parameters posed any serious health risk to users.
4.4.4 Results
The following is a list of the major findings of the investigation. It should be noted that the results of
the groundwater chemical analysis are classified information and not disclosed in this report.
4.4.4.1 Hydrocensus
A total of thirteen boreholes were located. Of these thirteen boreholes, a total of six samples were
collected for chemical analysis. Two of the boreholes sampled were within 10 m of the proposed
UCG gasifier area and the furthest sampled borehole was 6.5 km away.
The measured resting water levels measured were typical for Karoo type aquifers.
The measured borehole yields from five boreholes indicated the yield was typical of Karoo type
aquifers.
The surveyed boreholes were used for either domestic or irrigation purposes.
The field geochemical parameter measurements indicated that the water quality from the
sampled boreholes was generally good and suitable for domestic use.
The inorganic chemical results indicated that the collected samples exceeded the ideal guideline
for domestic use but still fell within the marginal to no health effect range.
Of the organics analysed, only TPH, styrene, and monochlorobenzene were detected at very low
ranges in three of the six sampled boreholes.
4.4.4.1.1 Exploration borehole drilling and logging
From the wireline logs, it was noted that two of the nine boreholes were drilled to approximately
370 mbgl, through the target coal seam.
A dolerite intrusion was encountered at approximately 240250 mbgl.
4.4.4.1.2 Hydraulic testing
Packer testing provided reliable permeability values for the intervals tested.
The calculated hydraulic conductivities from the packer testing indicated that the formations
overlying and underlying the target coal seam had relatively low permeabilities. Pumping tests
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were not conducted due to the low permeability values of the formations encountered during
packer testing.
4.4.4.1.3 Conceptual model
The conceptual model represented the basis of the numerical model. The lithological units were
translated into geohydrological units based on their hydraulic characteristics.
The conceptual side model presents a lately extensive dolerite dyke above the coal zone of interest
for UCG development. It was stated that the dolerite dyke above the gasifier is a very good
geological cap and that the dyke, combined with the low permeability values of the formations,
are favourable for UCG.
4.4.4.1.4 Numerical model
The created model was a preliminary model; it was stated that the model was constructed with
sufficient geometric refinement to be used in detailed simulations. The simulations from the model
indicated the following:
The piezometric surface of the shallow aquifer did not change during the 10-year simulation
period.
The UCG process did not have any effect on the upper aquifer after five years.
There was no risk of groundwater contamination due to the UCG process.
The low hydraulic conductivity geohydrological units maintained their pre-UCG hydraulic head
outside the gasifier which would restrict regional groundwater flow.
The results of the specialised follow-up sampling campaign are not known and the report was not
available during the time of writing this dissertation. However, it is known that the results from the
sampling event would have been used to calibrate the existing numerical model.

It was stated that the hydrocensus results provided a reliable first-order baseline for the general
groundwater quality and quantity before any UCG activities have occurred. Further, it was stated that,
based on the findings of the investigation, there was no risk of groundwater contamination of the
deeper groundwater system during UCG as the numerical model predicted that the groundwater flow
direction would be into the gasification chamber and that no components would be mobilised into
the groundwater system during UCG operations.
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4.5 SUGGESTIONS FOR CASE STUDY TWO
In addition to the suggestions made for Case Study One, listed as A to O (in superscript, bold format
at the end of a paragraph), the following additional suggestions, based on the investigation, design
and activities conducted, are proposed for Case Study Two according to the suggested methodology
for establishing a groundwater baseline for unconventional gas projects presented in this dissertation.
With respect to the Desk study, the following suggestions are made:
No desk study was conducted on the study area to assess what information was already available
before conducting any of the activities. It is essential to conduct a desk study as the available
information is used to define the area size of the preliminary baseline study area and to construct
a preliminary conceptual site model. The preliminary conceptual site model is used to highlight
areas where data gaps exist which is essential in planning for the next phases of establishing a
groundwater baseline.
Also, the preliminary conceptual site model should be created during the desk study and updated
with new information as the groundwater baseline establishment process continues to construct
a final conceptual site model which illustrates the potential sources of contamination; the
pathways through which the contaminants may migrate; and also the potential receptors which
may be affected by the contaminants. This information should be taken into account when
constructing a numerical model of the study area.
Further, by not conducting a desk study on the study area, it was not known what geological and
geohydrological information was already available before collecting geological and
geohydrological data. Therefore, unnecessary data may have been collected during the different
investigations, which may have led to wasteful expenditure.
It is therefore suggested that a desk study of the area should have been conducted before
undertaking any field investigations to determine where data gaps exist; to gain a better
understanding of the natural groundwater system spatially and temporally; and to help plan the
investigations.
With regard to defining an Areal extent of the preliminary baseline study, no suggestions could be
formulated on how the areal extent could have been better defined.
During the planning stage of the Geological and geohydrological investigations, the following
suggestion is made:
Geohydrological and geological information were only collected from two exploration boreholes,
one on-site and one near the proposed gasifier area. The established conceptual and numerical
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models were based on the geological and geohydrological information collected from the on-site
exploration borehole. Therefore, the simulated contamination that may potentially occur due to
UCG activities is based on a single borehole for the entire site and study area.
It is therefore suggested that in order to better simulate the potential contamination, more
geological and geohydrological information from more on-site boreholes should have been
collected and used in the model. Furthermore, it is suggested that additional exploration
boreholes should have been drilled off-site in the direction of groundwater flow near potential
receptors in a radial pattern, ideally near preferential flow features at different depths. By
collecting geological and geohydrological information from these additional boreholes would have
allowed for more accurate simulations regarding the change in potentiometric surfaces with time,
the effect that the UCG process would have had on the aquifer systems with time, and the
potential risk which the UCG process posed to groundwater contamination.
During the Geological investigation, the following additional activities are suggested:
The core sample collected from one of the exploration boreholes was used to construct the
lithological log for the site. From the log, it was determined that a dolerite intrusion was present
in the proposed gasification chamber above the target coal seam of interest for UCG development.
Based on the core log collected from one exploration borehole, the dolerite intrusion was
incorporated into the conceptual model extending over the entire study area as a dolerite sill. This
model was then used for simulations using a numerical model. It is suggested that geophysical
surveys and/or more off-site exploration boreholes should have been drilled over the study area
to determine the true extent, orientation, thickness, and dimensions of the dolerite intrusion,
instead of using the information collected from one on-site core log to represent the geology of
the entire site. This would have allowed for more accurate numerical model simulations.
Furthermore, the additional exploration boreholes could be used for groundwater sampling and
monitoring purposes.
With regard to the Geohydrological investigation the following suggestion is made:
Packer and pumping test (hydraulic tests) were conducted on two of the newly drilled exploration
boreholes (one on the north-western side of the proposed gasifier and one on the south-eastern
side of the proposed gasifier) at selected intervals to determine the hydraulic parameters of
geohydrological units which would be used as inputs into the numerical model. It is suggested that
additional exploration, or geohydrological boreholes, should have been drilled in a radial pattern
near existing geological preferential flow features closer to the in-use domestic and irrigation
boreholes of adjacent properties in the direction of groundwater flow. These boreholes should
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have been used to conduct aquifer tests as higher modelling accuracy is required near the
receptors when predicting the potential contamination plume migration of the UCG project.
With regard to Updating the preliminary conceptual site model and performing a gap analysis, the
same suggestion made in Case Study One, listed as E, is also suggested for this case study.
The following suggestions on Drilling new boreholes are made:
It was reported that a total of eight monitoring boreholes will be installed to be monitored
throughout the life of the UCG project. Two boreholes at one location, of which one of the
boreholes will be installed at an intermediate depth (80 m) and one deep (350 m). Three of these
borehole installation locations (which equals six of the eight boreholes) will be installed up-
gradient of the proposed construction area, and one of the borehole installation locations (which
equals two of the eight boreholes) will be installed down-gradient of the proposed construction
area.
Although the construction information of these boreholes is not known, it is essential that when
installing the borehole casing, the aquifer which water quality is not of interest is cased-off, to
prevent mixing of different aquifer groundwater and also to prevent creating migration pathways,
for example, from deep geological formations to shallower formations through the newly drilled
borehole.
It is suggested that these monitoring wells should be drilled at least 3 years before UCG gas
production begins, to be able to use these wells to establish a groundwater baseline for the
intermediate and deep(er) aquifer systems, which can be used to differentiate the units from one
another, which would help to determine if groundwater mixing occurred between the different
aquifers before, during and after the UCG process. It would also help to determine if the UCG
process affected the groundwater quality and hydraulic heads of the different aquifer systems.
Furthermore, it is suggested that the majority of these boreholes should be drilled in a radial
pattern down-gradient of the proposed UCG construction area, in the direction of potential off-
site receptors in a radial pattern.
During Planning for the initial and subsequent sampling events it is suggested that the following
should have been done:
During the hydrocenus, only six of the ten located boreholes which contained water were sampled
to establish a groundwater baseline for the entire study area. It is suggested that all the boreholes
should have been sampled in order to establish groundwater quantity ranges for the different
parameters analysed over the entire study area. Also, it is necessary that all the boreholes within
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5 km of the site are sampled during baseline establishment as it would help resolve disputes
regarding claims of groundwater contamination after UCG activities have taken place.
Also, a larger number of boreholes should have been sampled (or installed for sampling), and
analysed for during the investigation, this would have assisted in establishing a more reliable
groundwater baseline for the study area.
As samples were collected only once each year once during the dry season (shallow boreholes)
and once during the wet season (shallow and deep boreholes) it would be difficult to determine
if the differences in chemical constituent values were due to seasonal variation or laboratory bias.
Therefore, as suggested in this dissertation, a sampling frequency of once every three months for
two years is suggested. By following the suggested sampling frequency the seasonal variations
would have been evaluated accurately and it would have provided reasonable concentration
ranges for the chemical parameters suggested to be analysed for.
During the hydrocensus, the collected groundwater samples were analysed for a list of inorganic
compounds by two different laboratories to establish a groundwater baseline for the study area.
During the specialised follow-up sampling event, the hydrocensus boreholes were sampled again
and analysed for a list of inorganic compounds to confirm the baseline water chemistry results,
and also to investigate the occurrence of different aquifer systems. During the specialised follow-
up sampling event, the samples were analysed for a different list of inorganic compounds than the
initial hydrocensus samples, and were also analysed by a different laboratory than the initial
laboratory. It is therefore suggested that to be able to confirm the results from the hydrocensus,
the same list of inorganic compounds should have been analysed for by the same laboratory as
during the hydrocensus, as laboratory analytical methods and procedures may differ from one
another.
The existing boreholes on the adjacent farms were not inspected before selecting the appropriate
sampling devices to collect representative samples during the hydrocensus. This is because bailers
and discharge hoses from the borehole pumps were used to collect samples. Disposable bailers
and discharge hoses are much easier to use for sampling groundwater than using positive
displacement bladder pumps, piston pumps or syringe samplers as they are either cheap, easy and
quick to use and do not require initial field inspection, thus saving time and money. Bailers and
discharge hoses from boreholes should, however, not be used when attempting to collect
representative groundwater samples (Lapham et al., 1997; Powell and Puls, 1993; Wilde et al.,
2005). It is therefore recommended that syringe samplers should have been used as they can be
used to collect representative groundwater samples at any depth, they can serve as the sampling
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container and bladder pumps and piston pumps are not always available; too expensive; and
cannot be installed in boreholes with permanent pumps installed.
For the Initial and subsequent sampling events, the following suggestion is made:
Quality control samples were not collected during the hydrocensus and specialised sampling
events in order to determine the integrity and reliability of the analytical laboratory data. It is
suggested that field quality control samples should have been collected to validate and ensure the
reliability of the analytical results.
With regards to Establishing a groundwater baseline for the study area, the same suggestion made
in Case Study One, listed as O, is also suggested for this case study.
Additional suggestions:
Contractor A recommended in their report that before the start of UCG, a monitoring network should
be installed and groundwater samples collected according to an accepted groundwater monitoring
protocol. It is recommended that geophysical surveys should be conducted, and the suggestions made
for drilling monitoring boreholes in this dissertation followed when drilling new boreholes.
It should be noted that although the geohydrological investigations in Case Study One and Case Study
Two were undertaken by the same environmental consultancy company, more information could be
collected for Case Study Two as a larger financial budget was available for the project. Therefore, the
results for Case Study Two are deemed more comprehensive and reliable than the results of Case
Study One.
4.6 CASE STUDY THREE
A study was undertaken by Ricky Murray, Kelley Swana, Jodie Miller, Siep Talma, Gideon Tredoux,
Avner Vengosh and Tom Darrah in 201517 to determine whether sub-thermal spring waters (>25 C)
are suitable sampling alternatives for deep Karoo groundwater during groundwater hydrochemical
baseline studies for shale gas development, as there were no functional boreholes that tapped
>1 500 m groundwater at the time of the investigation.
17 The use of chemistry, isotopes and gases as indicators of deeper circulating groundwater in the Main Karoo Basin,
published as a research report of the South African Water Commission, Report no. 2254/1/15.
245
The study was aimed at fingerprinting the deep groundwater of the MKB and to improve the
understanding of the deep groundwater system geochemistry within the MKB. This understanding
would have helped differentiate between the shallow and deep groundwater, and by being able to
differentiate between the two, a groundwater baseline for future contamination monitoring projects
could be established to monitor potential contamination.
The project was based on the fact that deep and shallow groundwater have different hydrochemical
characteristics because they are hosted in different units and because deeper groundwater has been
underground for longer times and has undergone more waterrock interactions (with deep water
equating to older water).
It should be noted that Case Study Three was not focussed on establishing a groundwater baseline for
an unconventional gas project before any unconventional gas activities, but rather to determine
whether sub-thermal spring waters (>25 C) are suitable sampling alternatives for deep Karoo
(hydraulic fracturing). This case study was, however, included as the findings of the study were used
to modify the established baseline methodology, specifically which chemical parameters to analyse
for during groundwater baseline establishment, and also how these parameters could be used to
establish groundwater quantity ranges for shallow, medium and deep groundwater. Suggestions on
how the study could have been improved based on the established baseline methodology, are also
provided.

The study had the following main objectives:
To determine if sub-thermal springs can be used as alternatives for boreholes which tap deep
Karoo groundwater.
To improve the understanding of the deep groundwater systems geochemistry of the MKB.
To identify determinants which can be used to distinguish shallow groundwater from deep
groundwater.
To develop a list of determinants for regulatory purposes that should be analysed for in both
shallow and deep boreholes in shale gas development areas.

