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Doctor of Philosophy
March 2015
ACKNOWLEDGEMENTS
extensive knowledge in chemistry and mineralogy which made the project possible. His
guidance, support and encouragement throughout has been greatly appreciated. I would
also like to thank my co-supervisor Professor Peter Leverett for his invaluable
assistance and perspectives on my thesis which have been greatly appreciated. Dr Ric
Wuhrer and the Advanced Materials Characterisation Facility provided assistance with
X-ray diffraction as well as support, guidance and equipment training. Jim Sharp is
thanked for his assistance with fieldwork and sharing his experience in mineralogy and
X-ray diffraction. John Rankin is acknowledged for sharing his knowledge on the
I would like to thank my fellow PhD students Matthew Sciberras, Adam Roper,
Mitchel Nancarrow and Simon Hager for their invaluable help, support and friendship
throughout the project. Finally I would like to thank the people who have helped and
especially my Mother, Father and Sister whose help, support, encouragement and love
This thesis contains work that, to the best of my knowledge and belief, is original except where
due acknowledgment appears in the text. I declare that material in this thesis has not been
submitted in any form for a degree or diploma at any other university or institution of tertiary
education.
..........…………………
March 2015
TABLE OF CONTENTS
Chapter 1 Introduction 1
1.1 Abstract 2
1.2 Geochemical Exploration 3
1.3 Bismuth as a path finder element 6
1.4 Project Outline 13
1.5 References 13
2.1 Abstract 23
2.2 Introduction 23
2.2.1 Bismite, bismoclite, bismutite, cannonite and riomarinaite 23
2.2.2 Rare and other bismuth oxide, carbonates, chloride, and sulfate minerals 26
2.3 Experimental 28
2.3.1 Syntheses of cannonite and riomarinaite 28
2.3.2 Solubility Studies 29
2.4 Results 30
2.4.1 Synthesis of cannonite and riomarinaite 30
2.4.2 Solubility Studies 30
2.5 References 40
3.1 Abstract 46
3.2 Introduction 46
3.3 Experimental 50
3.3.1 Syntheses of rooseveltite, tetrarooseveltite, atelestite and preisingerite 50
3.3.2 Solubility Studies 51
3.4 Results 51
3.4.1 Syntheses of rooseveltite, tetrarooseveltite, atelestite and preisingerite 51
3.4.2 Solubility Studies 55
3.5 References 60
Chapter 4 Russellite, Koechlinite and Sardignaite 66
4.1 Abstract 67
4.2 Introduction 67
4.3 Experimental 73
4.3.1 Syntheses of russellite, koechlinite and sardignaite 73
4.3.2 Solubility Studies 74
4.4 Results 75
4.4.1 Syntheses of russellite, koechlinite and sardignaite 75
4.4.2 Solubility Studies 79
4.5 References 84
5.1 Abstract 91
5.2.1 Introduction 91
5.3 Experimental 94
5.3.1 Syntheses of smirnite and chekhovichite 94
5.3.2 Solubility Studies 95
5.4 Results 95
5.4.1 Syntheses of smirnite and chekhovichite 95
5.4.2 Solubility Studies 98
5.5 References 102
Appendix A 137
CHAPTER 1
INTRODUCTION
1|Page
1.1 ABSTRACT
Bismuth minerals associated with Mo, W, and Sn, are often found amongst the
highly acidic deposits of the eastern ranges of Australia (Plimer, 1975; Weber et al.,
the supergene zone and make an assessment of these areas, as they have been the focus
the literature on bismuth as a pathfinder element, with respect to its ground water and
industrial and government reports, the use of various sampling methods, and the use of
assumptions in previous studies due to the information and techniques available at the
time (MacDuff, 1971; 1971a; 1971b; 1972; Siegal, 1974; Roes et al., 1979; Levinson,
1980; Plant et al., 1989; Plant et al., 1991; Fiella; 2010). Furthermore, information on
the Gibbs free energy of formation values was limited to 3 out of the 65 known bismuth
(Rankin et al., 2001, 2002; Sharpe and Williams, 2004) showed that even though
fact quite common. Examples of this can be found in certain deposits in eastern
Australia such as the New England Orogen. Therefore, the geochemical modelling
carried out in this thesis has focused on eastern Australia and examines potential
Furthermore this work can be been applied to exploration sites around the world where
2|Page
Bi is employed as a pathfinder element. To do this, a rigorous investigation including
Due to the nature and growth of manufacturing and consumption worldwide and
the need for mineral resources to meet these demands, the discovery of large-scale
near-surface deposits are in decline and thus the push to find deeper deposits has
review and scrutinise new, current and historic exploration techniques to discover
hidden ore bodies that are commercially significant. Exploration geochemistry is used
more chemical properties of a natural occurring material e.g. Hawkes and Webb, 1962.
The earliest reports of geochemical research date back to the 1930’s which were
carried-out in the former Soviet Union, and were known as metallometric surveying,
which we know today as geochemical surveys (Hawkes and Webb, 1962). It was not
until the late 1930’s to 1940’s that there was a rise in geochemical research by Western
countries, largely due to the increased resource requirements of World War II. Since
understanding to be obtained
3|Page
Geochemical exploration strategies include a number of key phases such as
critical and exploration geologists have to be cautious at each phase to ensure the
integrity of the data that is to be applied to the succeeding stages. Although for a variety
geological setting have, on average, the same profile or type deposit settings with
specific environments within this may contain deposits with a degree of uniqueness (i.e.
from which geochemical exploration studies can be undertaken while others do not.
between anomalous and background concentration in soils and ground waters. A review
of mining reports and reported data created by Siegal (1974), Rose et al. (1979), Roes
et al. (1979), Levinson (1980), Plant et al. (1989) and Plant et al. (1991) provide a solid
in site. However, due to the targeted nature of these reports extraction of additional data
requires the application of newer analytical methods which were/may not have been
available (or un-needed for the specific task) at the time. For example, for the elements
Bi and W, in some cases (MacDuff, 1971; 1971a; 1971b; 1972 and Fiella, 2010) reports
have honestly stated that because of a lack of references in the literature to similar
sampling programs, the results of their survey and previous data have to be arbitrarily
interpreted.
4|Page
Exploration across depositional landforms, both simple and complex, and with
shallow to deep transported regolith cover by using various geochemical techniques has
reaffirmed the important need to conduct and understand surface geochemistry and to
make it effective for new green field locations. Australia exhibits a unique landscape
with many of the landforms having their origins 300 Ma ago at the beginning of the
break-up of Gondwana (Aspandiar, 2008). Since that time the Australian land mass has
been exposed to wide ranging climatic conditions, from tropical to glacial periods as
well as undergoing various tectonic events which have been well documented (Anand,
2005). The impact of these weathering events has impacted the chemical and physical
R.R., 2005). Furthermore, during most of the Phanerozoic era (0 to 540 Ma), eastern
and south-eastern Australia were undergoing active plate tectonic processes leading to
the amalgamation of various accreted terranes from east to west from approximately
550 Ma up to approximately 200 MA. It has only been recently, during the Quaternary
period where the weathered crust has mostly formed over the last few million years.
This has preserved the weathered mantle as a wide spread cover, 20 to 100m thick, over
causes the destruction of primary ore deposits and the dispersion of ore and pathfinder
elements into the surrounding regolith. Conversely, it may also result in the supergene
enrichment of some deposits and promote the formation of secondary ore bodies. To
understand the history and potential mechanisms and pathways of migration of ore and
5|Page
1.3 BISMUTH AS A PATHFINDER ELEMENT
principally associated with high-temperature acid intrusives, related skarn deposits and
epithermal systems (Angino and Long, 1979; Lang and Baker, 2001; Baker et al.,
2005). It is (together with Te, W, Sn and other accessory elements) often associated
with gold mineralisation (Angino and Long, 1979; Baker et al., 2005). In the Australian
Figure 1.1: Location of the Cobar, Kingsgate, Wolfram Camp, Tennant Creek and
context (Figure 1.1) accessory Bi mineralisation is a feature of the Cobar- style deposits
(Stegman and Reynolds, 2005), the Henty and Mount Julia gold deposits, Tasmania
6|Page
(Callaghan, 2001), certain deposits in the Western Australian shield (Roberson et al.,
2001; Hassan and Clarke, 2005) and the Cu-Au-Bi deposits of the Tennant Creek area,
Northern Territory (Skirrow, 2002). Bismuth minerals are also important constituents
of the New England Orogen of eastern Australia (Figure 1.2), where they have reported
associations with Mo, W and Sn, and with highly acidic and very rich (albeit of low
tonnage) gold deposits of the eastern ranges of Australia (Plimer, 1975; Weber et al.,
1978). It is important to remember that this group of sites is indicative only, and is far
from being comprehensive but allows for a good starting point for the study of
7|Page
Bi has been extensively used as a pathfinder element in geochemical exploration
for a variety of deposits (Angino and Long, 1979; Hale, 1981; Robertson et al., 2001;
function of pH is well-established (Baes and Mesmer, 1976; Smith and Martell, 1976:
Norman, 1998; Thurston et al., 2005) and provides a general first order assessment of
its mobility in pore solution in the regolith. However, very little is known of the
chemistry, and the investigation of the secondary Bi minerals that serve to buffer the
ppb, whereas rhyolites and granites average 900 and 270 ppb, respectively. However,
not all granites exhibit this degree of enrichment (Lueth, 1999). Sedimentary rocks
contain higher amounts, with shales having the greatest average (0.26 ppm) and
limestone the least (30 ppb) (Lueth, 1999). Coal (5 ppm on average) and other organic-
Concentrations greater than 20 ppm have been reported for deep-sea manganese
nodules (Ahrens and Erlank, 1978) and similar enrichment occurs in bauxite and
average Bi concentration in soils of 0.2 ppm, much lower than previous reports in the
literature where the limits of detection were 5 ppm (McDuff and Snow, 1971).
8|Page
To understand the use of bismuth as a pathfinder element in fresh and marine
waters, Filella (2010) collated and critiqued data and analytical techniques from 125
published papers and tested methods to establish a reasonable typical range of total
dissolved bismuth in natural waters. She concluded that this was impossible to achieve
due to the wide, unexplained and dated dispersion of the data, as well as inadequate
published to date. Furthermore, Filella (2010) asserted that it was not possible to make
a confident estimation of bismuth concentrations in seawater and that it was also not
possible to identify a range of probable concentration values for fresh waters which
were not heavily polluted. Thus, in most cases, the use of bismuth as a pathfinder
element is untested to draw any conclusions for the geochemist with respect to
(McPhail, 1995). The speciation of Te has been established (McPhail, 1995) and the
thermodynamic properties for Te-bearing mineral, aqueous and gaseous species have
been reported (Ahmad et al., 1987; Afifi et al., 1988; Jaireth, 1991; Zhang and Spry,
1994; McPhail, 1995). The literature to date forms a solid starting point to assess the
role Te plays in different mineral systems, yet the exact thermodynamic and solubility
data for specific minerals in various geochemical settings are still to be reported. With
this in mind, along with themes presented in previous chapters, there are a number of
reports from geological surveys of various environments (Lett et al. 1998) where Te
and Bi anomaly values have been reported. However, these numbers are arbitrarily
9|Page
To understand the dispersion of bismuth in the supergene environment a review
of the secondary bismuth minerals and their occurrences has been undertaken which is
summarised in Table 1.1. In-depth reviews of specific minerals are indicated at the
beginning of chapters 2 to 5.