In order to achieve the objectives of the project the researchers had to face two major challenges:
The first was to obtain groundwater samples which would reflect deep groundwater flow paths.
246
The second was to select and identify parameters to sample for, which would illustrate deep
groundwater flow paths.
The sections that follow, describe how the investigation was conducted in order to achieve the
objectives of the project and the steps that were taken to approach the challenges (such as selecting
boreholes and sites from which to collect water samples, and selecting parameters or tracers that
demonstrate deep flow paths), together with other actions/steps taken that are of interest for
establishing a groundwater baseline methodology for unconventional gas projects.
Figure 4.4 illustrates the sequence in which activities of the investigation took place in order to meet
the objectives of the study, together with the purpose of each activity. The green coloured boxes
indicate the activities and the yellow boxes indicate the different purposes of each activity.
From Figure 4.4 it can be seen that after grouping/differentiating the sites into deep, shallow and
mixed categories, the deep and shallow groundwater was then characterised and determinants were
identified which were able to differentiate these waters. A list of determinants could then be
developed which should be analysed for in both shallow and deep boreholes in shale gas development
areas.
The sections that will be covered which were not the focus of the study and were only discussed
briefly, were the selected sampling devices, procedures and methods used, and the sampling
frequency. These sections are of more importance for establishing a groundwater baseline for
unconventional gas projects and are therefore included.
4.6.3.1 Groundwater sampling methodology
The sampling methodology was aimed at obtaining groundwater samples which would reflect deep
groundwater flow paths and to select and identify parameters to sample for, which would confirm
deep groundwater flow paths.
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4.6.3.1.1 Selecting boreholes and springs for sampling
One of the major tasks of the project was to select suitable sampling sites from the vast number of
boreholes in the MKB. The location and hydrochemistry of the boreholes and springs were obtained
from the National Groundwater Database (NGDB), the National Groundwater Archive (NGA), and the
Water Management System (WMS), all provided by the Department of Water and Sanitation (RSA
DWS).
Potential sites were then selected, based on the criteria listed below. After the initial visit, specific
sites were then selected for further study. Hot water springs, deep boreholes, and boreholes that had
previously been suspected to contain deep groundwater, had been selected to sample for deep
groundwater. At each of these locations, a shallow counterpart was sampled from a borehole for
comparative purposes.
After the site selection, two sampling field trips were organised. A total of 33 sites (25 boreholes and
8 springs at 11 locations) were sampled during the first sampling trip. A total of 19 sites (13 boreholes
and 6 springs at 8 locations) were selected for the second sampling trip based on the results from the
first sampling trip.
Potential sites were selected based on the following criteria:
The borehole or spring needed to be within the lithologies of the MKB and within the Karoo
sequence. This information was derived from borehole information and from the Council for
Geoscience published 1:250 000 geological maps.
The presence of warm water.
Unusual groundwater chemistry (high EC values) which show similarities to known warm water
boreholes or springs.
A GIS approach was used to determine the location of unusual groundwater chemistry. EC values for
a number of boreholes were used to isolate high EC boreholes and springs to identify areas with
exceptionally high EC values. Further, to identify study sites with warm water boreholes and warm
springs, meetings with hydrogeologists, drillers, pump test contractors and other experts were held
to identify such sites (such as sites with unusual chemistry and warm water). Shallow boreholes within
several kilometres of the deep sites were selected for sampling for comparative purposes.
By using the above-mentioned method, a final list of eight areas were identified as suitable for further
detailed investigations. From these 8 areas, 33 sites (deep boreholes and springs, as well as shallow
boreholes) were sampled during the initial sampling event and the results of these samples were then
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used to select 20 sites (deep boreholes and springs, as well as shallow boreholes) for the second
sampling event.
Furthermore, 250 ml bottles had been collected from each site during the initial sampling event as
backups; these samples were sent for strontium isotope analysis and the results were used to refine
the final sampling site list.
4.6.3.1.2 Selecting parameters for sampling
Eight widely dispersed locations throughout the Karoo Basin were sampled. At each location, a shallow
cold water (<25 C) borehole, together with a sub-thermal (>25 C) spring or borehole, was sampled.
The following field measurements were taken at each site: temperature, EC, pH and alkalinity.
The parameters selected to be sampled and analysed for were based on three basic components, each
having their own geochemical signature: (1) the host rock (which is predominantly shales);
(2) groundwater of variable compositions (which would depend on the lithology of the aquifers); and
(3) the fracturing fluid introduced into the system.
The following data were collected during the first sampling run from 33 sites:
1. EC, pH, temperature, alkalinity, DO and ORP

2. Major ions
3. Trace elements
4. Rare earth elements (REE)
5. 18 OH2O and DH2O
6. 87 Sr /86 Sr
7. 222 Rn
After analysing the data from the first sampling run, deep and shallow site pairs were identified for
each of the eight areas where more detailed analysis was conducted.
The following data were collected during the second sampling run from the pairs identified in the first
sampling run 20 sites:
1. EC, pH, temperature, alkalinity, DO, ORP

2. Major ions
3. Trace elements
4. 18 OH2O and DH2O
5. 87 Sr /86 Sr
6. 3 H and 14 C
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7. 36 Cl
8. 11 B
9. 226 Ra and 228 Ra
10. 13 C in TIC
11. 13 CCH4
12. 13 CCO2
13. Gases: 222 Rn, 4 He, 3 He, Ar, CH 4 , N2 , O2 , CO2 , H2 S
See Appendix D, Table D 1, for the full list of chemical constituents analysed.
From the second sampling run, all the data was quantitatively and qualitatively assessed to group the
sites into deep mixed and shallow categories.
The deep and shallow groundwater were then characterised and determinants were identified to
differentiate the waters from one another.
4.6.3.1.3 Rationale for sampling and analysing for the selected chemical parameters
In the study, a variety of parameters were used as geochemical tracers and indicators of groundwater
flow. A summary of the rationales mentioned for selecting the different chemical parameters which
were analysed for in the study is provided below.
C h e m i c a l c o n s t i tu e n ts a n d t h e i r r a t i o s
Chemical ratios have been used to differentiate between shallow and deep groundwater as some
chemical constituents will exist in lower concentrations in shallow groundwater due to shorter
interaction times with the host rocks when compared to deep groundwater (Vengosh et al., 2013).
I sotopes
Because environmental tracers are unreactive towards catchment materials, they can be used as
tracers of solutes and water in catchments when compared to most chemical tracers. The isotopes
selected for sampling and analysis were chosen as they can potentially be used to:
characterise different water types;
determine when mixing of water types has occurred;
determine groundwater residence time;
determine the travel times and flow rates of different groundwater types; and
gain a better understanding of the waterrock interactions.
Table 4.2 provides a list of isotopes sampled and analysed for, together with the mentioned rationales
for selecting the specific isotopes (references are provided in the study report).
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TABLE 4.2: LIST OF SAMPLED AND ANALYSED ISOTOPES TOGETHER WITH THE RATIONALE FOR SELECTING THE
SP ECIFIC ISOTOPE(S)
Type of isotope Isotopes Rationale
Stable isotope 18O/16O and 2H/1H Tracers of groundwater flow
ratios To estimate evaporation
To determine the origin of groundwater
11B
To determine the source of groundwater
13C/12C
The ratio is indicative of the source of the carbon
13C in TIC Determine the origin of the carbon
13CCH4 Determine the source of methane
Radiogenic 3He and 4He Tracers of groundwater flow
isotopes To determine residence time
To determine the presence of migrated exogenous fluids
Potential indicator of deep groundwater
87Sr and 86Sr
To distinguish different sources of water
To indicate the lithology through which groundwater has travelled
Radiogenic 14C
To date groundwater up to the age of 40 000 years
isotopes 3H
To distinguish pre-1995 water from younger recharge water
36Cl To determine the recharge date of groundwater
It has a half-life of 301 000 years which makes it useful for identifying
very old water
Its movement is restricted to water in the subsurface
It does not participate in any geochemical or biochemical reactions and
it does not adsorb onto negatively charged silicates
Many aquifers show decreasing 36Cl/Cl ratios with time, which makes ita
useful tracer for subsurface residence time
222Rn To determine the source of groundwater
Dissolved gases
Rationales for sampling and analysis was only mentioned for the dissolved gases presented in Table
4.3. Nitrogen, argon, oxygen and carbon dioxide were also analysed but the data were deemed not be
useful.
TABLE 4.3: LIST OF SAMPLED AND ANALYSED DISSOLVED GASES TOGETHER WITH THE RATIONALE FOR
SELECTING THE GASES FOR ANALYSIS
Dissolved gas Rationale
Hydrogen sulphide (H2S) Indicator of groundwater conditions
Boron (B) Potential indicator of deep groundwater
I n d i c ato rs o f d e e p g r o u n d w at er
In the study, the presence of deep groundwater was assessed using the parameters listed in Table 4.4.
Together with the indicators listed in Table 4.4, the following parameters can also be used as indicators
of deep groundwater: 3 He/4 He, boron, 18 O, 14 C, 3 H, 36Cl (see above text for additional rationales for
sampling and analysing for these parameters).
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It is noted in the report that most of the parameters listed in Table 4.4 relate more to the residence
time rather than the circulation depth and should not be used to indicate deep flow of groundwater
on their own. One of the major reasons for selecting the parameters listed in Table 4.4 is because the
parameters have been used in previous studies to suggest deep flow of groundwater in the Karoo and
elsewhere.
TABLE 4.4: INDICATORS OF DEEP GROUNDWATER
Indicator Rationale
Temperature Groundwater within the Karoo with elevated temperature can be used to indicate a deep
source since there are no significant shallow heat sources.
Sodium (Na +) Groundwater that has been underground for longer periods of time generally have higher Na
concentrations and higher (Na+K)/(Ca+Mg) ratios. This has been recognised in Karoo aquifers.
Magnesium (Mg+) Deep groundwater generally has lower Mg concentrations.
Nitrate (NO3-) If low nitrate groundwater concentrations are found in areas where agricultural activities take
place or in (semi-) arid regions, it may indicate older water which has reduced nitrate levels
due to reducing conditions that developed over the course of time.
Fluoride (F) Kent (1949), as well as Vogel and Talma (1980), reported that warmer groundwater in South
Africa is associated with higher fluoride concentrations . Also, Woodford and Chevallier (2002)
found that sub-thermal, old, groundwater of deep origin is related to elevated fluoride
concentrations.
Lithium (Li) Kent (1949) reported that deeper groundwater had elevated lithium concentration s when
compared to shallower groundwater. Darrah et al. (2014) also indicated that lithium has the
potential to be used as a tracer in shale gas exploration areas.
S a m p l i n g d e vi ce ( s )
The selected sites were suitable for sampling, as they were either flowing springs, boreholes with
existing pumps, or unused boreholes in which a sampling pump could be installed. All the water
samples were collected in the same manner, except for noble gases, radiocarbon, and radon.
Samples for different chemical parameters were collected from the pump discharge. (The sampling
device(s) were not discussed in detail).
S a m p l i n g p r o ce d u re
Before sampling, all the boreholes were pumped or purged for at least 30 minutes, while monitoring
the EC value until it stabilised. This was done to remove any stagnant water from the borehole, and
to ensure that fresh groundwater was sampled. Field alkalinity was determined using the titration
method. (The sampling procedure was not discussed in detail).
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The flowing spring samples were collected in the pools into which the springs discharged. The samples
were collected by using a pump with sampling pipes installed, to collect the samples where the springs
discharged into the pools.
S a mp ling me t hods
The sampling method for the different parameters are as follows (the sampling methods were not
discussed in detail):
Major ions were filtered on-site with 0.45 m cellulose acetate filters and then collected in acid-
washed polypropylene bottles (unknown volume) and kept at <4 C in the field. Cations were
acidified to a pH <2 using ultrapure concentrated nitric acid.
Trace metals were filtered on-site with 0.45 m cellulose acetate filters collected in sample bottles
(of unknown material and volume) and kept at less than 4 C in the field.
Dissolved gases were filtered on-site with 0.45 m cellulose acetate filters collected in sample
bottles (of unknown material and volume) and kept at less than 4 C in the field.
36 C samples were collected in acid-washed high-density polyethylene bottles (unknown volume)
and kept at less than 4 C in the field. They were then filtered in the laboratory during processing.
14 C and 3 H samples were filtered on-site with 0.45 m cellulose acetate filters and then collected
in acid-washed high-density polyethylene bottles (unknown volume) and kept at less than 4C in
the field.
87 Sr/86 Sr and 18 O
H2O samples were filtered on-site with 0.45 m cellulose acetate filters collected
in sample bottles (of unknown material and volume) and kept at less than 4 C in the field.
During sampling, additional 250 ml, and 1 000 ml bottles were collected as backups at each sampling
location.
4.6.3.1.5 Selected sampling frequency
Samples were collected during two seasons, winter and summer, in order to evaluate the seasonal
variations.
During the first season of sampling (summer: March 2014), 33 sites were sampled and analysed for
standard geochemical tracers, which included cations, anions, trace elements, REEs and stable
isotopes of both oxygen and hydrogen. The purpose of these analyses was to assist in selecting which
boreholes and springs should be sampled during the second sampling trip (winter: June/July 2014).
During the second sampling trip, only 20 sites were selected for sampling and were analysed for most
of the geochemical tracers listed in Section 4.6.3.1.2.
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4.6.3.1.6 Selected laboratories
Nine different laboratories were selected to analyse for the different chemical constituents. Different
laboratories analysed for different chemical constituents.
After receiving the data from the second sampling run, all the sampling data were qualitatively and
quantitatively assessed to be able to group or differentiate the sites (springs and boreholes) into deep,
shallow and mixed categories by using Stiff diagrams and cross-plots.
The deep and shallow groundwater were then characterised and determinants were identified to
differentiate these water samples. A guide with limits was then developed for these determinants;
they were then grouped according to their reliability and prioritised for future monitoring
programmes.
4.6.4 Results
The samples were initially grouped according to temperatures measured in the field as either deep
(>25 C) and shallow (<25 C). The two groups were then assessed using a stiff diagram and found that
there are three groups, namely the deep, intermediate, and shallow groundwater. These three groups
all had markedly different 14 C values with the warm groundwater having the lowest values, the
shallow water the highest values and the intermediate groundwater having values in-between the
warm and cold groundwater.
From the three assessments, the groundwater could be classified as deep (sub-thermal and old),
shallow (cold and young) and mixed (hotter and colder than 25 C, with intermediate residence times).
These three groups were then used as a framework to assess the suitability of potential indicators of
deep groundwater.
The following is a description of the major findings of the assessment.
Comparison between 1 8 O and 2 H

By comparing 18 O and 2 H values on an xy plot, a clear distinction between the shallow and deep
groundwater could be seen. The deep groundwater is depleted in heavy isotopes with respect to the
shallow groundwater, with the intermediate/mixed groundwater having values in-between the two.
Comparison between 1 8 O and 1 3 C D IC

The 13 CDIC values do not show a clear distinction between the shallow and the mixed groups, with the
deep groundwater having variable values.
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B and 1 1 B
Overall, the comparison of B and Cl concentrations and 11 B values allowed differentiation of deep
from shallow groundwater, but not mixed from deep groundwater.
8 7 Sr/ 8 6 Sr
The 87 Sr/86 Sr ratios suggested that this determinant might not be a good groundwater depth indicator
in the Karoo Basin.
Nitrate (NO 3 )
Nitrate (NO3 ) had an elevated concentration in shallow groundwater as a result of anthropogenic and
natural factors. Deeper groundwater had either no nitrogen source or the nitrate had already been
removed by bacterial reduction processes.
Fluoride (F ) and lithium (Li)

Fluoride (F) and lithium (Li) concentrations were higher in deeper groundwater compared to shallow
groundwater, which supports the findings by Kent (1949) that higher fluoride and lithium
concentrations are found in deeper hotter groundwater of the MKB.
Chloride and its isotopes

36 Cl cannot be used to accurately differentiate between shallow and intermediate water, and also
between deep and intermediate water as there is a significant overlap of concentrations. However,
36 Cl/Cl is used, a clear differentiation between deep groundwater and other groups emerge with deep
groundwater having lower ratios and shallow groundwater having higher ratios.
Methane and its isotopes

Methane did not have distinct high or low concentrations in the boreholes sampled. Further 13 CCH4
concentration; and 13 CCH4 concentration correlation to C1 /C2+ ratio did not indicate a clear distinction
between shallow and deep groundwater in the Karoo as was expected. It was mentioned by Murray
et al. (2015) that further studies in the MKB were underway to provide more clarity on why the
different sources of methane did not correlate well to the deep and shallow methane classification.
%Na, Mg, V, U, 2 2 2 R n, HCO 3 , pH and H 2 S

%Sodium (Na), magnesium (Mg), vanadium (V), uranium (U), radon (222 Rn), bicarbonate (HCO3 ) , pH
and hydrogen sulphide (H2 S) were found to be a useful differentiator between shallow and deep
groundwater.