Table 1.1 The secondary minerals of bismuth. The number after the formula is the
Aiolosite Na2(Na2Bi)(SO4)3Cl 1
“Arsenowaylandite” BiAl3(AsO4)2(OH)6 1
Asselbornite1,2 Pb(BiO)3(UO2)4(AsO4)2(OH)7·4H2O 2
Atelestite Bi2(AsO4)O(OH) 35
Beyerite Ca(BiO)2(CO3)2 27
Bismite Bi2O3 174
Bismoclite BiOCl 50
Bismutite (BiO)2CO3 543
Bismutoferrite Fe2Bi(SiO4)2(OH) 47
“Bismutostibiconite” BiSb2O7 6
Bleasdaleite1 (Ca,Fe3+)2Cu5(Bi,Cu)(PO4)4(H2O,OH,Cl)13 1
Bouazzerite Bi6(Mg,Co)11Fe3+14(AsO4)18(OH)4·86H2O 1
Brendelite (Bi,Pb)2(Fe3+,Fe2+)(PO4)O2(OH) 2
Cannonite Bi2(SO4)O(OH)2 16
Chekhovichite Bi2Te4O11 4
Chiluite1 Bi3TeMoO10.5 1
Chrombismite Bi16CrO27 1
Clinobisvanite BiVO4 32
Cobaltneustädtelite Bi2Fe3+(Co,Fe3+)2(AsO4)2(OH,O)4 6
Daubréeite BiO(OH,Cl) 10
Dreyerite BiVO4 3
Dukeite Bi24Cr8O57(OH)6·3H2O 2
Francisite Cu3Bi(SeO3)2O2Cl 2
Gelosaite BiMo6+(2-5x)Mo5+6xO7(OH)·H2O 2
Hechtsbergite Bi2(VO4)O(OH) 4
Juanitaite1 Bi(Cu,Ca,Fe)10(AsO4)4(OH)11·2H2O 4
Kettnerite CaBi(CO3)OF 29
Koechlinite Bi2MoO6 26
Medenbachite Bi2Fe3+(Cu,Fe3+)(AsO4)2(OH,O)4 3
Mixite BiCu6(AsO4)3(OH)6·3H2O 139
Montanite1 Bi2TeO6·2H2O; Bi2(OH)4TeO4 19
Mrázekite Bi2Cu3(PO4)2O2(OH)2·H2O 10
Namibite Cu(BiO)2(VO4)(OH) 23
Neustädtelite Bi2Fe3+(Fe3+,Co)2(AsO4)2(OH,O)4 16
Nickelschneebergite (Bi,Ca)(Ni,Co,Fe)2(AsO4)2·2(OH,H2O) 1
Orthowalpurgite (BiO)4(UO2)(AsO4)2·2H2O 1
Paganoite NiBi(AsO4)O 1
10 | P a g e
Paulkellerite (BiO)2Fe(PO4)(OH)2 1
Perite PbBiO2Cl 16
Petitjeanite Bi3(PO4)2O(OH) 13
Phosphowalpurgite3 (BiO)4(UO2)(PO4)2 3
Pingguite Bi6Te2O13 3
Pottsite1 HPbBi(VO4)2·2H2O 3
Preisingerite Bi3(AsO4)2O(OH) 39
Pucherite BiVO4 46
Riomarinaite BiSO4(OH)·H2O 2
Rooseveltite BiAsO4 26
Russellite Bi2WO6 23
Sardignaite BiMo2O7(OH)·2H2O 1
Schlegelite Bi7(AsO4)3(MoO4)2O4 1
Schneebergite (Bi,Ca)(Co,Ni,Fe)2(AsO4)2·2(OH,H2O) 2
Schumacherite Bi3(VO4)2O(OH) 11
Sillénite Bi12SiO20 14
Smirnite Bi2TeO5 4
Smrkovecite4 Bi2(PO4)O(OH) 2
Sphaerobismoite Bi2O3 2
Šreinite5 Pb(BiO)3(UO2)4(PO4)2(OH)7·4H2O 1
Tetrarooseveltite BiAsO4 1
Uranosphaerite Bi(UO2)O2(OH) 17
Walpurgite (BiO)4(UO2)(AsO4)2·2H2O 31
Waylandite BiAl3(PO4)2(OH)6 25
Ximengite BiPO4 3
Yecoraite1 Fe3Bi5(TeO4)2O9·9H2O 5
Zaïrite Bi(Fe,Al)3(PO4)2(OH)6 2
Zavaritskite BiOF 12
1
Structure unknown. 2Arsenate analogue of šreinite. 3Walpurgite structure type. 4Atelestite structure type.
5
Structure unknown; phosphate analogue of asselbornite ; “ “ unapproved mineral species.
Chemical formulae and mineral approval status derived from the IMA mineral database list (Rakovan,
2007).
An inspection of Table 1.1 indicates that the most common phases reported are
bismutite, bismite, mixite and bismoclite. Stoichiometries indicated in Table 1.1 are
based for the most part on single-crystal X-ray determinations (Anthony et al., 1990;
1995; 1997; 2000; 2003) and reference is made to these where appropriate or to other
are recognised as being imperfect and other localities for a number of the secondary
minerals may be gleaned from the literature (vide infra). Nevertheless, the tabulation
11 | P a g e
does indicate which phases are common and thus likely to be generally present in
Appendix A Some of the results are based upon more than 150 powder X-ray
diffraction determinations (Rankin et al., 2002; Sharpe and Williams, 2004). A further
study of some 40 specimens from the collections of the Australian Museum has
provided supplementary data for other deposits; rare minerals were encountered but a
This in turn has a bearing on the selection of species that should be incorporated
Bi2(SO4)O(OH)2, for example, are seen to be important even though they are found to
be rare. Of course, each secondary mineral has its own geochemical history and can
with a view towards a functional model for their influence on bismuth dispersion in the
regolith, very rare species may be largely passed over because they almost certainly
12 | P a g e
1.4 PROJECT OUTLINE
formed as a result of the oxidation of primary Bi-bearing mineralisation and forms the
basis of the argument for this thesis. To draw conclusions on a proper understanding of
temperature aqueous chemistry and knowledge of the secondary Bi minerals that serve
to buffer the element between the solid and solution states. Of the known bismuth
minerals reliable thermodynamic data are available only for bismite, bismoclite and
bismutite. This highlights the gap in the literature when attempting to construct a model
for the stability and dispersion of the bismuth secondaries. To determine their
ground waters (discussed in Chapter 6). The common and key phases that were taken
discussed in Chapter 2.
in Chapter 3.
13 | P a g e
1.5 REFERENCES:
Afifi, A., Kelly, M., and Essene, E.J. (1988) Phase relationships among tellurides,
Anand, R.R. (2005) Weathering history, landscape evolution and implications for
Ahmad, M. Solomon, M., and Walshe, J.L. (1987) Mineralogical and geochemical
studies of the Emperor gold telluride deposit, Fiji. Economic Geology, 82, 234-270.
Ahrens, L.H. and Erlank, A.J. (1978) Bismuth. In: Wedepohl, K.H. (Ed.) Handbook of
Angino, E.E. and Long, D.T. (Eds) (1979) Geochemistry of Bismuth. Dowden,
Anthony, J.W., Bideaux, R.A., Bladh, K.W. and Nichols, M.C. (1990) Handbook of
Tucson, Arizona.
Anthony, J.W., Bideaux, R.A., Bladh, K.W. and Nichols, M.C. (1995) Handbook of
14 | P a g e
Anthony, J.W., Bideaux, R.A., Bladh, K.W. and Nichols, M.C. (1997) Handbook of
Tucson, Arizona.
Anthony, J.W., Bideaux, R.A., Bladh, K.W. and Nichols, M.C. (2000) Handbook of
Anthony, J.W., Bideaux, R.A., Bladh, K.W. and Nichols, M.C. (2003) Handbook of
Tucson, Arizona.