The tracers and isotopes used, together with temperature and major ions sampled and analysed for,
indicated that there is generally a clear distinction between sub-thermal and shallow groundwater in
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the Karoo. From the results, a list of parameters could be identified which could be used to
differentiate deep, intermediate and shallow groundwater of which magnesium, %sodium, nitrate,
fluoride, boron, 18 O and 2 H, uranium, alkalinity, pH, temperature, 222 Rn, vanadium, lithium, and H2S
proved most useful. As they are the easiest to obtain, they are cost-effective and can be analysed for
in South Africa. Furthermore, the results show that most sub-thermal groundwater has relatively long
residence times indicating that they are derived from deeper source regions.
4.7 SUGGESTIONS FOR CASE STUDY THREE

Based on the suggested methodology for establishing a groundwater baseline for unconventional gas
projects presented in this dissertation, the following additions are proposed for Case Study Three,
based on the investigation design and the activities that were conducted:
Samples were collected from either flowing springs, boreholes with existing pumps or unused
boreholes in which a sampling pump could be installed. Also, it was stated that samples for
different chemical parameters were collected from the pump discharge. Furthermore, it was
stated that all of the samples were collected in the same manner, except for noble gases,
radiocarbon, and radon. The exact procedures and methods of sample collection are, however,
not known. If it is assumed that all the samples were collected directly from the discharge pump
into the sample bottles, then according to the referenced material in Section 3.9.5.2 of this thesis,
when collecting the groundwater samples, representative samples would not have been collected.
Therefore, in order to collect representative samples for all of the parameters sampled and
analysed for in this case study, it is advised that the sampling procedures and methods suggested
in Section 3.9.5.3 should be followed over the proposed sampling frequency, in order to collect
representative, comparable samples over time. Also, by using the sampling procedures, methods,
and quality control procedures suggested in this thesis, it is believed that analytical errors would
be identified.
Note that this suggestion is based on an assumption that all samples were collected directly from
the discharged pump into the sample bottle, due to lack of information provided in the report on
sampling devices, sampling procedures and sampling methods used, and does not discredit the
findings of this case study.
It is not known what type of pump was used to collect the samples; it is, however, known that the
same pump was used for unused boreholes in which a sampling pump could be installed. If it is
assumed that a piston pump was used for groundwater sampling (which can collect representative
groundwater samples for most chemical parameters at the deepest depth of all the different types
of pumps), it can only be used to collect representative groundwater samples to a depth of 900 m
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(Sundaram et al., 2009). It was, however, reported that samples were collected to depths as deep
as 4 368 m below the surface. Therefore, it is suggested that syringe samplers should have been
used, as they can be used to collect representative groundwater samples for most parameters at
any depth.
Existing pumps were also used in some cases to collect groundwater samples from boreholes at
discharge pipes. These boreholes may have been selected because they were used to correlate
their analytical data to a near deeper borehole or springs. However, these boreholes are not ideal
for collecting groundwater samples as the pumps may have long-lasting effects on the chemistry
of water entering the borehole from the aquifer(s) (Lapham et al., 1997), and therefore not
recommended for collecting representative groundwater samples. It is recommended that if there
were openings in the casing of these pumps along which a device could be lowered that syringe
samplers should have been used to collect representative samples.
During sampling, it was not known from which formation the sampled water originated; therefore
it is recommended that dedicated boreholes should have been drilled into specific
hydrostratigraphic units at different depths, with the casing isolating the units of interest (or
alternatively, at different temperatures according to the classification provided in this case study
for deep, intermediate, and shallow water). In sampling dedicated boreholes would have allowed
accurate determination of deep, intermediate, and shallow groundwater qualities, and allowed
for easier interpretation and comparison of analytical data.
Before sampling, all the boreholes were pumped or purged for at least 30 minutes while
monitoring the EC value until it stabilised. This was done to remove stagnant water from the
borehole. It is suggested that the following field parameters should also have been monitored to
collect representative samples: temperature (C) and pH. Temperature and pH were two of the
parameters of interest for determining if they could be used as deep groundwater depth
indicators; therefore, it is suggested that these parameters should also have been monitored
during the purging process until they stabilised, in order to collect representative samples for
temperature, pH, and all the other parameters to be analysed.
Because samples were only collected in one year during two seasons, it would be difficult to
determine if the differences in the values of chemical constituents were due to seasonal variation
or laboratory bias. Therefore, the sampling frequency which has been suggested in this
dissertation for shallow and deep boreholes is suggested for this case study to accurately evaluate
seasonal variations and provide reasonable quantity ranges for the chemical parameters
suggested to be sampled and analysed for.
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Although 14 C was used in the study to accurately differentiate between the different groundwater
depths from some of the samples collected, not all the samples could be analysed for 14 C due to
budget and logistical constraints. As there are other reliable and cheaper alternatives, it is
suggested that 14 C should not have been analysed for due to these constraints, including the
following:
The 14 C of groundwater can be altered by exchange with rocks. 13 C values for local organic soil,
local aquifer rocks and the local groundwater need to be determined to correct for these
alterations.
This mode of correction has serious drawbacks because the 13 C values vary over a wide range
in soil material and aquifer rocks.
It was reported that in some cases two data sets were produced for the same analytes but from
different laboratories. One of the datasets were from the March sampling event and the other
one from the June sampling event. Mention was made that because of the two different data sets
from two different laboratories, it made it difficult to determine if the differences in values were
due to seasonal variations or due to laboratory bias. Therefore, it is suggested that the same
laboratory should have been used in order to eliminate this bias and be able to effectively assess
the seasonal variations.
A larger number of boreholes should have been sampled and analysed for during the investigation;
this would have assisted in identifying deep groundwater sources in the Karoo, interpreting the
data and drawing conclusions from the results.
It is suggested that deep boreholes need to be drilled into the shale layer, which is of interest for
potential hydraulic fracturing operations, in order to collect representative methane and other
dissolved gas samples. These samples may be used to gain a better understanding of the methane
concentration that would be expected from shale formation water and to be able to establish
C1 /C2+ ratios which would be expected from deep shale groundwater.
It is suggested that conceptual and numerical models of the different sites should have been
created. The models would have assisted in interpreting the data collected, and also to gain a
better understanding of the processes which control the groundwater chemistry; and the features
which control groundwater flow at the sites.
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4.8 DISCUSSION
In this section the shortcomings and areas where the established baseline methodology could have
been improved based on the practices and the results or findings of the case studies, are listed. These
improvements should essentially be incorporated into the established groundwater baseline
methodology.
4.8.1 Case Study One

From the practices and the results or findings of Case Study One, the following are deemed to be of
most significance with respect to groundwater baseline establishment for unconventional gas
projects:
In order to establish groundwater baseline quantity ranges for specific parameters analysed for,
the average and standard deviation concentrations for the analysed parameters should be
calculated to establish the range of concentrations to expect for the parameter analysed for,
which is lower, average, and upper concentration range. It was, however, suggested in this
dissertation that the upper and lower concentrations of a specific parameter should be used to
establish ranges for the specific parameters analysed for. By using the average and standard
deviation to calculate the upper and lower quantity ranges for a specific parameter analysed for,
would aid in decreasing the impact that human sampling error, laboratory analysis errors, and
anomalies may have on the data, therefore providing more reasonable, representative
groundwater baseline quantity ranges for parameters analysed for.
PDBs can be installed in boreholes were increased groundwater flow is suspected to occur (due to
possible fracture or fault at depth) based on packer test results, by comparing the downhole fluid
profiles of the boreholes before and after aquifer tests, to be able to establish the variability of
groundwater chemistry amongst the different geological formations at the site and to determine
where different aquifer systems may be present.
Geochemical sampling can be conducted during the geological field visit. The samples can be used
to assess the likely influence of the materials on the quality of drainage from the UCG processes.
By geochemically assessing the samples, it can be determined which inorganic parameters are
most likely to be present in the UCG formation and produced water.
It is essential to determine which aquifer system is mostly utilised in the area, as this aquifer is the
most important potential groundwater contaminant receptor due to unconventional gas
operations.
259
It is necessary to determine which formations/lithologies act as aquicludes as the
formations/lithologies may potentially prevent potential contaminant transport from the burn
zone to upper potable groundwater resources. This information is required for numerical
modelling purposes.
4.8.2 Case Study Three

From Case Study Three, the following findings are deemed to be of most significance with respect to
groundwater baseline establishment for unconventional gas projects:
The following determinants can be used to differentiate deep from shallow groundwater
accurately:
18 O and 2 H, B and 11 B14 C, alkalinity, pH, magnesium, %sodium, fluoride and uranium can
be used to differentiate between deep and shallow groundwater and determine if there is any
interconnection between the deep and shallow groundwater sources.
Table 4.5 presents the four groups which can be considered to differentiate deep groundwater
from shallow groundwater. Groups 13 should be the first choice in any groundwater baseline
establishment and monitoring programme in the MKB, with Group 1 having the highest priority.
These groups are aimed at identifying areas of deep groundwater flows.
From this table, the following parameters were chosen as the most useful, as they are the easiest
to obtain, they are cost effective, and can currently be analysed for in South Africa:
Magnesium, %sodium, nitrate, fluoride, boron, 18 O and 2 H, uranium, alkalinity and pH,
temperature, 222 Rn, vanadium, lithium and H 2 S.
TABLE 4.5: P RIORITISATION OF DETERMINANTS FOR IDENTIFYING DEEP GROUNDWATER
Group Determinants
Group 1 14C, 18O, fluoride, %sodium, magnesium, uranium, alkalinity
Group 2 Boron, vanadium, lithium, 11B, 36Cl/Cl, 222Radon, H2S
Group 3 Sodium, pH, tritium, nitrate, temperature, 4He, 3He/4He, CH4
Group 4 87Sr/86Sr, 13C, rare earth elements, other trace elements
It is recommended to analyse for all the determinants in Table 4.5 when aiming to identify deep
groundwater sources (even though 13 CCH4 did not indicate a clear distinction in the Karoo as was
expected) and distinguish deep groundwater from shallow groundwater.
87 Sr/86 Sr ratios and 13 CDIC are not good groundwater depth indicators or differentiators in the
MKB and are not suggested to be sampled and analysed for during groundwater baseline
establishment project for unconventional gas projects in the MKB.
260
Nitrate may be analysed for during groundwater monitoring at hydraulic fracturing operations,
where fresh surface water may be used during hydraulic fracturing treatment processes, to
indicate that the fresh groundwater migrated from the production zone into the surrounding deep
strata.
The deep groundwater indicators may be used during groundwater monitoring at unconventional
gas projects to indicate that preferential flow features may have been created due to
unconventional gas activities, such as fracture creation in the overlying strata connecting
concentrations of, for example, deep high concentrations fluoride and lithium groundwater to
shallow, low fluoride and lithium concentrations groundwater (if it was found during groundwater
baselines establishment that the shallow groundwater had low fluoride and/or lithium
concentrations).
36 Cl/Cl ratios can be used to accurately differentiate between shallow and deep groundwater;
therefore, if groundwater monitoring values differ considerably with groundwater baseline ratios,
it may indicate that groundwater contamination occurred due to unconventional gas activities and
that preferential flow features such as fractures may have been created.
Although 4He and 3He 11B 36Cl/Cl may be used to differentiate between shallow and deep water to
varying extents, there are other more cost-effective alternatives which can be analysed for in
South Africa.
The results of the study indicated that methane and its isotopes cannot be used to clearly
distinguish between shallow and deep groundwater of the Karoo.
If possible, instead of establishing groundwater quantity ranges for each hydrostratigraphic group
as suggested in Section 3.10, of the suggested baseline establishment methodology, only three
groups should be used based on the depth of the groundwater: shallow, medium, and deep. This
would decrease drilling costs by not having to install boreholes into each hydrostratigraphic unit.
These three groups can be distinguished from each other by using the determinants listed in Table
4.5. The three depth categories are suggested in Murray et al. (2015) as:
Shallow: Cool (<25 C) groundwater with a chemistry that indicates shallow circulation and
no obvious blending with deeper sources.
Deep: Warm (>25C) or cool groundwater with a chemistry that is clearly different from
shallow groundwater and includes indicators of long residence times and/or deep flow.
Mixed: Cool or warm groundwater that contains indicators of both shallow and deep
groundwaters.
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When establishing a groundwater baseline that only the isotopes listed in Table 4.5 need to be
sampled and analysed for, because these isotopes have previously been recognised to suggest
deep flow of groundwater in the Karoo and elsewhere.
Interconnection between the shallow groundwater and deep groundwater already existed (before
shale gas development) and may potentially serve as pathways for contaminant transport during
or after hydraulic fracturing and UCG operations.
A modified list of chemical parameters suggested to be analysed for during groundwater baseline
establishment for hydraulic fracturing and UCG projects is presented in Appendix D, Table D 1. The
modified list is based on:
the practices and findings of Case Study Three;

the rationales for selecting and analysing the different chemical parameters in Case Study Three;
and
the rationales for selecting the different suggested chemical parameters to be analysed for in this
dissertation.
4.9 CONCLUSION
In this section the investigation sequence, practices and the results/findings of three case studies
which covered different aspects of groundwater baseline establishment for unconventional gas
projects in South Africa were reviewed. Suggestions on how the case studies could have been
improved, were provided.
After the suggestions were provided, the practices and the results or findings were reviewed to
determine if the established baseline methodology could be improved. From the discussion section,
it could be seen that the practices and the results or findings of Case Study One cannot be used to
modify the investigation sequence of the established baseline methodology. However, the practices
and the results or findings of Case Study One listed in the discussion section could be used to refine
the established baseline methodology. None of the practices and results or findings of Case Study Two
could be used to refine, improve or modify the established baseline methodology. The findings of Case
Study Three could be used to modify and refine the chemical parameters suggested to be analysed for
in the established baseline methodology.
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Chapter 5
CONCLUSION AND RECOMMENDATIONS
Since conventional natural gas resources are steadily being depleted internationally, and due to the
prospects of increased gas production by utilising technology such as hydraulic fracturing and UCG,
unconventional natural gas has become one of the main exploration targets in recent years.
Unconventional natural gas development has a number of claimed benefits, such as job creation, and
also a number of risks, of which the biggest concern is the potential risk of unconventional natural gas
technologies polluting the potable groundwater in the area of development. This risk has led to the
call for establishing a groundwater baseline before any unconventional gas activities take place.
Establishing a groundwater baseline has a number of advantages such as (a) helping to resolve
disputes regarding the causes of groundwater contamination; and (b) early detection of changes in
natural water quality and quantity trends due to unconventional gas activities, which can be used to
design appropriate management and mitigation systems before adjacent groundwater users are
impacted.
The main aim of the study was to construct a standard methodology which may be used as a guideline
to establish a groundwater baseline prior to unconventional gas development projects in South Africa,
specifically for hydraulic fracturing and UCG operations.
To construct the methodology, literature which covers different topics applicable to establishing a
groundwater baseline for unconventional gas projects were extensively reviewed. Also, by reviewing
the literature, it is believed that the different questions which this study aimed at answering, such as
which chemical parameters to analyse for, have received reasonable solutions.
It is, however, recommended that the methodology be to be tested prior to actual hydraulic fracturing
and UCG operations to determine if the methodology can be used effectively to acquire high-quality
data, while being both cost-effective and practical.
Based on the findings and limitations of the study the followings recommendations are made for
future and further investigations:
It is recommended that future baseline investigation studies focus on establishing groundwater

baseline methodologies specifically for CBM and tight gas extraction techniques.
It is recommended that future baseline investigation studies take into account the fate and
transport and physiochemical properties of specific chemicals, as it would aid in determining the
263
distance and depth from the wellpad to sample for specific chemicals after the chemicals have
been released into the subsurface via different preferential flow paths.
As drilling fluids may potentially contaminate the groundwater resources during drilling of
exploration, injection and production wells, a more detailed literature review or study should be
conducted to determine which chemicals may potentially be used, and to add these chemicals to
the list of chemical parameters to analyse for when establishing a groundwater baseline for
unconventional gas projects.
Although a sampling frequency was proposed, it is recommended that future investigations focus
more on determining when to sample and analyse for specific parameters, because some
parameters are more variable with time due to seasonal variations, whereas other remain
relatively unchanged over long periods of time and therefore require lower sampling frequencies.
More studies should be undertaken on the distance to which groundwater contaminants may
migrate through preferential flow features from the wellpad area. The information can be used to
modify the suggested local baseline study size of 5 km radius from the hydraulic fracturing and
UCG wellpad areas.
More attention should be given to surface water sample collection when establishing a
groundwater baseline as surface water may potentially contaminate the groundwater resources
through seepage of contaminants from the surface water to the groundwater resources through
the overlying strata.
Figure 5.1 illustrates the suggested sequence of activities which should be undertaken to establish a
groundwater baseline for hydraulic fracturing and UCG operations in South Africa. From the diagram
it can be seen that the activities are presented together with the sections which should be referred to
when undertaking a specific activity.
264
Figure 5.1: Flow diagram for establishing a groundwater baseline for hydraulic fracturing and underground coal gasification operations
265
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292
Appendix A
SUMMARY OF POTENTIAL CONTAMINATION
POTENTIAL CONTAMINATION DUE TO SURFACE HANDLING AND TRANSPORTATION ISSUES

RELATED TO HYDRAULIC FRACTURING OPERATIONS
Table A 1 presents a summary of the potential issues related to surface handling and transportation
issues related to hydraulic fracturing operations. The numbers in Table A 1, for example 1(A) under
the column pathway corresponds to the number in Figure 5.1. The figures serves to illustrate the
migration pathways of the contaminants due to a specific potential impact. The green lines indicate
migration of mostly fluids and the purple lines indicate migration of mostly gases according to the
literature reviewed.
Under the worst-case scenario all of these different fluid spills and leaks can penetrate the soil and
reach the groundwater resources through infiltration into the subsurface through fractures and
macrospores. The spills may also reach surface water bodies such as rivers or stream, via overland
flow and seep into the groundwater if the stream is a losing/influent stream (Bamberger and Oswald,
2012; CCA, 2014; Folkes, 1982; Krupnick et al., 2014; Rozell and Reaven, 2012; Wang et al., 2014).
TABLE A 1 : SUMMARY OF POTENTIAL CONTAMINATION, DUE TO SURFACE HANDLING AND TRANSPORTATION

ISSUES, RELATED TO H YDRAULIC FRACTURING O P ERATIO NS
Potential impact
on drinking Concern Pathway References
water resources
Spills on the Drinking water resource 1(A) Surface runoff to surface water (CCA, 2014; Gross et al., 2013;
drilling site contamination from spills from bodies and infiltration of Krupnick et al., 2014; NYSDEC, 2011;
storage tanks due to ruptures, contaminants through overlying Peduzzi and Harding Rohr Reis,
improper operations, human strata into the groundwater 2013; Rozell and Reaven, 2012;
error, equipment failures, resource. USEPA, 2015b; Vidic et al., 2013;
overfills, vandalism, accidents, Wang et al., 2014)
and ground fires.
Drilling site surface 1(B) Surface runoff from leaks from (Bamberger and Oswald, 2012;
contamination from pond leaks. the side of the pond to surface CCA, 2014; Folkes, 1982;
Drinking water resource water bodies. Krupnick et al., 2014; Rozell and
contamination due to leaks and Overflow from the ponds. Reaven, 2012; Wang et al., 2014)
overflows from lined retention Infiltration of contaminants through
ponds which may contain overlying strata into the
flowback and produced water. groundwater.
Drilling mud seepage from 1(C) Seepage through surface pits (Haris et al., 2013)
surface pits. and infiltration through overlying
Drilling mud is kept at the formations.
surface in mud pits, which are
open to the environment.
If seepage occurs, it can change
the composition of underground
water beneath that pit.
Blowouts may occur during 1(D) Surface runoff to surface water (USEPA, 2015b)
production phase, and cause bodies and infiltration of
spills on the surface which may contaminants through overlying
contaminate drinking water strata into the groundwater
resources. resource.
293
Potential impact
on drinking Concern Pathway References
water resources
Produced water and flowback 1(E) Seepage through surface pits (Gwpc and Iogcc, 2014)
water are transported from the and infiltration through overlying
wellhead to storage tanks or pits, formations.
through pipes, spills could occur
due to faulty pipe connections at
either end.
Fluid spills on the surface 1(F) Surface runoff to surface water (Malone and Ely, 2007)
because of hose and line failure, bodies and infiltration of
due to damaged inlet and outlet contaminants through overlying
connections, general wear and strata into the groundwater
tear with age, damage to resource.
washers, and erosion of high
pressure flow lines.
Spills due to blender 1(G) Surface runoff to surface water (Halliburton, 1988; Malone and
malfunction. Blender bodies and infiltration of contami- Ely, 2007)
malfunction due to excessive nants through overlying strata into
flow rates during treatment. the groundwater resource.
Spills due to improperly tested 1(H) Surface runoff to surface water (Malone and Ely, 2007)
parts on the manifold ends. The bodies and infiltration of
manifold has different com- contaminants through overlying
ponents that need to be installed strata into the groundwater
manually; if these components resource.
are installed incorrectly and not
pre-tested the components are
more likely to break.
Spills from high-pressure pump 1(I) Surface runoff to surface water (Company, 2009; Upstream,
trucks. Large pump trucks are bodies and infiltration of 2015)
able to move greater volumes of contaminants through overlying
fluids, with the downside that strata into the groundwater
larger volumes may be spilled if resource.
failure occurs.
Smaller pump trucks require
more maintenance, therefore
there is an increased possibility
of human error which could
potentially cause a spill.
Spills and leaks from the 1(J) Surface runoff to surface water (Halliburton, 1988; USEPA,
wellhead. With time the bodies and infiltration of 2015b)
wellhead may become damaged contaminants through overlying
by highly pressurised abrasive strata into the groundwater
fluids. Cracks in the wellhead resource.
may allow the leakage of fluids.
Spills away from Transportation spills of flowback 2(A) Surface runoff, or direct spills (CCA, 2014; Krupnick et al., 2014;
the drilling site water, produced water, into surface water bodies, Peduzzi and Harding Rohr Reis,
fracturing fluid away from the Infiltration of contaminants through 2013; Rozell and Reaven, 2012;
site, via trucks and pipes, due to overlying strata into the Schmidt, 2011; USEPA, 2015b)
accident, may reach rivers, dams, groundwater.
and streams and contaminate
the surface water resources.
Infiltration of transportation
spills into the ground which may
reach the groundwater and
contaminate the groundwater
resources.
294
Figure A 1: Potential contamination due to surface handling and transportation issues. Corresponds to Table A1: 1(A) to 1(D)
295
Figure A 2: Potential contamination due to surface handling and transportation issues. Corresponds to Table A1: 1(E) to 2(A)
296
POTENTIAL CONTAMINATION DUE TO WASTEWATER MANAGEMENT AND DISPOSAL ISSUES
RELATED TO HYDRAULIC FRACTURING OPERATIONS
Table A 2 presents a summary of the potential issues related to wastewater management and disposal
issues related to hydraulic fracturing operations. The numbers in Table A 2, for example 1(A) under
the column pathway corresponds to the number in Figure A 3. The figures serve to illustrate the
migration pathways of the contaminants due to a specific potential impact. The green lines indicate
migration of mostly fluids and the purple lines indicate migration of mostly gases according to the
literature reviewed.
Under the worst-case scenario all of these different waste management and disposal methods may
contaminate the groundwater, either directly, such as deep well injection, or indirectly through
discharged wastewater from streams which reach the groundwater (Kaushal et al., 2005; Krupnick et
al., 2014; Peduzzi and Harding Rohr Reis, 2013; Pettyjohn, 1982; Rozell and Reaven, 2012; USEPA,
2015b).
TABLE A 2: SUMMARY OF POTENTIAL CONTAMINATION DUE TO WASTEWATER MANAGEMENT AND DISPOSAL

ISSUES RELATED TO HYDRAULIC FRACTURING OPERATIONS
Potential impact
on drinking water Concern Pathway References
resources
Leachate from The drill cuttings can contain 1(A) Surface runoff to surface water (Resnikoff et al., 2010)
disposed formation fluid and radioactive bodies and infiltration of
radioactive drill material such as Radium-266. contaminants through overlying
cuttings During precipitation, the strata into the groundwater
radioactive material can become resource.
mobilised and leach into the soil,
or reach surface water bodies
through overland flow.
Deep well Deep disposal of wastewater into 2(A) Leaky disposal wells. (CCA, 2014; Rozell and Reaven,
injection of used injection wells can contaminate 2012)
fracturing fluid groundwater through leaky
wells, seals and high injection
pressures.
Discharge of These wastewater treatment 3(A) The fluid/water may be directly (Blauch et al., 2009; Krupnick et
flowback and facilities are not designed to injected into the streams from the al., 2014; Rozell and Reaven,
produced water handle high concentrations of municipal wastewater treatment 2012; USEPA, 2015b; Warner et
to streams from salts or radioactivity associated facility. al., 2013)
municipal and with hydraulic fracturing
industrial wastewater.
wastewater After standard treatment, the
treatment fluid/water may be discharged
facilities into streams.
Land application When treated, wastewater such 4(A) Surface runoff to surface water (Kaushal et al., 2005; Krupnick
of wastewater as produced water is applied to bodies and infiltration of et al., 2014; Peduzzi and Harding
the land, it may still contain high contaminants through overlying Rohr Reis, 2013; Pettyjohn, 1982;
concentrations of total dissolved strata into the groundwater Rozell and Reaven, 2012; USEPA,
salts (TDS). resource. 2015b)
It may also be used as road salts.
Direct discharge Untreated wastewater can be 5(A) Direct discharge of untreated (Hammer et al., 2012)
of untreated discharged directly into streams wastewater into streams and rivers,
wastewater into without undergoing proper and infiltration of contaminants
rivers treatment. through overlying strata into the
groundwater resource.
297
Potential impact
on drinking water Concern Pathway References
resources
Direct discharge There have been reports of 6(A) Surface runoff to surface water (Warner et al., 2013)
of untreated outfalls of wastewater at the bodies and infiltration of
wastewater into treatment plants. contaminants through overlying
rivers strata into the groundwater
resource.
Disposal of Constituents from drilling waste 7(A) Infiltration through overlying (Onwukwe and Nwakaudu, 2012)
drilling waste on can infiltrate the groundwater layers into the groundwater
site resources. resource.
298
Figure A 3: Potential contamination due to wastewater management and disposal issues. Corresponds to Table A2: 1(A) to 4(A)
299
Figure A 4: Potential contamination due to wastewater management and disposal issues. Corresponds to Table A 2: 5(A) to 7(A)
300
POTENTIAL CONTAMINATION DUE TO WELL-RELATED ISSUES RELATING TO HYDRAULIC
FRACTURING AND UNDERGROUND COAL GASIFICATION OPERATIONS
Table A 3 presents a summary of the potential well-related issues relating to hydraulic fracturing and
UCG operations. The numbers in Table A 3, for example, 1(A) under the column pathway,
corresponds to the number in Figure A 5.
TABLE A 3: SUMMARY OF POTENTIAL CONTAMINATION DUE TO WELL-RELATED ISSUES RELATING TO

HYDRAULIC FRACTURING OPERATIONS
Potential
impact on
Hydraulic fracturing
drinking Concern Pathway UCG references
references
water
resources
Well casing Migration of gas and fluids from 1(A) Through (Davies et al., 2014; (Bahl et al., 2014;
leaks leaky wells, or into leaky corroded Groat and Grimshaw, Burton et al., 2006;
damaged wells which may casing/tubing. 2012; Jackson et al., Moorhouse et al., 2010;
contaminate the potable 2013; Rozell and Wobus and Ritter,
groundwater resources and Reaven, 2012; Xu et al., 2010)
surface water bodies. 2006)
1(B) Along a sheared (Davies et al., 2014; (Bahl et al., 2014;
If land subsidence occurs during wellbore and/or Groat and Grimshaw, Burton et al., 2006;
UCG operations, well integrity casing. 2012; Jackson et al., Moorhouse et al., 2010;
failure may occur which may 2013; Rozell and Wobus and Ritter,
release production gases and Reaven, 2012; Xu et al., 2010)
contaminants into the potable 2006)
groundwater resources. 1(C) Along bursts. (USEPA, 2015b) (Bahl et al., 2014;
Burton et al., 2006;
Moorhouse et al., 2010;
Wobus and Ritter,
2010)
1(D) Along stretches. (USEPA, 2015b) (Bahl et al., 2014;
Wobus and Ritter,
2010)
1(E) Along collapsed (USEPA, 2015b) (Bahl et al., 2014;
areas. Burton et al., 2006;
Wobus and Ritter,
2010)
1(F) Along bends. (USEPA, 2015b) (Bahl et al., 2014;
Wobus and Ritter,
2010)
Incorrect Stray gas migration through drilled 2(A) Abandoned (CCA, 2014; Celia et al., (Sury et al., 2004)
construc- gas wells that have been abandoned leaking wells. 2005; IOGC, 2008)
tion and not properly plugged. The wells
practices may serve as conduits for stray gas
to migrate from the production
zone or shallower shale units to
groundwater aquifers or to surface
water bodies.
Drilling mud is not cleaned from 2(B) Mud channels- (Celia et al., 2005;
the hole before cementing. If through the central Dusseault et al., 2000)
drilling mud is not properly portion of the annulus,
cleaned from the hole before or along the cement
cementing, the mud channels formation interface.
301
Potential
impact on
references
water
resources
may allow gas migration and
contaminate the groundwater
resource.
During cementation, the casing 2(C) Gaps between the (CCA, 2014)
was not centralised in the casing and the
borehole, this prevented cement surrounding formation.
to penetrate right around the
well; therefore, there would be
no insulation between the casing
and the surrounding formation,
which may serve as a possible
pathway for gas migration to the
surrounding rock formation if gas
were to migrate through a
damaged/leaky casing.
Drilling fluid contaminating the 2(D) Through porous (Brufatto et al., 2003;
groundwater resources during and permeable layers. Haris et al., 2013)
drilling.
Pressure within the annulus falls
right after cementa-tion due to
fluid loss to the surrounding
formation.
Surface casing does not extend to 2(E) Through leaky (USEPA, 2015b)
the base of the drinking water intermediate casing.
resource; the groundwater
resource is more vulnerable to
contamination if the
intermediate casing is leaky.
When wells are too close to each 2(F) Connection (ERCB, 2012) (Moorhouse et al.,
other, the induced fractures of between induced 2010)
one well can communicate with fractures of adjacent
the induced fractures of the wells.
adjacent well.
For instance, in the case of
hydraulic fracturing when a
horizontal well is drilled too close
to a production well. The
hydraulic fracture stimulation in
the horizontal well can cause
fluids and gases to migrate to the
induced fractures of the
production well; this can lead to
unintended discharge of fluids,
gas, sand or mud into the
groundwater resource,
intermediate zone aquifers and
onto the surface.
Gas Hydration or drying of the 3(A) Cracks within the (BAPE, 2011; Brufatto
migration cement can result in crack annulus. et al., 2003; CCA, 2014;
up the development within the annulus Dusseault et al., 2000)
annulus which could serve as a possible
pathway if gas migration through
a damaged/leaky casing would
occur, and also for stray gas
migration from the production
zone and intermediate zone into
302
Potential
impact on
references
water
resources
a groundwater resource and
surface water body.
Cement may crack because of
repeated pulses of high pressure
during hydraulic fracturing.
The cement in the annulus may
shrink because it is not of
adequate thickness to prevent
cracking during hydration or as a
result of drying.
Gas may migrate through gas 3(B) Through gas (Brufatto et al., 2003;
pockets and channels. Gas pockets and channels in Watson, 2004)
pockets and channels were the cement.
formed during cementation
when migrating gas was caught
in the cement.
Not enough cement was used 3(C) Gaps between the (CCA, 2014)
between the casing and the casing and the
surrounding formation to reach surrounding formation.
the appropriate depth; gas
migration into the groundwater
resource through leaky casings
may occur.
The cement did not properly 3(D) Gaps between (CCA, 2014)
bond to the casing and/or to the casing and cement or
surrounding environment. gaps between the
Because the bonding between surrounding formation
the casing and the surrounding and cement.
formation was not effective, gaps
could exist along the interface
between the cement and the
casing or the cement and the
surrounding formation, which
could serve as a possible
pathway for stray gas migration
into the groundwater resource.
During well drilling micro- 3(E) Micro-fractures in (Eklund and Stille,
fractures are created in the the surrounding rock 2008)
surrounding rock formation; the formation.
annulus cement is not expected
to fully seal these micro-fractures
because of the large grain size of
the cement, the areas that are
not fully sealed may offer
pathways for slow upward gas
migration towards a
groundwater resource and to the
surface.
Inadequately cemented casing in 3(F) Along the annulus (Bair et al., 2010)
a hydraulically fractured well can from the deep zone.
contribute to the built-up of gas
causing high pressures along the
outside of the production well.
This could ultimately result in
movement of natural gas into
local groundwater resources.
Fractures from the production 3(G) Across the (Davies et al., 2014;
zone might reach the cement cement outside the Groat and Grimshaw,
303
Potential
impact on
references
water
resources
outside the production casing casing and then 2012; Jackson et al.,
and fracture the cement, which between the cement 2013; Rozell and
might create possible pathways and the casing. Reaven, 2012)
for fluid and gas to migrate out of
the deep zone to the
Pressure within the annulus falls 3(H) Along porous (Brufatto et al., 2003)
right after cementa-tion due to and permeable
fluid loss to the surrounding formations.
formation. Gas may invade 3(I) Gas pockets and (Brufatto et al., 2003)
creating channels through which channels.
gas can flow. Further reduction in 3(J) Along gaps (Brufatto et al., 2003)
volume creates gaps through between the casing
which gas can migrate. and cement, and gaps
The lost fluid from the cement between the cement
may contaminate groundwater and the surrounding
resources directly. Furthermore, rock formation.
groundwater resources can be
contaminated by migrating gas.
Hydrostatic pressure of the 3(K) Fractures in the (Rogers et al., 2004)
cement is too high, causing surrounding
fractures in the surrounding formation.
formation through which the
cement slurry can migrate to the
Unforeseen Drilling into a rock formation that 4(A) Movement of (Vidic et al., 2013)
accidents contains pre-existing high annular gas either
during pressure native gas. through or around the
drilling The high-pressure gas can have cement sheath.
deleterious effects on the
integrity of the outer cement
annulus in the upper portion of
the wellbore, such as creation of
micro-channels through which
gas may migrate out of the well
either through or around the
cement sheath into a
Drilling may open surficial fractures 4(B) Movement of (Gorody, 2012)
that may possibly allow pre-existing annular gas through
native gas to leak into water fractures into
wells. groundwater
resources.
Drilling into a rock formation 4(C) Uncemented (Howarth et al., 2011;
containing pre-existing high annulus. Kelly et al., 1985;
pressure native gas. USEPA, 2015b; Vidic et
The gas could move upward along al., 2013)
the uncemented annulus into
overlying formations. As a result,
near-surface groundwater can be
contaminated with large
amounts of methane.
Shutting in gas before the annular 4(D) Cracks and (LIU et al., 2007)
gas is vented sufficiently. opening along the
annulus.
304
Figure A 5: Potential contamination due to well-related issues. Corresponds to the pathway numbers listed in Table A 3
305
306
307
POTENTIAL CONTAMINATION DUE TO ISSUES RELATED TO UNDERGROUND COAL GASIFICATION
Table A 4 provides a summary of the potential contamination issues unique to UCG operations. The
numbers in Table A 4, for example, 1(A) under the column pathway, corresponds to the numbers in
Figure A 8
TABLE A 4: P OTENTIAL CONTAMINATION OF GROUNDWATER RESOURCES UNIQUE TO UNDERGROUND COAL
GASIFICATION OPERATIONS
Potential
impact on
Concern Pathway UCG references
groundwater
resources
Air and oxygen The high pressure may fracture the 1(A) Induced fractures in (Burton et al., 2006; LIU
are injected overlying strata, which causes some of the overburden. et al., 2007)
under high the gasification products to be lost to the
pressure into surrounding permeable media.
the gasification
zone.
After coal These by-products of gasification contain 2(A) Faults, fractures and (Creedy et al., 2001; LIU
gasification, contaminants which may be leached out other preferential flow et al., 2007)
solid residue by groundwater influx. paths.
(char and ash)
and tar is left in
the cavity.
Land When land subsidence occurs , fractures 3(A) Faults and fractures. (Burton et al., 2006;
subsidence are formed (or opened) in the Creedy et al., 2001; LIU
occurs due to overburden and faults may form next to et al., 2007)
cavity cave-in. the subsidised overburden. These faults 3(B) Faults and fractures (Burton et al., 2006; LIU
and fractures may be connected to connected to preferential et al., 2007)
groundwater resources or interconnect geological flow features.
with other preferential flow paths which 3(C) Faults and fractures (Burton et al., 2006; LIU
may be connected to groundwater connected to leaky casings et al., 2007)
resources. or fractured casing cement.
High injection When the pressure inside the gasification 4(A) Fractures in the (Burton et al., 2006;
pressures are zone is increased above the pressure of overburden. Shafirovich and Varma,
required to the surrounding groundwater (to prevent 2009; Verma et al.,
displace cavity the influx of groundwater into the 2014)
water. gasification zone), it could cause fracture
dilation, crustal uplift and induce
fractures. These fractures may serve as
pathways for fluid and gas migration out
of the gasification zone and towards
groundwater resources.
Pressure The produced CO2 in the gasification 5(A) Preferential flow (Burton et al., 2006)
increase in the chamber would remain supercritical and features such as faults,
cavity due to buoyant. This may create an upward fractures and leaky wells.
CO2 free-phase pressure on the cavity. The CO2 may
build-up. escape through preferential pathways
into the groundwater resources.
The injection The linkage can be done by hydraulic 6(A) Fractures, faults, and (Bahl et al., 2014; Bhutto
well and fracturing the coal seam to create a leaky casings. et al., 2013; Blinderman
production well connection through fractures. These et al., 2008; Creedy et
needs to be fractures may connect to naturally al., 2001)
linked within occurring factures or leaky wells, which
the coal seam, are connected to groundwater resources.
in order to
collect the
produced
syngas.
308
Figure A 8: Potential contamination of groundwater resources unique to underground coal gasification operations. Corresponds to Table A 4: 1(A) to 6(A)
309
POTENTIAL CONTAMINATION DUE TO GEOLOGY-RELATED ISSUES FOR
HYDRAULIC FRACTURING AND UNDERGROUND COAL GASIFICATION OPERATIONS
Table A 5 provides a summary of potential contamination due to geology-related issues for hydraulic
fracturing and UCG operations. The numbers in Table A 5, for example, 1(A) under the column
pathway, corresponds to the numbers in Figure A 9 and Figure A 10.
Note that potential contamination pathways through geological-related issues are only illustrated on
a schematic cross-section for hydraulic fracturing operation. The principal, however, stays the same
for UCG operations. Furthermore, if the UCG references row does not contain a reference for a specific
geological pathway and/or concern, the reference could not be found. It, however, does not mean
that the pathway and/or concern does not exist.
TABLE A 5: SUMMARY OF POTENTIAL CONTAMINATION, VIA GEOLOGY-RELATED ISSUES ASSOCIATED WITH