Aspandiar, M.F., Anand, R.R. and Gray, D.J., (2008) Geochemical dispersion
Baes, C.F. Jr and Mesmer, R.E. (1976) The Hydrolysis of Cations. Plenum Press, New
York.
Baker, T., Pollard, P.J., Mustard, R., Mark, G. and Graham, J.L. (2005) A comparison
15 | P a g e
Brooks, R. R. (1972) Geobotany and biogeochemistry in mineral exploration: New
Mitteilungen, 7, 260-269.
Callaghan, T. (2001) Geology and host-rock alteration of the Henty and Mount Julia
Champion, D.C., Kositcin, N., Huston, D.L., Mathews, E. and Brown, C. (2009)
Clissold, M.E. (2007) Aspects of the supergene geochemistry of copper nickel and
Collins, P., Hooper, B. and Cornelius, M. (2004) Whim Creek Cu-Zn-Pb deposit,
Pilbara, WA. In: Butt, C.R.M., Cornelius, M., Scott, K.M. and Roberson, I.D.M.
(Eds), Regolith Expression of Australian Ore Systems. CRC LEME, Perth, pp. 1-3.
Emsley, J. (1991) The Elements. Second edition, Oxford University Press, Oxford.
Filella, M. (2010) How reliable are environmental data on 'orphan' elements? The case
12, 90-109.
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Goldschmidt, V.M. (1970) Geochemistry. Oxford University Press, Oxford.
Hassan, L.Y. and Clarke, R.M., (2005) Some unusual gold and bismuth mineralization
references therein.
Hawkes, H.E. and Webb, J.S. (1962) Geochemistry in Mineral Exploration. Harper and
precious metal deposits. Economic Geology, 37. James Cook University of North
Queensland, Australia.
Kabata-Pendias, A. (2001) Trace Elements in Soils and Plants. 3rd Edition, CRC Press,
Lang, J.R. and Baker, T. (2001) Intrusion-related gold systems: the present level of
techniques for base and precious metals in the Kootenay Terrane. Geological
17 | P a g e
Levinson, A.A., (1980) Introduction to Exploration Geochemistry: The Supplement,
Lueth, V.W. (1999), Bismuth: Element and Geochemistry. In: Fairbridge, R.W. (Ed.)
MacDuff, R. and Snow, A. (1971) Quarterly Report Period to 8th January 1971, EL208,
AOG Minerals PL. New South Wales Department of Primary Industries (Mineral
MacDuff, R. and Zerwick, J. (1971a) EL208, Quarterly Report Period to 8th July 1971,
AOG Minerals PL. New South Wales Department of Primary Industries (Mineral
MacDuff, R. and Zerwick, J. (1971b) EL208, Quarterly Report Period to 8th October
1971, AOG Minerals PL. New South Wales Department of Primary Industries
MacDuff, R. and Zerwick, J. (1972) EL208, Quarterly Report Period to 8th January
1972, AOG Minerals PL. New South Wales Department of Primary Industries
18 | P a g e
Norman, N.C., (1998) Chemistry of Arsenic, Antimony and Bismuth. Blackie, London.
Plant, J.A., Breward, N., Forrest, M.D. and Smith, R.T. (1989) The gold pathfinder
98, B91-101.
Plant, J.A., Cooper, D.C., Green, P.M., Reedman, A.J. and Simpson, P.R. (1991)
Queensland. In: N Knight C.L. (Ed.), Economic Geology of Australia and Papua
Rakovan, J. (2007) Words to the Wise- More than 4000 To Be Exact. Rocks and
Rankin, J., Sharpe, J.L. and Williams, P.A. (2001) Betpakdalite from the tin deposits of
Mineralogy, 7, 15-17.
19 | P a g e
Rankin, J., Lawrence, L.J., Sharpe, J.L. and Williams, P.A., (2002) Rare secondary
bismuth, tungsten and molybdenum minerals from Elsmore, New England district
Roberson, I.D.M., King, J.D. and Anand, R.R., (2001) Regional geology and
geochemical exploration around the Stellar and Quasar gold deposits, Mt Magnet,
Rose, A.W., Hawkes, H.E. and Webb, J.S., (1979) Geochemistry in Mineral
Siegel, F. R., (1974) Applied Geochemistry: New York, John Wiley and Sons, 353p.
Sharpe, J.L. and Williams, P.A., (2004) Secondary bismuth and molybdenum minerals
from Kingsgate, New England district of New South Wales. Australian Journal of
Smith, R.M. and Martell, A.E., (1976) Critical Stability Constants. 4. Inorganic
20 | P a g e
Stegman, C. and Reynolds, I., (2005) Primary mineralisation in Cobar deposits, with
Thurston, J.H., Swenson, D.C. and Messerle, L., (2005) Solvolytic routes to new
Weber, C.R., Paterson, I.B.L. and Townsend, D.J., (1978) Molybdenum in New South
Wales. Geological Survey of New South Wales Mineral Resources Series, 43.
Zhang, X. and Spry, P.G. (1994) Calculated stability of aqueous tellurium species,
1166.
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CHAPTER 2
22 | P a g e
2.1 ABSTRACT
various conditions, further develops our understanding of the dispersion and mobility of
2.2 INTRODUCTION
The minerals of interest that were studied in this chapter were bismite,
bismoclite, bismutite, cannonite and riomarinaite. The discovery and associations are
discussed below in section 2.2.1. These were chosen due to their known associations
and their common assemblage associations as shown in the compiled data of Appendix
A. Other rare or uncommon phases which are of note, however, were not studied in
was first reported in 1848 (Frondel, 1943). The single-crystal structure of bismite was
23 | P a g e
reported by Sillén (1940) and refined by Malmros (1970). The Colavi mine in the
taken to be the type locality and bismite is reported in the vast majority of bismuth
Two basic carbonates of bismuth are known, bismutite, Bi2O2CO3 (Figure 2.1),
stabilities of these phases are known (Clissold, 2007). Bismutite was first named by
single type locality cannot be definitely ascribed. Frondel (1943) reviewed the available
evidence and concluded that the mineral had the composition Bi2O2CO3. The single
crystal structure was originally reported by Lagerkrantz and Sillén (1948) and refined
by Grice (2002). The predominance of bismutite amongst the vast majority of Bi-rich
Bi2O3, is a rare phase by comparison and it should be noted again that Bi2O3 reacts with
The bismuth halide bismoclite, BiOCl, was first described from Jackal’s Water,
The structure was reported by Bannister (1935) and refined by Keramidas et al. (1993).
cerussite.
24 | P a g e
Figure 2.1: Bismutite from Schmiedestollen dump, Wittichen, Schenkenzell, Black
Forest, Baden-Württemberg, Germany (Bonacina, 2011)
was reported by Golic et al. (1982), Sadanaga and Bunno (1974) first reported
cannonite from the Ashio mine, Ashio, Tochigi Prefecture, Japan, where it was
However, a specimen from the Tunnel Extension No. 2 mine, Bullion Canyon, Piute
County, Utah, USA is taken to be the type locality (Stanley et al., 1992). The structure
According to Rögner (2005) riomarinaite was found at the Falcacci stope, Rio Marina
mine, Elba Island, Tuscany, Italy and it was associated with primary phases including
25 | P a g e
bismuth, bismuthinite, Bi sulfosalts and molybdenite and secondary minerals
Figure 2.2: Cannonite from the Duadello mine (Baitello mine), Palotto Valley (Palot
Valley), Fraine, Pisogne, Camonica Valley, Brescia Province, Lombardy, Italy
(Bonacina, 2009).
2.2.2 Rare and other bismuth oxide, carbonates, chloride, and sulfate minerals
The structure for sphareobismoite was reported by Blower and Greaves (1988)
the reported type locality (Walenta, 1995), where it was found to be the oxidation
with bismutite and mixite. Other associated secondary Bi minerals include atelestite,
26 | P a g e
walpurgite (Walenta, 1992, 1995). Sphaerobismoite is a rare phase compared to
which was first reported by Frondel (1943) where it was associated with bismutite.
Reported as a carbonate of Bi and Ca, a definite formula was not confirmed until later
reported by Lagerkrantz and Sillén (1948) and later refined by Grice (2002).
(1960) space group Bmmb, a = 5.591, b = 5.431 and c = 12.200 Å. However, Bridge
(1976) reported that perite from Glen Florrie Station, Western Australia, was tetragonal
(a = 5.579(3) and c = 12.45(1) Å). Both orthorhombic and tetragonal forms are known
synthetically (Deschanvres et al., 1970; Ketterer and Krämer, 1985; Lopatkin, 1987).
al., 2013; Garavelli et al., 2013). As such, they have not been negated from the future
27 | P a g e
2.3 EXPERIMENTAL
(500 rpm) at room temperature. After 1 hour the initially yellow powder changed colour
to white, however the mixture was left to stir for a further 5 days. The solid was then
collected at the pump on GF/F grade filter paper, rinsed with DI water and acetone, and
sucked dry.
stirred (500 rpm). The mixture was again observed to change colour after 1 hour from
yellow to white but was left to stir for 5 days. The precipitate was isolated as above.
and 30 mA). Traces were produced between 5-70o 2θ, with a step size of 0.02o and a
rate of 1.2 o min–1. Diffraction Technology Data processing software (Eva) and JCPDS-
ICDD data base files were used to identify the phases produced.
28 | P a g e
2.3.2 Solubility Studies
Solubility studies were undertaken using sealed 250 cm3 conical QuickfitR flasks
ION450 apparatus fitted with a combination electrode. The solubility studies were
conducted by precipitation of the desired product following the synthetic procedures for
cannonite and riomarinaite. Bismuth oxide (ca 0.5 g) was added to a series of seven
conical flasks containing 49.97 cm3 of standardised H2SO4; 0.1067 M for cannonite and
1.067 M for riomarinaite. The flasks were left for 10 weeks during which time the pH
of a paired flask was monitored periodically until the pH of the test mixture remained
stable. The solutions were filtered using GF/F grade filter paper and the filtrates
29 | P a g e
2.4 RESULTS
High purity, single phase samples of cannonite and riomarinaite were obtained
powder X-ray diffraction. Unit cell parameters were refined in LAPOD (Langford,
1973) and values obtained were a = 7.690(2), b = 13.861(6) and c = 5.682(2) Å for
are in good agreement with those reported by Golic et al. (2007) and Graunar and
Equilibrium was achieved after 6 weeks for cannonite but not for riomarinaite,
X-ray diffraction examination of the original riomarianite samples after 2 weeks and 10
riomarinaite were not pursued due to the apparent metastability. The apparent
metastability of riomarinaite in contact with its mother liquor is shown in the X-ray
30 | P a g e
1200
1100
1000
900
800
700
Lin (Counts)
600
500
400
300
200
100
5 10 20 30 40 50 60 70
2-Theta - Scale
Figure 2.3: Powder XRD trace of riomarinaitre with peak positions of the ‘type’ pattern from JCPDS-ICDD file 01-076-1103 (red).
34 | P a g e
430
420
410
400
390
380
370
360
350
340
330
320
310
300
290
280
270
260
250
Lin (Counts)
240
230
220
210
200
190
180
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0
6 10 20 30 40 50 60 70 80
2-Theta - Scale
Figure 2.4: Powder XRD trace of riomarinaite after 2 weeks showing a mixture of riomarinaite and cannonite with peak positions of the ‘type’
patterns from JCPDS-ICDD files for riomarinaite 01-076-1103 (red) and cannonite 00-045-1439 (blue).
35 | P a g e
600
500
400
Lin (Counts)
300
200
100
6 10 20 30 40 50 60 70
2-Theta - Scale
Figure 2.5: Powder XRD trace of riomarinaite after 10 weeks converted to cannonite with peak positions of the ‘type’ pattern for
36 | P a g e
Cannonite dissolved incongruently in aqueous H2SO4 as expressed in equation
(1).
3 = 0.093 2 = 0.348 and = 0.768. In all instances, o is taken to be unity. The
corresponding activity a(Bi3+), was calculated from the solubility data (Table 2.1).
speciation using COMICS (Perrin and Sayce, 1967). Reliable lg K values for equation
(2), (4), (6), (8), (10), (12) and (14) of lg K(298.15 K) = –1.11, –3.30, –8.21, 2.01, 3.41,
4.60 and 4.88 at I = 0 mol dm–3 were reported by Fedorov et al. (1971) and van Der Lee
37 | P a g e
and Lomenech (2004). Correction to I = 0.128, mol dm–3 by the method of Baes and
Mesmer (1976), yields lg K(298.15 K) = –1.73, –4.30 and –9.33. Using the
relationships shown by equations (3), (5) and (7), (9), (11), (13) and (15), the
38 | P a g e
This yields a value of lg K for equation (1) –8.00 ± 0.50 and yields a
takes into account the analytical error of the solubility experiments and errors quoted
39 | P a g e
2.5 REFERENCES
Baes, C.F. Jr and Mesmer, R.E. (1976) The Hydrolysis of Cations. Plenum Press, New
York.