HYDRAULIC FRACTURING AND UNDERGROUND COAL GASIFICATION OPERATIONS
Potential impact Hydraulic
Number
on drinking water Concern Pathway fracturing UCG references
on model
resources references
Contaminant 1 Migration fluid (A) Fracture or shear (Lavoie et al., (Burton et al., 2006;
fluid and/or gas and/or gas into that intercepts a 2014; Myers, Shafirovich and Varma,
migration groundwater and leaky well, or is the 2012; Rozell and 2009; Sury et al., 2004;
through fractures. surface water cause of the leaky Reaven, 2012; Verma et al., 2014)
resources. well, and is RSA DMR, 2012;
connected to a USEPA, 2015b)
groundwater
resource.
(B) Induced fractures (Lavoie et al., (Burton et al., 2006;
or faults that 2014; Myers, Moorhouse et al., 2010;
propagate from the 2012; Rozell and Shafirovich and Varma,
production zone Reaven, 2012; 2009; Sury et al., 2004)
through the overlying RSA DMR, 2012;
strata towards the USEPA, 2015b)
potable groundwater
resource.
(C) Induced fractures (Lavoie et al., (Burton et al., 2006;
that connect to 2014; Myers, Shafirovich and Varma,
naturally occurring 2012; Rozell and 2009; Sury et al., 2004)
secondary fractures Reaven, 2012;
in the overlying strata RSA DMR, 2012;
that are connected to USEPA, 2015b)
a groundwater
and/or surface water
resource.
(D) Fractures created (USEPA, 2015b) (Burton et al., 2006;
during hydraulic Shafirovich and Varma,
fracturing may 2009)
intersect nearby wells
or their fracture
networks resulting in
the flow of gases and
fluids into those
wells.
(A) Opened-up pre- (USEPA, 2011) (Sury et al., 2004)
existing fractures due
hydraulic fracture
stimulation, and as a
results of air injection
310
Number
on model
during UCG
operations.
(F) Migration of gas (Lavoie et al., (Burton et al., 2006;
from the production 2014; Myers, Shafirovich and Varma,
zone along the 2012; Rozell and 2009)
cement annulus into Reaven, 2012;
secondary fractures RSA DMR, 2012;
which are connected USEPA, 2015b)
to the groundwater
resource.
(G) Induced fractures (Myers, 2012) (Sury et al., 2004)
intersecting
abandoned gas wells.
(H) Upward gas (CCA, 2014;
leakage along faults Gorody, 2012)
and fractures due to
hydraulic fracturing
stimulated
earthquakes, slight
distortion of the rock
mass or drilling.
(I) Faults connected (Vidic et al., 2013) (Sury et al., 2004)
to abandoned wells;
the wells may serve
as natural conduits
for upward
contaminant
transport.
(J) Extensional (CCA, 2014)
fractures from the
production zone
which are caused by
fluid injection into
the shale zone.
Gas migration 2 The dolerite (A) Fractures along (Rowsell and De (Shafirovich and Varma,
through intrusions, dykes and dolerite dykes and Swardt, 1976; 2009; Sury et al., 2004;
preferential sills are possible sills. RSA DMR, 2012; Wobus and Ritter,
pathways pathways for Talma and 2010)
contaminant fluid Esterhuyse, 2013)
towards groundwater
and surface water
resources.
Breccia pipes are (B) Along the baked (Jamtveit et al., (Jamtveit et al., 2004;
possible pathways for fractured bedrock 2004); (Svensen Sury et al., 2004;
contaminant fluids next to the breccia et al., 2007) Svensen et al., 2007;
towards groundwater pipe and also through Wobus and Ritter,
and surface water the pipes. 2010)
resources.
Hydrothermal vents (C) Along the baked (Sury et al., 2004;
are possible fractured bedrock Wobus and Ritter,
pathways for next to the 2010)
contaminant fluid hydrothermal vent,
towards groundwater and also through the
and surface water vent.
resources.
Kimberlite pipes/ (D) Joints parallel to (RSA DMR, 2012) (Sury et al., 2004;
fissures are possible the kimberlite pipe. Wobus and Ritter,
pathways for 2010)
fracturing
311
Number
on model
contaminants
towards groundwater
and surface water
resources.
Faults and springs are (E) Faults and springs (Van Tonder et (Moorhouse et al.,
possible pathways for which are inter- al., 2013) 2010)
contaminant fluid connected and under
towards groundwater artesian pressures
and surface water can transport fluid
resources. towards the surface.
Horizontal drilling (F) Mineralised veins, (CCA, 2014; (Burton et al., 2006;
and fracturing can preferential pathways Myers, 2012) Sury et al., 2004)
stimulate mineralised for fluid and gas to
veins, fractures, joints migrate towards the
and increase surface.
secondary hydraulic
connectivity. It can
also create or
enhance preferential
pathways for saline
water and gas to
move upward from
the intermediate
zone to the
groundwater
resource.
312
Figure A 9: Potential contamination due to geology-related issues. Corresponds to the pathway numbers listed in Table A 5
313
Figure A 10: Potential contamination due to geology-related issues. Corresponds to the pathway numbers listed in Table A
5
314
Appendix B
INFORMATION SHEET (HYDROCENSUS FORM)
Project Description:
Project No: Recorded by:
Existing BH name/no: Recorded BH name/no:
Village/Farm: Date + time:
GPS Coordinates: Lat/long:

(Cape System)
Photo: Yes/No
1:50 000 Map No:

Elevation (mamsl):
Topography:
General location and accessibility:
BOREHOLE INFORMATION
Owner (and/or assistant) name + phone no:
Historical BH Depth(m):
Present BH Depth(m):
Casing type:
Casing diameter (cm):
Casing height above ground level (cm):
(S)WL: (m below measuring point)

Piezometer depth and (S)WL: (m below measuring
point)
Height (m): (measuring point above ground level)
Casing depth (m): (if known)
Slotted/screened interval(s) depth (m): (if known)
PARAMETERS
pH: EC (mS/m): Temp (C): DO (mg/l):
TDS (mg/l): ORP (mV): Smell:
PUMPING EQUIPMENT INSTALLED
Pump Type: Driven By:
Pump Depth (m): Horse Power:
Discharge: (l/h) or (Gal/h)
Pumping Period and Duration: (hrs/day)

Diameter of Discharge Pipe: (mm) (Estimated)
315
Condition of facility:
Use (domestic, irrigation, observation etc.):
How many dependants:
Livestock units/game animals: Hectares:
Extra comments (approximate slope, weather,

vegetation, proximity to carrel, geologic unit, aquifer
name, condition of borehole collapsed, sealed shut,
dry etc.)
316
Appendix C
HYDRAULIC FRACTURING CHEMICAL PARAMETER FROM STUDIES
REVIEWED
List of parameters different companies and groups sampled and analysed for or recommendations of
parameters to be sampled and analysed for during groundwater baseline establishment (for hydraulic
fracturing, unconventional gas projects, and oil and gas projects), contaminant investigations, and
wastewater characterisation at a hydraulic fracturing site.
Study number 1 2 3 4
Reference (COGA, 2011) (Senior, 2014) (Eckhardt and Sloto, (WOGCC, 2014)
2012)
Scale Local and regional Regional baseline Regional baseline Local and regional
baseline establishment establishment establishment baseline establishment
Type of project Oil and gas Hydraulic fracturing Hydraulic fracturing Oil and gas
Characteristics pH pH pH Alkalinity (total,

bicarbonate, and
Specific conductance Specific conductance Specific conductance Total dissolved solids

Total dissolved solids Total dissolved solids Hardness as CaCO3
Alkalinity (total, Acid neutralising Alkalinity as CaCO3

bicarbonate, and content
Total dissolved solids
Chemical oxygen
demand (COD)
Major cations Calcium (Ca +) Calcium (Ca +) Calcium (Ca +) Calcium (Ca +)
Magnesium (Mg+) Magnesium (Mg+) Magnesium (Mg+) Magnesium (Mg+)

Potassium (K+) Potassium (K+) Potassium (K+) Potassium (K+)
Sodium (Na +) Sodium (Na +) Sodium (Na +) Sodium (Na +)

Major anions Bromide (Br) Bromide (Br) Chloride (Cl ) Bromide (Br)
Chloride (Cl ) Chloride (Cl ) Fluoride (F) Chloride (Cl )
Sulphate (SO42) Fluoride (F-) Sulphate (SO42) Fluoride (F)
Nitrate (NO3) and Nitrogen (N2), Nitrite (NO2) Sulphate (SO42)
nitrite (NO2) ammonia (NH3) as and nitrate (NO3)
as N nitrogen (N2) as nitrogen (N2)
Phosphorus (P) Nitrogen (N2), nitrite Orthophosphate as Total phosphorus

(NO2) phosphate (P)
as nitrogen (N2)
Bicarbonate (HNO3) Nitrite (NO2) Nitrate (NO3) and

and nitrate (NO3) Nitrite (NO2)
as nitrogen (N2) as N (NO2-N)
Orthophosphate as P Bicarbonate (HNO3)
317
Trace elements Selenium (Se) Aluminium (Al) Aluminium (Al) Barium (Ba)
Strontium (Sr) Antimony (Sb) Antimony (Sb) Boron (B)
Boron (B) Arsenic (As) Arsenic (As) Iron (Fe)

Iron (Fe) Barium (Ba) Barium (Ba) Selenium (Se)
Manganese (Mn) Beryllium (Be) Beryllium (Be) Strontium (Sr)

Boron (B) Boron (B) Manganese (Mn)
Cadmium (Cd) Cadmium (Cd)

Chromium (Cr) Chromium (Cr)
Cobalt (Co) Cobalt (Co)

Copper (Cu) Copper (Cu)
Lead (Pb) Iron (Fe)

Lithium (Li) Lead (Pb)
Manganese (Mn) Lithium (Li)
Molybdenum (Mo) Manganese (Mn)

Selenium (Se) Molybdenum (Mo)
Silver (Ag) Nickel (Ni)

Strontium (Sr) Selenium (Se)
Thallium (TI) Silver (Ag)

Tungsten (W) Strontium (Sr)
Uranium (U) Thallium (TI)

Zinc (Zn) Uranium (U)
Vanadium (V) Vanadium (V)

Iron (Fe) Zinc (Zn)
Dissolved Methane (CH4) Methane (CH4) Methane (CH4) Methane (CH 4)

gases
Ethane (C2H6) Ethane (C2H6) Argon (Ar) Ethane (C2H6)
Propane (C3H8) Ethylene (C2H4) (C2H4) Nitrogen (N2) Propane (C3H8)

Fixed Gases C1-C6 Carbon dioxide (CO2) Fixed Gases C1-C6
Liquid Gasoline range

hydrocarbons organics
Diesel range organics

VOCs Benzene Benzene
Toluene Ethylbenzene
Ethylbenzene Toluene
Xylenes (o-xylene, m- + Xylenes, Total

p-xylene, total xylene)
Polycyclic Naphthalene
aromatic
hydrocarbons
Stable isotopes 1HCH4 13CCH4 1HCH4
DCH4 DCH4 DCH4