Barreca, D., Morazzoni, F., Rizzi, G.A, Scotti, R. and Tondello, E. (2001) Molecular
Blower, S.K. and Greaves, C. (1988) The structure of β-Bi2O3 from powder neutron
Palotto Valley (Palot Valley), Fraine, Pisogne, Camonica Valley, Brescia Province,
<http://www.mindat.org/photo-245067.html>.
Clissold, M.E. (2007) Aspects of the supergene geochemistry of copper nickel and
40 | P a g e
Cox, J.D., Wagman, D.D. and Medvedev, V.A. (1989) CODATA Key Values for
Fedorov, V.A., Kalosh, T.N., Chernikova, G.E. and Mironov, V.E. (1971) Sulphato-
Grice, J.D. (2002) A solution to the crystal structures of bismutite and beyerite.
41 | P a g e
Graunar, M. and Lazarini, F. (1982) Di-μ-hydroxo-bis[aquasulfatobismuth(III)]. Acta
Kaye, G.W.C. and Laby, T.H. (1995) Tables of Physical and Chemical Constants. 16th
and CaBi2O2(CO3)2 (beyerite). Arkiv för Kemi, Mineralogi och Geologi, 25, 1-21.
Langford, J.I. (1973) Least-squares refinement of cell dimensions from powder data by
Lovreček, B., Mekjavić, I. and Metikoš-Huković, M. (1985) Bismuth. In: Bard, A.J.,
International Union of Pure and Applied Chemistry and Marcel Dekker, New York,
180-187.
Malmros, G. (1970) The crystal structure of α-Bi2O3. Acta Chemica Scandinavica, 24,
384-396.
Martell, A.E. and Smith, R.M. (1982) Critical Stability Constants. Volume 5:First
42 | P a g e
Mountain, E.D. (1937) Two new bismuth minerals from South Africa. Mineralogical
Perrin, D.D. and Sayce, I.G. (1967) Computer calculation of equilibrium concentrations
Rögner, P. (2005) Riomarinait, ein neues Wismutmineral vom Abbau Falcacci, Rio
206-207.
Stanley, C.J., A.C. Roberts, D.C. Harris, A.J. Criddle, and J.T. Szymański (1992)
Taylor, P., Sunder, S. and Lopata, V.J. (1984) Structure, spectra, and stability of solid
van der Lee, J. and Lomenech, C. (2004) Towards a common thermodynamic database
43 | P a g e
Walenta, K. (1992) Die Mineralien des Schwarzwaldes. Weise, Munich.
Walenta, K. (1995) Sphaerobismoite, a new mineral of the composition Bi2O3 from the
44 | P a g e
CHAPTER 3
45 | P a g e
3.1 ABSTRACT
immobilisation. Solubilities in aqueous HNO3 were determined at 298.2 K and the data
obtained used to calculate values of ΔGfө at the same temperature. The derived ΔGfө
(298.2 K) values for atelestite, (–1102.58 ± 5.6 kJ mol–1), preisingerite, (–1823.29 ± 2.5
kJ mol–1) and rooseveltite (–716.91 ± 1.5 kJ mol–1) have been used in subsequent
calculations to determine their relative stabilities and relationships with other secondary
Bi minerals.
3.2 INTRODUCTION
tetrarooseveltite, BiAsO4 and rooseveltite, BiAsO4, have been reported from multiple
localities worldwide (Chapter 2, Table 1) and are the most abundant of the Bi-As
minerals found. Bismuth arsenates are rare minerals, but they can be a common feature
preisingerite have been reported from the Elsmore mine, Elsmore, New South Wales,
Australia (Rankin et al., 2002, 2013), yet atelestite to date has never been reported.
(Rankin et al., 2013) at this locality. Bismuth and bismuthinite are primary phases.
46 | P a g e
Other secondary Bi minerals identified from Elsmore included bismite, bismutite,
(Rankin et al., 2002, 2013). This chapter has focused on the chemical modelling of
bismuth arsenates the data presented cab be used to determine the roles theses phases
play at different mine sites globally. As such the use of data from previous chapters can
Atelestite (Figure 3.1) was first reported from the Neuhilfe mine, Schneeberg,
bismutoferrite and paulkellerite (Breithaupt, 1832; Dunn et al., 1988; Weiss, 2007)
mixite, preisingerite, rooseveltite and walpurgite (Palache et al., 1951; Walenta, 1972,
1995a). The structure of atelestite was reported by Mereiter and Preisinger (1986).
Figure 3.1: 0.5 mm balls of yellow atelestite overgrowing spherules of bismutite. From
Hérival, Val-d'Ajol, Vosges, Lorraine, France. (Valverde, 2006)
47 | P a g e
Both the structure and the mineral occurrence of preisingerite, Bi3(AsO4)2O(OH),
(Figure 3.2) were first reported from the San Francisco de los Andes, Calingasta, San
Juan, Argentina (Bedlivy and Mereiter, 1982b) where it was found to be associated with
bismuth, bismuthinite, Bi sulfosalts and rooseveltite (Bedlivy et al., 1972; Bedlivy and
Figure 3.2: Preisingerite from the Clara Mine, Rankach valley, Oberwolfach, Wolfach,
Black Forest, Baden-Württemberg, Germany, picture width 2 mm (Wolfsried, 2007).
whereby the specimen analysed was from the Santiaguillo, Macha, Chayanta Province,
have been reported from this site. Rooseveltite’s structure was first reported by Bedlivy
48 | P a g e
and Mereiter (1982a). Rooseveltite has had few reported localities (Anthony et al.,
2000) and, as mentioned previously, was reported from Australia at the Elsmore mine,
NSW.
Figure 3.3 : Rooseveltite aggregates (white to pale yellow: ~1mm) and marcasite,FeS2,
(metallic green) from the Lagoa Mine, Estorãos, Ponte de Lima, Viana do Castelo
District, Portugal (Alves, 2010).
Tetrarooseveltite, BiAsO4, has a known structure (Mooney, 1948). The type locality
and only known specimen reported to date is the Moldava deposit, Krušnéhory
Mountains, Bohemia, Czech Republic. The specimen was associated with bayldonite,
primary Bi phases are bismuth, bismuthinite and Bi sulfosalts; other secondary minerals
are bismutite, mixite, preisingerite, rooseveltite and zavaritskite (Sejkora, 1994; Sejkora
49 | P a g e
3.3 EXPERIMENTAL
3.3.1 Syntheses
riomarinaite (0.5 g) in an acid digestion bomb, which was sealed and heated at 180 oC
for three days. The mixture was allowed to cool to ambient temperature in the bomb.