13CCH4 18OH2O 13CCH4
318
12CCH4 DH2O 12CCH4

Isotopes of DIC ( 13C)
(87Sr /86Sr)
11B
Radioactive Radon (Rn 222) Radon (Rn 222)

constituents
Radium-226 Gross-alpha
radioactivity
Gross-alpha Gross-beta
radioactivity radioactivity
Gross-beta
radioactivity
Other CFC-11
CFC-12
CFC-13
SF6
Silica (Si +4) Silica (Si +4) Silica (Si +4)

Sulphide Sulphide Sulphide
concentrations concentrations concentrations
Continued
Reference (Sloto, 2013) (Sloto, 2014) (Palacios, 2012) (USEPA, 2010a)
Local and regional

Regional baseline Regional baseline Local and regional
Scale baseline
establishment establishment baseline establishment
establishment
Contamination
Type of project Hydraulic fracturing Hydraulic fracturing Hydraulic fracturing investigation after
hydraulic fracturing
pH pH Total dissolved solids
Specific conductance Specific conductance Alkalinity as HCO3-
Characteristics Alkalinity as CaCO3 Alkalinity as CaCO3 Total organic carbon
Total dissolved solids Total dissolved solids

Dissolved oxygen Dissolved oxygen
Calcium (Ca +) Calcium (Ca +) Calcium (Ca +) Sodium (Na +)

Magnesium (Mg+) Magnesium (Mg+) Magnesium (Mg+)
Major cations Potassium (K+) Potassium (K+) Potassium (K+)
Sodium (Na +) Sodium (Na +) Sodium (Na +)
Nitrite (NO2)
Bromide (Br) and nitrate (NO3) Bromide (Br) Chloride (Cl )
Major anions as nitrogen (N2)
Nitrate (NO3),
Chloride (Cl ) Chloride (Cl )
dissolved as N
319
Nitrite (NO2),
Fluoride (F) Nitrate (NO3)
dissolved as N
Orthophosphate, as
Sulphate (SO42) Sulphate (SO42)
phosphorus
Nitrite (NO2)
and nitrate (NO3) Ammonia (NH3) as N Phosphorus (P)
as nitrogen (N2)
Nitrate (NO3),
Manganese (Mn)
dissolved as N
Nitrite (NO2),
dissolved as N
Orthophosphate, as
phosphorus
Ammonia (NH3) as N
Aluminium (Al) Aluminium (Al) Aluminium (Al)
Antimony (Sb) Antimony (Sb) Antimony (Sb)

Arsenic (As) Arsenic (As) Arsenic (As)
Arsenic (As) Barium (Ba) Barium (Ba)
Barium (Ba) Beryllium (Be) Beryllium (Be)
Barium (Ba) Boron (B) Boron (B)

Beryllium (Be) Cadmium (Cd) Cadmium (Cd)
Boron (B) Chromium (Cr) Chromium (Cr)

Cadmium (Cd) Cobalt (Co) Cobalt (Co)
Chromium (Cr) Copper (Cu) Copper (Cu)

Cobalt (Co) Iron (Fe) Iron (Fe)
Copper (Cu) Lead (Pb) Lead (Pb)
Trace elements
Iron (Fe) Lithium (Li) Mercury (Hg)
Lead (Pb) Manganese (Mn) Molybdenum (Mo)
Lithium (Li) Molybdenum (Mo) Nickel (Ni)

Manganese (Mn) Nickel (Ni) Selenium (Se)
Molybdenum (Mo) Selenium (Se) Silver (Ag)

Nickel (Ni) Silver (Ag) Strontium (Sr)
Selenium (Se) Strontium (Sr) Sulphur (S)

Silver (Ag) Uranium (U) Titanium (Ti)
Strontium (Sr) Zinc (Zn) Uranium (U)

Strontium (Sr)
Zinc (Zn)
Uranium (U)
Methane (CH4) Methane (CH4) Methane (CH 4) Methane (CH4)
Dissolved Ethane (C2H6) Ethane (C2H6) Ethane (C2H6) Ethane (C2H6)

gases Propane (C3H8) Ethylene (C2H4) Propane (C3H8) Propane (C3H8)
Argon (Ar) Propane (C3H8) Hexane Hexane
320
Nitrogen (N2) Propylene

Carbon dioxide (CO2) Iso-butane
Oxygen N-butane
Total petroleum Total petroleum
Iso-pentane
hydrocarbons hydrocarbons
Liquid
Gasoline range
hydrocarbons N-pentane Crude oil
organics
Hexane Diesel range organics

Benzene Benzene
Ethylbenzene Toluene
VOCs
Toluene
Xylenes, Total
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a) anthracene
Benzo-(a)-pyrene
Benzo(ghi)perylene
Benzo(k)fluora nthene
Polycyclic
aromatic Chrysene
hydrocarbons Dibenzo (ah)
anthracene
Fluoranthene
Fluorene
lndeno (1,2,3-cd)
pyrene
Naphthalene
Pherianthrene
Pyrene
1HCH4 Carbon isotopes 13CCH4
DCH4 DCH4
Stable isotopes
13CCH4
12CCH4
Radon (Rn 222) Radon (Rn 222) Alpha radioactivity
Gross-alpha
Gross-alpha
radioactivity 72-hour Beta radioactivity
Radioactive radioactivity
recount
constituents
Gross-alpha
Gross-beta
radioactivity 30-hour Gamma radioactivity
radioactivity
recount
321
Gross-beta
radioactivity 72-hour
recount
Gross-beta
radioactivity 30-hour
recount
Radium 226, 228

Radon (Rn 222) 222
Potassium (K+)-40
Silica (Si +4) Silica (Si +4) Silica (Si +4)
Continued
Study number 9 10 11 12 13
Reference (DiGiulio et al., (Osborn et al., (OBrien et al., (Johnson, 2012) (Cranch, 2014)
2011) 2011) 2013)
Scale Local and regional Regional baseline Regional baseline Regional baseline Local and
baseline establishment establishment establishment regional baseline
establishment establishment
State of Illinois
Type of project Contamination Contamination Unconventional Gas Oil and gas
investigation after investigation after gas
hydraulic fracturing hydraulic fracturing
Characteristics pH Alkalinity as HCO3 pH Alkalinity (total, pH
bicarbonate, and
carbonate; as
CaCO3)
Specific Specific Total dissolved Alkalinity as

conductance conductance solids HCO3
Dissolved organic Alkalinity as HCO3 Specific

carbon conductance
Dissolved inorganic Dissolved organic Total dissolved
carbon carbon solids
Total dissolved Dissolved inorganic
solids carbon
Total dissolved
solids
Major cations Calcium (Ca +) Calcium (Ca +) Calcium (Ca +) Calcium (Ca +) Calcium (Ca +)
Magnesium (Mg+) Magnesium (Mg+) Magnesium (Mg+) Magnesium (Mg+) Magnesium
(Mg+)
Potassium (K+) Sodium (Na +) Sodium (Na +) Potassium (K+)

Sodium (Na +) Sodium (Na +)
Major anions Chloride (Cl ) Chloride (Cl ) Nitrate (NO3), Nitrate (NO3), Chloride (Cl )
dissolved as N dissolved as N
Sulphate (SO42) Ammonia (NH3) Nitrite (NO2), Sulphate (SO42)

dissolved as N
Fluoride (F) Phosphorus (P) Orthophosphate as

P
322
Nitrate (NO3), Bromide (Br)

dissolved as N
Nitrate (NO3) and Chloride (Cl )

nitrogen (N2)
Ammonia (NH3) Fluoride (F)
Phosphorus (P) Sulphate (SO42)

Bicarbonate
(HNO3)
Trace elements Aluminium (Al) Boron (B) Aluminium (Al) Aluminium (Al) Arsenic (As)
Silver (Ag) Antimony (Sb) Antimony (Sb) Barium (Ba)

Boron (B) Arsenic (As) Arsenic (As) Cadmium (Cd)
Barium (Ba) Barium (Ba) Barium (Ba) Chromium (Cr)

Beryllium (Be) Boron (B) Beryllium (Be) Iron (Fe)
Cobalt (Co) Bromide (Br-) Cadmium (Cd) Lead (Pb)

Iron (Fe) Cadmium (Cd) Chromium (Cr) Manganese (Mn)
Molybdenum (Mo) Chromium (Cr) Cobalt (Co) Mercury (Hg)

Antimony (Sb) Cobalt (Co) Copper (Cu) Selenium (Se)
Strontium (Sr) Copper (Cu) Iron (Fe) Silver (Ag)

Titanium (Ti) Iron (Fe) Lead (Pb)
Zinc (Zn) Lead (Pb) Manganese (Mn)

Arsenic (As) Lithium (Li) Nickel (Ni)
Cadmium (Cd) Manganese (Mn) Selenium (Se)

Chromium (Cr) Mercury (Hg) Silver (Ag)
Copper (Cu) Molybdenum (Mo) Thallium (TI)

Mercury (Hg) Nickel (Ni) Uranium (U)
Nickel (Ni) Rubidium (Rb) Vanadium (V)
Lead (Pb) Selenium (Se) Zinc (Zn)

Selenium (Se) Strontium (Sr)
Thorium (Th) Vanadium (V)
Uranium (U) Zinc (Zn)
Dissolved gases Methane (CH 4) Methane (CH 4) Methane (CH 4) Methane (CH4) Ethane (C2H6)
Ethane (C2H6) Ethane (C2H6) Ethane (C2H6) Ethane (C2H6) Methane (CH 4)
Propane (C3H8) Propane (C3H8) Radon (Rn 222) Ethylene (C2H4) Propane (C 3H8)
Fixed Gases C1-C6
Liquid Gasoline range Total petroleum Gasoline range

hydrocarbons organics hydrocarbons organics (GRO)-C6-
C10
Diesel range Diesel range

organics organics (C10-C28)
VOCs Benzene Benzene Benzene

Ethylbenzene Ethylbenzene Ethylbenzene
323
Toluene Toluene Toluene

Xylenes, Total Xylenes, Total Xylenes, Total
Trimethylbenzenes
Glycols Diethylene glycol
Triethylene glycol
Aromatic
Hydrocarbons
Alcohols Isopropanol Propanol
Ethanol Methanol
Isopropanol
Stable Isotopes 18OH2O 11B 13CCH4
DH2O 18OH2O DCH4

Isotopes of DIC DH2O 18OH2O
(13C)
13CCH4 DH2O
DCH4 Isotopes of DIC
(13C)
Isotopes of DIC 13CC2H6
(13C)
DC2H6
Radioactive Radium-226 Gross-alpha Gross-alpha Gross-alpha
constituents radioactivity radioactivity radioactivity
Gross-beta Gross-beta Gross-beta
radioactivity radioactivity radioactivity
Phenols Phenols Phenols
Semi-volatile Semi-volatile sVOC sVOC

organic carbons organic carbons
Pesticides Pesticides
Polychlorinated Polychlorinated
biphenyls (PCB) biphenyls (PCB)
Total inorganic Total inorganic

carbon carbon
Bacteria Bacteria
Low molecular Low molecular

weight acids weight acids
Silica (Si +4) Silica (Si +4)
324
Continued
Study
14 15 16 17 18
number
Reference (Cranch, 2014) (Cranch, 2014) (Cranch, 2014) (Cranch, 2014) (Cranch, 2014)
Scale Local and regional Local and regional Local and regional Local and regional Local and regional
baseline baseline baseline baseline baseline
establishment establishment establishment establishment establishment
State of Colorado State of Texas State of Wyoming State of State of Ohio
Pennsylvania
Type of Oil and gas Oil and gas Oil and gas Oil and gas Oil and gas
project
Character- pH Total dissolved pH pH pH
istics solids
Alkalinity as HCO3 Alkalinity as HCO3 Alkalinity as HCO3 Alkalinity as HCO3
Specific Specific Specific Specific

conductance conductance conductance conductance
Total dissolved Total dissolved Total dissolved Total dissolved
solids solids solids solids
Major Calcium (Ca +) Sodium (Na +) Magnesium (Mg+) Calcium (Ca +) Calcium (Ca +)
cations
Magnesium (Mg+) Calcium (Ca +) Magnesium (Mg+) Sodium (Na +)
Potassium (K+) Potassium (K+) Potassium (K+) Potassium (K+)

Major Chloride (Cl ) Chloride (Cl ) Sulphate (SO42-) Chloride (Cl -)
anions
Sulphate (SO42) Fluoride (F) Sulphate (SO42-)
Sulphate (SO42)
Nitrate (NO3)
Nitrite (NO2),
dissolved as N
Trace Arsenic (As) Barium (Ba) Barium (Ba) Barium (Ba)
elements
Barium (Ba) Strontium (Sr) Boron (B) Barium (Ba)
Chromium (Cr) Bromide (Br-) Iron (Fe)
Iron (Fe) Iron (Fe) Lead (Pb)

Selenium (Se) Manganese (Mn) Manganese (Mn)
Selenium (Se) Manganese (Mn)
Strontium (Sr) Strontium (Sr)
Strontium (Sr)
Dissolved Ethane (C2H6) Oxygen
gases
Ethane (C2H6)
Methane (CH4)
Propane (C3H8)
325
Study
14 15 16 17 18
number
Free gas Ethane (C2H6) Ethane (C2H6)
Methane (CH 4) Methane (CH 4)

Liquid Total petroleum Total petroleum Total petroleum
hydro- hydrocarbons hydrocarbons hydrocarbons
carbons


aromatic
hydro-
carbons
Continued
Study number 19 20
Reference (WVWRI, 2013) (Al et al., 2013)
Scale Local baseline establishment Regional baseline establishment
Type of project Water and waste quality characterisation at

a hydraulic fracturing site
Characteristics pH pH
Total alkalinity Alkalinity as HCO3
Specific conductance Specific conductance

Total dissolved solids
Major cations Calcium (Ca +) Calcium (Ca +)

Magnesium (Mg+) Magnesium (Mg+)
Potassium (K+) Sodium (Na +)

Sodium (Na +) Potassium (K+)
Major anions Chloride (Cl ) Ammonia (NH3) as N

Nitrite (NO2) Chloride (Cl )
Nitrate (NO3) Fluoride (F)

Sulphate (SO42) Nitrate (NO3)
Bicarbonate (HNO3) Phosphate (PO4)

Phosphate (PO4) Sulphate (SO42)
Trace elements Aluminium (Al) Antimony (Sb)

Arsenic (As) Arsenic (As)
Barium (Ba) Barium (Ba)

Bromide (Br) Bromide (Br)
Chromium (Cr) Bromide (Br)

Iron (Fe) Chromium (Cr)
Manganese (Mn) Cobalt (Co)
326
Study number 19 20
Mercury (Hg) Copper (Cu)

Nickel (Ni) Iron (Fe)
Selenium (Se) Lead (Pb)

Silver (Ag) Manganese (Mn)
Strontium (Sr) Molybdenum (Mo)

Zinc (Zn) Nickel (Ni)
Sulphur (S) Selenium (Se)

Strontium (Sr)
Thorium (Th)
Uranium (U)
Vanadium (V)
Zinc (Zn)
Dissolved gases Methane (CH 4) Methane (CH4)
Ethane (C2H6) Ethane (C2H6)

Propane (C 3H8) Propane (C3H8)
Liquid hydrocarbons Total petroleum hydrocarbons

VOCs Benzene
Ethylbenzene
Toluene
Xylenes, Total
Stable isotopes DCH4
13CCH4
18OH2O
DH2O
Radioactive constituents Gross-alpha radioactivity
Gross-beta radioactivity
Lead (Pb)-210
Radium-226
Radium-228
Thorium (Th)-230, -228, -232

Uranium (U)-238
Potassium (K+)-40
Sulphide concentrations Hydrogen sulphide (H 2S)
327
UCG CHEMICAL PARAMETER FROM STUDIES REVIEWED
List of parameters by different companies and groups sampled and analysed for, or recommendations
of parameters to be sampled and analysed for during groundwater baseline establishment (for coal
bed methane, UCG, unconventional gas projects and oil and gas projects).
Study
1 2 3 4 5
number
(Cheung and (OBrien et al.,
Reference (COGA, 2011) (WOGCC, 2014) (Cranch, 2014)
Mayer, 2009) 2013)
Scale Local and regional Regional baseline Local and regional Regional baseline Local and regional
baseline establishment baseline establishment baseline
establishment establishment establishment
State of Illinois
Type of Oil and gas Coal bed methane Oil and gas Unconventional Oil and gas
project gas
Character- pH Alkalinity (total, Alkalinity (total, pH pH
istics bicarbonate, and bicarbonate, and
carbonate; carbonate;
as CaCO3) as CaCO3)
Specific Total dissolved Specific Alkalinity as
conductance solids conductance HCO3
Total dissolved Alkalinity as Specific
solids HCO3 conductance
Alkalinity (total, Dissolved organic Total dissolved
bicarbonate, and carbon solids
carbonate; as
CaCO3)
Dissolved
inorganic carbon
Total dissolved
solids
Major Calcium (Ca +) Calcium (Ca +) Calcium (Ca +) Calcium (Ca +) Calcium (Ca +)
cations Magnesium (Mg+) Magnesium (Mg+) Magnesium (Mg+) Magnesium (Mg+) Magnesium (Mg+)
Potassium (K+) Potassium (K+) Potassium (K+) Sodium (Na +)
Major Bromide (Br) Chloride (Cl ) Bromide (Br ) Ammonia (NH3) Chloride (Cl )
anions Chloride (Cl ) Sulphate (SO42) Chloride (Cl ) Nitrate (NO3), Sulphate (SO42)
dissolved as N
Sulphate (SO42) Nitrate (NO3) Fluoride (F) Phosphorus (P)
Nitrate (NO3) and Fluoride (F) Sulphate (SO42)
nitrite (NO2) as N
Phosphorus (P) Bicarbonate Total phosphorus
(HNO3)
Bicarbonate Nitrate (NO3) and
(HNO3) Nitrite (NO2) as N
(NO2-N)
Bicarbonate
(HNO3)
Trace Selenium (Se) As 3+ and As 5+ Barium (Ba) Aluminium (Al) Arsenic (As)
elements Strontium (Sr) Total chromium, Boron (B) Antimony (Sb) Barium (Ba)
Cr6+ and Cr3+
Boron (B) Complete trace Iron (Fe) Arsenic (As) Cadmium (Cd)
metal analysis
Iron (Fe) Iron (Fe) Selenium (Se) Barium (Ba) Chromium (Cr)
Manganese (Mn) Manganese (Mn) Strontium (Sr) Boron (B) Iron (Fe)
Manganese (Mn) Bromide (Br ) Lead (Pb)
328
Study
1 2 3 4 5
number
Cadmium (Cd) Manganese (Mn)
Chromium (Cr) Mercury (Hg)
Cobalt (Co) Selenium (Se)
Copper (Cu) Silver (Ag)
Iron (Fe)
Lead (Pb)
Lithium (Li)
Manganese (Mn)
Mercury (Hg)
Molybdenum
(Mo)
Nickel (Ni)
Rubidium (Rb)
Selenium (Se)
Strontium (Sr)
Vanadium (V)
Zinc (Zn)
Dissolved Methane (CH4) Methane (CH4) Methane (CH 4) Methane (CH 4) Ethane (C2H6)
gases Ethane (C2H6) Ethane (C2H6) Ethane (C2H6) Ethane (C2H6) Methane (CH 4)
Propane (C3H8) Carbon dioxide Propane (C3H8) Radon (Rn 222) Propane (C3H8)
(CO2)
Fixed Gases C1-C6 Fixed Gases C1-C6
Free gas Methane (CH4)
Ethane (C2H6)
Carbon dioxide
(CO2)
Liquid Gasoline range Total petroleum
hydro- organics hydrocarbons
carbons Diesel range
organics
VOCs Benzene Benzene Benzene Benzene
Toluene Toluene Ethylbenzene Ethylbenzene
Ethylbenzene Ethylbenzene Toluene Toluene
Xylenes (o-xylene, Xylenes (o-xylene, Xylenes, Total Xylenes, Total
m- + p-xylene, m- + p-xylene,
total xylene) total xylene)
Polycyclic Naphthalene Naphthalene
Aromatic Acenaphthylene
Hydro-
carbons Acenaphthene
Fluorene
Phenanthrene
Anthracene
Acridine
Fluoranthene
Pyrene
Benzo(a)
anthracene
Chrysene
Benzo(b)
fluoranthene
329
Study
1 2 3 4 5
number
Benzo(k)
fluoranthene
Benzo(a)pyrene
Indeno(1,2,3-c,d)
pyrene
Stable 1HCH4 18OH2O 1HCH4 13CCH4
Isotopes DCH4 DH2O DCH4 DCH4
13CCH4 13CCH4 13CCH4 18OH2O
12CCH4 13CC2H6 12CCH4 DH2O
13C CO2 Isotopes of DIC
(13C)
13CC2H6
DC2H6
Radioactive Gross-alpha Gross-alpha
constituents radioactivity radioactivity
Gross-beta Gross-beta
radioactivity radioactivity
Sulphide Sulphide
concentra- concentrations
tions
Continued
Study
6 7 8 9 10
number
Reference (Cranch, 2014) (Cranch, 2014) (Cranch, 2014) (Cranch, 2014) (Cranch, 2014)
Scale Local and regional Local and regional Local and regional Local and regional Local and
baseline baseline baseline baseline regional
establishment establishment establishment establishment baseline
State of Colorado State of Texas State of Wyoming State of establishment
Pennsylvania State of Ohio
Type of Oil and gas Oil and gas Oil and gas Oil and gas Oil and gas
project
Character- pH Total dissolved pH pH pH
istics solids
Alkalinity as HCO3 Alkalinity as HCO3 Alkalinity as HCO3 Alkalinity as
HCO3
Specific Specific Specific Specific
conductance conductance conductance conductance
Total dissolved Total dissolved Total dissolved Total dissolved
solids solids solids solids
Magnesium (Mg+) Calcium (Ca +) Calcium (Ca +)
Calcium (Ca +) Magnesium (Mg+) Sodium (Na +)
Major Calcium (Ca +) Sodium (Na +) Potassium (K+) Potassium (K+) Potassium (K+)
cations
Magnesium (Mg+) Sodium (Na +) Sodium (Na +)
Potassium (K+)
Sodium (Na +)
330
Study
6 7 8 9 10
number
Major Chloride (Cl ) Chloride (Cl ) Sulphate (SO42) Chloride (Cl )

anions
Sulphate (SO42) Fluoride (F) Sulphate (SO42)
Sulphate (SO42)
Nitrate (NO3)
Nitrite (NO2),
dissolved as N
Trace Arsenic (As) Barium (Ba) Barium (Ba) Barium (Ba)
elements
Barium (Ba) Strontium (Sr) Boron (B) Barium (Ba)
Chromium (Cr) Bromide (Br ) Iron (Fe)
Iron (Fe) Iron (Fe) Lead (Pb)
Selenium (Se) Manganese (Mn) Manganese (Mn)
Selenium (Se) Manganese (Mn)
Strontium (Sr) Strontium (Sr)
Strontium (Sr)
Dissolved Ethane (C2H6) Oxygen Ethane (C2H6)

gases
Methane (CH4) Ethane (C2H6) Methane (CH 4)
Methane (CH 4)
Propane (C3H8)
Liquid Total petroleum Total petroleum Total petroleum

hydro- hydrocarbons hydrocarbons hydrocarbons
carbons
Aromatic
Hydro-
carbons
331
Continued
Study
11 12 13 14
number
Reference (Ahern and Frazier, (Olness, 1981) (Dennis, 2006) (Niemczyk, 1978)
1982)
Scale Local Local Local Local
Type of Literature review of Groundwater baseline Groundwater baseline Groundwater baseline

project 300 reports on the establishment for UCG establishment for UCG establishment for UCG
water quality at UCG project project project
sites
Character- Dissolved organic pH pH Alkalinity
istics carbon
pH Specific conductance pH
Total dissolved solids Temperature Total dissolved solids Total dissolved solids
Specific conductance Alkalinity Specific conductance

Temperature
TOC
Major Calcium (Ca +) Calcium (Ca +) Calcium (Ca +)
cations
Magnesium (Mg+) Magnesium (Mg+) Magnesium (Mg+)
Potassium (K+) Potassium (K+) Potassium (K+)
Major anions Ammonium Ammonium Ammonia (NH3) Chloride (Cl )
Chloride (Cl ) Chloride (Cl ) Sulphate (SO42)
Sulphate (SO42) Sulphate (SO42) Fluoride (F)

Fluoride (F) Phosphate (PO4)
Nitrate (NO3),
dissolved as N
Nitrite (NO2),
dissolved as N
Ammonia (NH3) as N
Trace Boron (B) Boron (B) Boron (B) Antimony (Sb)

elements
Bromide (Br ) Cyanide (Cn) Cyanide (Cn) Cadmium (Cd)
Lithium (Li) Chromium (Cr)
Cyanide (Cn) Cobalt (Co)
Barium (Ba) Copper (Cu)

Lead (Pb) Iron (Fe)
Zinc (Zn) Lead (Pb)

Chromium (Cr) Nickel (Ni)
Copper (Cu) Strontium (Sr)

Mercury (Hg) Zinc (Zn)
Iron (Fe) Cyanide (Cn)

Manganese (Mn)
Aluminium (Al)
332
Study
11 12 13 14
number
Selenium (Se)
Cadmium (Cd)
Molybdenum (Mo)
Titanium (Ti)
Vanadium (V)
Arsenic (As)
Selenium (Se)
Dissolved Carbon monoxide (CO)

gases
(CO2)
Methane (CH 4)
Ethene (C2H4)
Ethane (C2H6) (C2H6)
Propane (C3H8) (C3H8)
Toluene Toluene
Xylenes Ethylbenzene
Naphthalene Xylenes
Acetone Naphthalene
Polycyclic Acenaphthene Methylnaphthalene
aromatic isomers
hydro-
carbons
Phenols Phenols Phenols Phenols
2-Methylphenol
(o-Cresol)
3-Methylphenol
(m-Cresol)
4-Methylphenol
(p-Cresol)
Semi volatile Pyridine
organic
Indolines
carbons
Quinolines
333
Appendix D
CASE STUDIES
TABLE D 1: CASE STUDIES LIST OF CHEMICAL CONSTITUENTS ANALYSED

Case Study Two
Case Study Case Study One Case Study Two specialised follow up Case Study Three
sampling parameters
Characteristics Temperature pH pH Temperature
Specific conductance (EC) Temperature Total conductivity Specific conductance
(EC)
pH Total conductivity Total dissolved solids pH
Total dissolved solids Total hardness Oxidation-reduction
dissolved (as CaCO3) potential (ORP)
Ca hardness Total alkalinity as Dissolved oxygen
CaCO3 (DO)
Mg hardness
Total hardness
P alkalinity
M alkalinity
Major cations Calcium (Ca +) Calcium (Ca +) Calcium (Ca +) Calcium (Ca +)
Magnesium (Mg+) Magnesium (Mg+) Magnesium (Mg+) Magnesium (Mg+)
Potassium (K +) Potassium (K +) Potassium (K +) Potassium (K +)
Sodium (Na +) Sodium (Na +) Sodium (Na +) Sodium (Na +)
Silica (Si 4+)
Major anions Chloride (Cl ) Chloride (Cl ) Fluoride (F) Chloride (Cl )
Sulphate (SO42) Sulphate (SO42) Sulphate (SO42) Sulphate (SO42)
Nitrate (NO3) Nitrite (NO2) Chloride (Cl ) Nitrate (NO3)
Phosphate (PO4) Nitrate (NO3) Ortho Phosphate as Bicarbonate (HNO3)
PO4
Ammonium as N (NH 4+-N) Nitrate as N (NO3-N) Nitrate (NO3) Carbonate (CO32)
Fluoride (F) Fluoride (F) NH3 as N Phosphate (PO4)
Phosphate (PO4)
Ammonia (NH 3)
Trace elements Aluminium (Al) Aluminium (Al) Arsenic (As) Aluminium (Al)
and heavy Arsenic (As) Arsenic (As) Barium (Ba) Arsenic (As)
metals
Barium (Ba) Antimony (Sb) Beryllium (Be) Barium (Ba)
Beryllium (Be) Barium (Ba) Cadmium (Cd) Beryllium (Be)
Cadmium (Cd) Beryllium (Be) Chromium (Cr) Boron (B)
Chromium (Cr) Boron (B) Copper (Cu) Cadmium (Cd)
Copper (Cu) Cadmium (Cd) Mercury (Hg) Chromium (Cr)
Iron (Fe) Caesium (Cs) Iron (Fe) Cobalt (Co)
Lead (Pb) Chromium (Cr) Manganese (Mn) Copper (Cu)
Manganese (Mn) Cobalt (Co) Nickel (Ni) Silver (Ag)
Mercury (Hg) Copper (Cu) Selenium (Se) Iron (Fe)
Nickel (Ni) Mercury (Hg) Vanadium (V) Lithium (Li)
Selenium (Se) Iron (Fe) Zinc (Zn) Manganese (Mn)
Vanadium (V) Lead (Pb) Mercury (Hg)
334
Case Study Two
sampling parameters
Zinc (Zn) Lithium (Li) Molybdenum (Mo)
Manganese (Mn) Nickel (Ni)
Molybdenum (Mo) Phosphorus (P)
Nickel (Ni) Lead (Pb)
Scandium (Sc) Rubidium (Rb)
Selenium (Se) Sulphur (S)
Silica (Si) Antimony (Sb)
Silver (Ag) Scandium (Sc)
Strontium (Sr) Silica (Si)
Tellurium (Te) Strontium (Sr)
Thallium (TI) Thallium (TI)
Tin (Sn) Thorium (Th)
Vanadium (V) Uranium (U)
Zinc (Zn) Vanadium (V)
Yttrium (Y)
Zinc (Zn)
Rare earth Cerium (Ce)
elements Dysprosium (Dy)
Erbium (Er)
Europium (Eu)
Gadolinium (Gd)
Holmium (Ho)
Lanthanum (La)
Lutetium (Lu)
Neodymium (Nd)
Praseodymium (Pr)
Samarium (Sm)
Terbium (Tb)
Thulium (Tm)
Ytterbium (Ub)
Gases Methane (CH4) Methane (CH 4) Radon (Rn)
Ethane (C2H6) Ethane (C2H6) Helium (3He)
Ethene (C2H6) Ethene (C2H6) Helium (4He)
Argon (Ar)
Methane (CH 4)
Nitrogen (N2)
Oxygen (O2)
Total CO2
Hydrogen sulphide
(H2S)
N2/Ar
Isotopes 18OH2O
DH2O
13C in TIC
11B
87Sr /86Sr
335
Case Study Two
sampling parameters
3H and 14C
13CCH4
13CCO2
226Ra and 228Ra
36Cl
Organics 1,1,1,2- 1,2,3,4-Tetrachlorobenzene Acenaphthene