The obtained solid was then collected at the pump on GF/F grade filter paper, rinsed
water (50 mL). The mixture was buffered to pH 4.39 with 2 M KOH. The bomb was
then placed in an oven (190oC) for eleven days. The bomb was removed and allowed to
round bottomed flask containing riomarinaite (0.5 g). The mixture was then refluxed for
40 kV, 30 mA). Traces were produced between 5-70o 2θ, with a step size of 0.02 o and a
rate of 1.2 o min–1. Diffraction Technology Data processing software (Traces Version 6)
and JCPDS-ICDD data base files were used to identify the phases produced.
50 | P a g e
3.3.2 Solubility Studies
Solubility studies were undertaken using sealed 250 cm3 conical QuickfitR flasks
ION450 apparatus fitted with a combination electrode. The minerals (ca 0.1 g) were
added to a series of conical flasks containing 100 cm3 of standardised HNO3; 0.0981 M.
The flasks were left for 10 weeks during which time the pH of a paired flask was
monitored periodically until no change was detected. The remaining solutions were
collected by filtration through WhatmanR GF/F fibreglass filter papers and stored in
clean PET bottles. Dissolved Bi/As concentrations were determined using ICP-MS by a
3.4 RESULTS
an essentially quantitative yield. Powder X-ray diffraction did not give any evidence for
any contaminating phase. Unit cell parameters were refined using the program LAPOD
(Langford, 1973), based on indices calculated using PowderCell (Kraus and Nolze,
1996a,b) and gave a = 6.878(1), b =7.159 (2) c =6.734(3) Å for rooseveltite, a = 9.993
(1), 7.404 (1) c = 6.937 (3) Å for preisingerite, and a = 7.000 (1), 7.430(1) c = 10.831
(2) Å for atelestite. These results are in excellent agreement with those reported
elsewhere (Bedlivy and Mereiter, 1982a, 1982b; Mereiter and Preisinger, 1986).
51 | P a g e
120
110
100
90
80
Lin (Counts)
70
60
50
40
30
20
10
9 10 20 30 40 50 60
2-Theta - Scale
Figure 3.4: Powder XRD trace of rooseveltite with peak positions of the ‘type’ pattern from JCPDS file 00-025-0089 (red).
52 | P a g e
280
270
260
250
240
230
220
210
200
190
180
170
Lin (Counts)
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
10 20 30 40 50
2-Theta - Scale
Figure 3.5: Powder XRD trace of preisingerite with peak positions of the ‘type’ pattern from JCPDS file 01-075-1629 (red).
53 | P a g e
120
110
100
90
80
70
Lin (Counts)
60
50
40
30
20
10
11 20 30 40 50 60 70
2-Theta - Scale
Figure 3.6: Powder XRD trace of atelestite with peak positions of the ‘type’ pattern from JCPDS file 00-025-0089 (red).
54 | P a g e
3.4.2 Solution studies
Solubility data for the three minerals are reported in Tables 3.1, 3.2 and 3.3. All
dissolution of atelestite was accounted for with respect to preisingerite. The dissolution
= 1.152,) was used in the determination of ion speciation patterns using the program
COMICS (Perrin and Sayce, 1967). Individual ion activity coefficients were calculated
rooseveltite I = 0.098 mol.dm–3, 3 = 0.081, 2 = 0.327 and = 0.756. For
preisingerite I = 0.090 mol.dm–3, 3 = 0.043, 2 = 0.246 and = 0.704 and for
atelestite I = 0.102 mol.dm–3, 3 = 0.1079, 2 = 0.372 and = 0.781. In all instances,
o is taken to be unity. The activity of H+(aq), a(H+), in HNO3 0.0981 M was then
calculated and corresponding activity a(Bi3+) was calculated from the solubility data
55 | P a g e
Table 3.1 Dissolved metal concentrations for rooseveltite
Solution [Bi] ppm [Bi] mol dm-3 [As] ppm [As] mol dm-3
1 0.41 1.96 x 10-06 0.91 9.49 x 10-06
2 0.35 1.67 x 10-06 0.72 7.50 x 10-06
3 0.41 1.96 x 10-06 0.76 7.92 x 10-06
4 0.36 1.72 x 10-06 0.80 8.34 x 10-06
5 0.35 1.67 x 10-06 0.75 7.82 x 10-06
6 0.43 2.06 x 10-06 0.71 7.40 x 10-06
7 0.34 1.63 x 10-06 0.78 8.13 x 10-06
8 0.36 1.72 x 10-06 0.86 8.96 x 10-06
9 0.34 1.63 x 10-06 0.76 7.92 x 10-06
Mean 0.36 1.73 x 10-06 0.85 8.08 x 10-06
Error 0.03 1.52 x 10-07 0.05 5.56 x 10-07
Solution [Bi] ppm [Bi] mol dm-3 [As] ppm [As] mol dm-3
1 0.59 2.8 x 10-06 1.8 2.4 x 10-05
2 0.52 2.5 x 10-06 2.1 2.8 x 10-05
3 0.58 2.8 x 10-06 1.9 2.5 x 10-05
4 0.61 2.9 x 10-06 1.7 2.3 x 10-05
5 0.37 1.8 x 10-06 3.1 4.1 x 10-05
Mean 0.46 2.2 x 10-06 2.1 2.8 x 10-05
Error 0.16 7.4 x 10-07 2.7 1.3 x 10-05
56 | P a g e
The pH at equilibrium for rooseveltite was used in the determination of
individual ion speciation using COMICS (Perrin and Sayce, 1967). Reliable Log K
values for equation (2), (4), (6), (8), (10), (12) and (14) of Log K(298.15 K) = –1.34, –
3.52, -8.44, +10.62, +17.75 and +19.48 at I = 0 mol dm–3 were reported by van Der Lee
and Lomenech (2004) and Wagman et al. (1982). Correction to I = 0.128, mol dm–3 by
the method of Baes and Mesmer (1976), yields lg K(298.15 K) = -1.54, –4.05, –9.07,
10.96, 17.29 and 19.52 Using the relationships shown by equations (5), (7), (9), (11),
HAsO42(aq),- and H2AsO42-(aq) are 7.10 x 10-7, 7.60 x 10-8, 2.3 x 10-12, 1.9 x 10-6, 6.2 x
57 | P a g e
Correction to I = 0.128, mol.dm–3 for preisingerite by the method of Baes and
Mesmer (1976), yields lg K(298.15 K) = –1.54, –3.94, –8.85, +10.96, 17.29 and 19.52.