Tetrachloroethane
1,1,1-Trichloroethane 1,2,3-Trichlorobenzene Acenaphthylene
1,1,2,2- 1,2,4-Trichlorobenzene Anthracene
Tetrachloroethane
1,1,2-Trichloroethane 1,3,5-Trichlorobenzene Benzo(a)anthracene
1,1-Dichloroethane 1245&1235 Benzo(a)pyrene
Tetrachlorobenzene
1,1-Dichloroethene (1,1 1-Chloronaphtalene Benzo(b)fluoranthene
DCE)
1,1-Dichloropropene 2,3,4,5-Tetrachlorophenol Benzo(bk)fluoranthene
1,2,3-Trichlorobenzene 2,3,4,6 / 2,3,5,6- Benzo(ghi)perylene
Tetrachlorophenol
1,2,3-Trichloropropane 2,3,4-Trichlorophenol Benzo(k)fluoranthene
1,2,4-Trichlorobenzene 2,3,5-/2,4,5- Chrysene
Trichlorophenol
1,2,4-Trimethylbenzene 2,3,6-Trichlorophenol Dibenzo(ah)anthracene
1,2-Dibromo-3- 2,3/3,5-Dimethylphenol + EPH (C8-C40)
chloropropane 4-Ethylphenol
1,2-Dibromoethane 2,3-Dichloronitrobenzene Fluoranthene
1,2-Dichlorobenzene 2,3-Dichlorophenol Fluorene
1,2-Dichloroethane 2,4 -DDD Indeno(123cd)pyrene
1,2-Dichloropropane 2,4 -DDE Naphthalene
1,3,5-Trimethylbenzene 2,4,6-Trichlorophenol PAH 16 Total
1,3-Dichlorobenzene 2,4/2,5-Dichlorophenol PAH Surrogate%
Recovery
1,3-Dichloropropane 2,4-Dichloronitrobenzene Phenanthrene
1,4-Dichlorobenzene 2,4-Dimethylphenol Pyrene
2,2-Dichloropropane 2,5-Dichloronitrobenzene TPH GRO (C4-C12)
2-Chlorotoluene 2,5-Dimethylphenol TPH GRO (C4-C8)
4-Chlorotoluene 2,6-Dichlorophenol TPH GRO (C8-C12)
4-Isopropyltoluene 2,6-Dimethylphenol
Benzene 3,4,5-Trichlorophenol
Bromobenzene 3,4-Dichloronitrobenzene
Bromochloromethane 3,4-Dichlorophenol
Bromodichloromethane 3,4-Dimethylphenol
Bromoform 3,5-Dichloronitrobenzene
Bromomethane 3,5-Dichlorophenol
Carbon tetrachloride 4,4 -DDD + 2,4 -DDT
Chlorobenzene 4,4 -DDE
Chloroethane 4,4 -DDT
Chloroform 4-Chloro-3-methylphenol
Chloromethane Acenaphtene
336
Case Study Two
sampling parameters
cis-1-2-Dichloroethene Acenaphtylene
cis-1-3-Dichloropropene a-Chlordan
Dibromochloromethane a-Endosulfan
Dibromomethane a-Endosulfansulphate
Dichlorodifluoromethane Aldrin
Dichloromethane (DCM) alfa-HCH
Ethylbenzene Ametryn
Hexachlorobutadiene Anthracene
Isopropylbenzene Atrazin
Methyl Tertiary Butyl Azinphos-ethyl
Ether
Naphthalene Azinphos-methyl
n-Butylbenzene Benzo(a)anthracene
o-Xylene Benzo(a)pyrene
p/m-Xylene Benzo(b+k)fluoranthene
Propylbenzene Benzo(ghi)perylene
sec-Butylbenzene beta-HCH
Styrene Bifenthrine
Surrogate Recovery 4- Biphenyl
Bromofluorobenzene
Surrogate Recovery Bromophos-ethyl
Toluene D8
tert-Butylbenzene Bromophos-methyl
Tetrachloroethene (PCE) Carbaryl
Toluene Chlordans (sum)
trans-1-2-Dichloroethene Chloropyriphos-ethyl
trans-1-3- Chloropyriphos-methyl
Dichloropropene
Trichloroethene (TCE) Chrysene
Trichlorofluoromethane Cresols (sum)
Vinyl Chloride Cumaphos
2,3,4,6- Cyanazine
Tetrachlorophenol
2,3,5,6- Cypermethrin A,B, C and D
Tetrachlorophenol
2,3-Dimethylphenol DDT/DDE/DDD (sum)
2,4,6-Trichlorophenol delta-HCH
2,4-Dichlorophenol Deltamethrin
2,4-Dimethylphenol Demeton-S/Demeton-O-
ethyl
2,6-Dichlorophenol Desmetryn
2,6-Dimethylphenol Diazinone
2-Chlorophenol Dibenzo(ah)anthracene
2-Methylphenol Dibenzofurane
2-Nitrophenol Dichloronitrobenzenes
(sum)
3,4-Dimethylphenol Dichlorophenols (sum)
3,5-Dimethylphenol Dichlorovos
337
Case Study Two
sampling parameters
3-Methylphenol Dieldrin
4,6-Dinitro-o-cresol Disulphotone
(DNOC)
4-Chloro-2-methylphenol Endrin
4-Chloro-3-methylphenol Fenitrothion
4-Methylphenol Fenthion
4-Nitrophenol Fluoranthene
Acenaphthene Fluorene
Acenaphthylene gamma-HCH
Anthracene Heptachlor
Benzo(a)anthracene Heptachloroepoxide
Benzo(a)pyrene Hexachlorobenzene
Benzo(b)fluoranthene Hexachlorobutadiene
Benzo(bk)fluoranthene Indeno(123cd)pyrene
Benzo(ghi)perylene Isodrin
Benzo(k)fluoranthene Linuron
Chrysene Malathion
Dibenzo(ah)anthracene m-Chloronitrobenzene
Fluoranthene m-Chlorophenol
Fluorene m-Cresol
Indeno(123cd)pyrene m-Ethylphenol
Naphthalene Miscellaneous Chlor. HCs
PAH 16 Total Monochlorobenzene
PAH Surrogate% Monochloronitrobenzenes
Recovery (sum)
Pentachlorophenol Monochlorophenols (sum)
Phenanthrene Naphtalene
Phenol Nitrobenzene
Pyrene o/p-Chloronitrobenzene
Total Speciated Phenols o-Chlorophenol
MS
o-Cresol
o-Ethylphenol
PAH 10 VROM (sum)
PAH 16 EPA (sum)
Parathion-ethyl
Parathion-methyl
PCB (6) (sum)
PCB (7) (sum)
PCB 101
PCB 118
PCB 138
PCB 153
PCB 180
PCB 28
PCB 52
338
Case Study Two
sampling parameters
p-Chlorophenol
p-Cresol
Pentachlorobenzene
Pentachlorophenol
Permethrin A
Permethrin B
Permethrins (sum)
Phenanthrene
Phenol
Prometryn
Propachlor
Propazine
Pyrazophos
Pyrene
Simazine
Sum 4 HCH-compounds
Sum Drins
Tedion
Telodrin
Terbuthylazine
Terbutryn
Tetrachlorobenzenes (sum)
Tetrachlorophenols (sum)
Thymol
TPH (sum C10-C40)
TPH C10-C12
TPH C12-C16
TPH C16-C21
TPH C21-C30
TPH C30-C35
TPH C35-C40
Triazophos
Trichlorobenzenes (sum)
Trichlorophenols (sum)
Trifluralin
y-Chlordan
339
Appendix E
CASE STUDY ONE: CONCEPTUAL SITE MODEL
340
APPENDIX F
Modified Parameters
Parameters
Major cations
Calcium (Ca +)
Magnesium (Mg+)
Potassium (K+)
Sodium (Na +)
Silica (Si +4)
Major anions
Chloride (Cl )
Sulphate (SO42)
Nitrate (NO3)
Bicarbonate (HNO3)
Carbonate (CO32)
Phosphate (PO4)
Ammonium as N (NH4+-N)
Nitrate as N (NO3-N)
Nitrite as N (NO2-N)
Fluoride (F)
Trace metals
Aluminium (Al)
Antimony (Sb)
Arsenic (As)
Barium (Ba)
Beryllium (Be)
Boron (B)
Bromide (Br -)
Bromine (Br)
Cadmium (Cd)
Chromium (Cr)
Cobalt (Co)
Copper (Cu)
Cyanide (Cn)
Iron (Fe)
Lead (Pb)
Lithium (Li)
Manganese (Mn)
Mercury (Hg)
Molybdenum (Mo)
Nickel (Ni)
Rubidium (Rb)
Selenium (Se)
Silver (Ag)
Strontium (Sr)
Thallium (TI)
Thorium (Th)
Titanium (Ti)
Tungsten (W)
Uranium (U)
Vanadium (V)
Zinc (Zn)
Dissolved gases
Argon (Ar)
341
Parameters
Ethane (C2H6)
Helium (He)
Hydrogen sulphide (H 2S)
Methane (CH 4)
Nitrogen (N2)
Propane (C3H8)
Radon (Rn 222)
DH2O
DCH4
DC2H6
18OH2O
13CCH4
13CC2H6
Alpha radioactivity
Beta radioactivity
Organics
VOCs
Benzene
Toluene
Ethylbenzene
Xylenes (o-xylene, m- + p-xylene, total xylene)
Isopropylbenzene
Chloroform
Carbon disulphide
Acetone
SVOCs
1,2-Diphenylhydrazine
1,4-Dioxane
7,12-Dimethylbenz(a)anthracene
Acetophenone
Benzidine
Benzyl alcohol
Bis(2-Chloroethyl)ether
Bis(2-Ethylhexyl)phthalate
Butyl benzyl phthalate
Diethylphthalate
Di-n-butylphthalate
Di-n-octylphthalate
Diphenylamine
Hexachlorobenzene
N-Nitrosodiphenylamine
N-Nitrosomethylethylamine
Phorate
Pyridine
PAHs
1,2,3,4-Tetrahydro-naphthalene
1-Methyl-7-(1-methylethyl)phenanthrene
1-Methylnaphthalene
2-Methylnaphthalene
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
342
Parameters
Chrysene
Decahydro-4,4,8,9,10-pentamethylnaphthalene
Dibenzo(a,h)arthracene
Dimethyl-naphthalene
Fluoranthene
Fluorene
Methylnaphthalene
Methyl-phenanthrene
Naphthalene
Perylene
Phenanthrene
Pyrene
Tetra-methyl-phenanthrene
Phenols
2,3-Dimethylphenol (2,3-Xylenol)
2,4-Dichlorophenol
2,6-Dichlorophenol
2,4-Dimethylphenol (2,4 Xylenol)
2-Methylphenol (o-Cresol)
3-Methylphenol (m-Cresol)
4-Methylphenol (p-Cresol)
Alkylphenol ethoxylates
Butylphenol
Hydroxybenzene
Methoxy-methylphenol
Nonyl phenol ethoxylate
Nonylphenols
Octylphenol
p-tert-butyl-phenol
Tert-butyl-phenol
Trichlorophenol
TPH (C6-C40)
Although it was found in the case study by Murray et al. (2015) that methane and its isotopes did not
indicate a clear distinction between shallow and deep groundwater of the MKB, it is still suggested
that they are sampled and analysed for as they may indicate potential contamination due to
unconventional gas activates, because methane is the main gas product from both hydraulic fracturing
and UCG operations. Furthermore, it was suggested in this dissertation that the boreholes selected to
be sampled on a monthly basis during baseline establishment, should ideally contain dissolved
methane concentrations in excess of 1 mg/l. This is done to determine the origin of the methane and
to minimise the number of boreholes sampled for each month, which would ultimately decrease field
sampling event time and cut analyses cost.
Parameters not suggested to be sampled and analysed for
Based on the findings of Case Study Three, the following parameters are not suggested to be sampled
and analysed for during groundwater baseline establishment for unconventional gas projects in South
343
Africa although they were previously suggested to be sampled and analysed for in this dissertation:
The rationale for not sampling and analysing for 87 Sr/86 Sr ratios and 13 CDIC
87 Sr/86 Sr ratios and 13 CDIC are not good groundwater depth indicators or differentiators in the
Karoo Basin and are not suggested to be sampled and analysed for during groundwater baseline
establishment projects in the Main Karoo Basin.
Because there are other parameters which can be used as groundwater depth indicators outside
of the Main Karoo Basin at unconventional gas projects in South Africa which are more easily
obtained, it is suggested that sampling and analysing for 87 Sr/86 Sr ratios and 13 CDIC would prove
redundant.
Although both can be used to determine if groundwater contamination has occurred due to
unconventional gas activities, there are many other parameters (from the case study) which can
be used for this purpose and can be sampled and analysed for more cost-effectively and are less
difficult to analyse for.
The rationale for not sampling and analysing for 34 Ssulphate and 18 Osulphate:
Although 34 Ssulphate and 18 Osulphate may be used to trace the origin of sulphate, to calculate the
proportions of mixing between different sources/aquifers and be used to determine whether the
system is anaerobic or aerobic, there are other parameters from this case study which have been
proved to be able to accurately indicate if mixing between different aquifers occurred.
The rationale for not sampling and analysing for 13 CCO2 :
13 CCO2 is not suggested to be analysed, even though it may be used to identify deep groundwater
and may be used to indicate the origin of methane, there are other parameters which can be used
more successfully to identify deep groundwater and used to indicate the origin of methane, and
are also more cost-effective.
The rationale for not sampling and analysing for Xenon (Xe), Krypton (Kr) and Neon (Ne)
Although it was suggested to analyse for xenon, krypton and neon during groundwater baseline
establishment in this dissertation, as these noble gases may be used as potential indicators of
groundwater mixing between produced water from coals and shales and the groundwater of
overlying geological groups by comparing the recharge temperatures. There are other more
reliable, less expensive and easier sampling alternatives to indicate if groundwater mixing has
occurred, such as magnesium, alkalinity, sodium, and vanadium.
344

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ESTABLISHING A GROUNDWATER BASELINE

FOR UNCONVENTIONAL GAS PROJECTS

Submitted in fulfilment of the requirements for the degree

at the Institute for Groundwater Studies

Supervisor: Dr Francois Fourie

Magiel Lourens Date: 30 / 01 / 2017

2.1 INTRODUCTION .................................................................................................................................................. 7

3.1 INTRODUCTION ..............................................................................................................................................100

4.1 INTRODUCTION ..............................................................................................................................................208

Table 2.2: EIA/ARI technically recoverable shale gas resource estimates.................................17

Table 2.14: Summary of the southern Ecca Formations..........................................................56

Table 2.15: Summary of the northern Ecca Formations ..........................................................57

Table 2.20: Compositional comparison between different shales ............................................77

Table 2.21: Compositional ratio comparison between different shales .....................................78

Table 2.22: baseline groundwater concentrations compared to produced water concentrations at

Table 2.24: Summary of the volume of water used per well....................................................92

Table 3.3: Suggested spacing of the observation wells ....................................................... 132

Table 3.11: List of suggested cations to be analysed for ....................................................... 161

Table 3.12: List of suggested anions to be analysed for ........................................................ 161

Table 3.15: List of suggested isotopes to be analysed for ..................................................... 165

Table 3.16: List of suggested radionuclides to be analysed for .............................................. 166

Table 3.17: List of suggested VOCs to be analysed for .......................................................... 168

Table 3.18: List of suggested SVOCs to be analysed for ........................................................ 169

Table 3.19: List of suggested PAHs to be analysed for .......................................................... 170

Table 3.20: List of suggested phenols to be analysed for ...................................................... 172

Table 3.22: Suggested field measurements ........................................................................ 173

Table 3.23: Suggested physical characteristics to be analysed for .......................................... 176

Table 4.1: Summary of activities completed before the geohydrological investigation by

Table 4.4: Indicators of deep groundwater ....................................................................... 252

Table 4.5: Prioritisation of determinants for identifying deep groundwater........................... 260

Table A 1: Summary of potential contamination, due to surface handling and transportation

Table A 2: Summary of potential contamination due to wastewater management and disposal

Table A 3: Summary of potential contamination due to well-related issues relating to hydraulic

Table A 4: Potential contamination of groundwater resources unique to underground coal

Table A 5: Summary of potential contamination, via geology-related issues associated with

Table D 1: Case Studies list of chemical constituents analysed ............................................. 334

Figure 1.1: Layout of the study ........................................................................................... 6

Figure 2.7: Typical surface infrastructure at a hydraulic fracturing operation............................20

Figure 2.8 : Different casing types.......................................................................................21

Figure 2.20: Groundwater level distribution in South Africa ....................................................66

Figure 2.26: Distribution of different intrusions in the Karoo Supergroup ..................................83

Figure 2.27: Schematic cross section of a breccia pipe ............................................................85

Figure 2.28: Diagram illustrating an idealised hydrothermal vent complex .................................86

Figure 3.6: Dedicated borehole construction ..................................................................... 135

Figure 3.8: Generalised flow diagram of groundwater sampling ........................................... 198

Figure A 1: Potential contamination due to surface handling and transportation issues.

Figure A 2: Potential contamination due to surface handling and transportation issues.

Figure A 3: Potential contamination due to wastewater management and disposal issues.

Figure A 4: Potential contamination due to wastewater management and disposal issues.

Figure A 5: Potential contamination due to well-related issues. Corresponds to the pathway

Figure A 6: Potential contamination due to well-related issues. Corresponds to the pathway

Figure A 7: Potential contamination due to well-related issues. Corresponds to the pathway

Figure A 8: Potential contamination of groundwater resources unique to underground coal

Figure A 9: Potential contamination due to geology-related issues. Corresponds to the pathway

ABA Acid-base accounting

Bq/R Becquerel per molar gas constant

Aquifer An aquifer is a water saturated geological formation that has sufficient

Piston pump A piston pump is a positive-displacement pumping device, where a

Pyrolysis Pyrolysis occurs as coal heats up in the absence of oxygen during

Reserve Reserves are a subset of discovered resources which have a specific

Keywords: Unconventional gas; Underground coal gasification; Hydraulic fracturing; Hydraulic

Na hierdie vrae beantwoord is en die grondwaterbasislynmetodologie ontwikkel is, is die metode

Sleutelwoorde: Onkonvensionele gas; Ondergrondse steenkoolvergassing; Hidrouliese breking;