Using the relationships shown by equations (5), (7), (9), (11), (13), and (15) the
and H3AsO40(aq) are 6.60 x 10-8, 5.10 x 10-9 7.53 x 10-9, 1.20 x 10-6, 2.8 x 10-12 , and
Mesmer (1976), yields lg K(298.15 K) = –1.54, –4.05, –9.07, 10.96, 17.29 and 19.52.
Using the relationships shown by equations (5), (7), (9), (11), (13), and (15) the
and H3AsO40(aq) are 2.20 x 10-5, 7.20 x 10-7 and 1.30 x 10-10 mol.dm–3 respectively. the
atelestite for equations (1) –9.65±0.50, (2) –41.43±0.50, and (3) –7.93±0.50
respectively and yields the corresponding ΔGrө and ΔGfө values for equations (1) to (3)
as follows:
716.91±1.5 kJ mol–1
58 | P a g e
The estimated error takes into account the analytical error of the solubility experiments
59 | P a g e
3.5 REFERENCES
Alves, P., (2010) Rooseveltite: Bi(AsO4), Marcasite: FeS2, Lagoa Mine, Estorãos, Ponte
http://www.mindat.org/photo-319350.html.
Anthony, J.W., Bideaux, R.A., Bladh, K.W. and Nichols, M.C. (2000) Handbook of
Baes, C.F. Jr and Mesmer, R.E. (1976) The Hydrolysis of Cations. Plenum Press, New
York.
compounds and aqueous species. John Wiley and Sons, New York.
Bedlivy, D., Llamblas, E.J. and Astarloa, J.F.H. (1972) Rooseveltit von San Francisco
de los Andes und Cerro Negro de la Aguadita, San Juan, Argentina. Tschermaks
from San Juan Province, Argentina: its description and crystal structure. American
60 | P a g e
Breithaupt, A. (1832) Vollständige Characteristik des Minerals-Systems, Second
Cox, J.D., Wagman, D.D. and Medvedev, V.A. (1989) CODATA Key Values for
Dunn, P.J., Grice, J.D., Wicks, F.J. and Gault, R.A. (1988) Paulkellerite, a new bismuth
870-872.
Kaye, G.W.C. and Laby, T.H. (1995) Tables of Physical and Chemical Constants. 16th
Kraus, W. and Nolze, G. (1996a) PowderCell - a program for the representation and
Kraus, W. and Nolze, G. (1996b) PowderCell 1.8 and Windows version 1.0. Federal
61 | P a g e
Langford, J.I. (1973) Least-squares refinement of cell dimensions from powder data by
Lovreček, B., Mekjavić, I. and Metikoš-Huković, M. (1985) Bismuth. In: Bard, A.J.,
International Union of Pure and Applied Chemistry and Marcel Dekker, New York,
180-187.
Meier, S. and Dünkel, B. (2010) Mineralien von der Dorschenmühle bei Lichtenberg,
Crystallographica, 1, 163-165.
62 | P a g e
Nordstrom, D.K. and Archer, D.G. (2003) Arsenic thermodynamic data and
Palache, C., Berman, H. and Frondel, C. (1951) Dana’s System of Mineralogy, seventh
Perrin, D.D. and Sayce, I.G. (1967) Computer calculation of equilibrium concentrations
Rankin, J., Lawrence, L.J., Sharpe, J.L. and Williams, P.A. (2002) Rare secondary
bismuth, tungsten and molybdenum minerals from Elsmore, New England district
Rankin, J., Sharpe, J.L. and Williams, P.A. (2013) Unpublished survey of secondary Bi,
Robie, R.A. and Hemingway, B.S. (1995) Thermodynamic properties of minerals and
related substances at 298.15K and 1 bar (105 Pascals) pressure and at higher
63 | P a g e
Sejkora, J. (1994) Minerály ložiska Moldava v Krušných horách. Bulletin
http://www.mindat.org/photo-50845.html.
van der Lee, J. and Lomenech, C. (2004) Towards a common thermodynamic database
Wagman, D. D., Evans, W. H., Parker, V. B, Schumm, R. H., Halow, I., Bailey, S.
M., Churney, K. L., and Nuttall, R. L. (1982) The NBS tables of chemical
Supplement 2, 1-392.
64 | P a g e
Walenta, K., (1995) Sphaerobismoite, a new mineral of the composition Bi2O3 from the
Weiss, S., Green, D.H., Hooper, J.J., and Elton, N. (2007) Erzgänge und “Alpine”
Klüfte: Die Mineralien des Hingston quarry, Calstock, Cornwall. Lapis, 32(11), 13-
25.
65 | P a g e
CHAPTER 4
66 | P a g e
4.1 ABSTRACT
with high-temperature acid intrusives, related skarn deposits and epithermal systems
(Angio and Long, 1979; Baker et al., 2005; Lang and Baker, 2001). It is, together with
Te, W, Sn and other accessory elements, often associated with gold mineralisation
(Angio and Long, 1979; Baker et al., 2005). The association of Bi minerals at the Mo-
Bi deposits of Kingsgate and surrounding deposits found in the New England Orogen,
New South Wales, commonly give rise to koechlinite, Bi2MoO6, and russellite,
Bi2WO6, in the oxidised zone (Rankin et al., 2002; Sharpe and Williams, 2004;
Clissold, 2007). The Gibbs free energy of formation values for russellite, koechlinite,
and are used to determine the roles they play in the immobilisation of bismuth in the
oxidised environment.
4.2 INTRODUCTION
are currently recognised by the IMA and most of them are rare mineral phases (Anthony
et al., 1990, 1995, 1997, 2000, 2003; Gaines et al., 1997). The molybdate salts
powellite, CaMoO4, and wulfenite, PbMoO4, are the most common, and have been both
reported in small amounts from Kingsgate (England, 1985). Basic Cu(II) molybdates
occur in certain porphyry Mo deposits and several uranyl molybdates are associated
with oxidised, U-rich ores. No carbonates are known and the simple oxides molybdite,
MoO3, and sidwillite, MoO3·2H2O, are very rare. This study has recognised that much
67 | P a g e
fact more often koechlinite Bi2MoO6. Ferrimolybdite can only form at pH values less
than about 3 and is thus characteristic of acid oxidising conditions (Sarafian and
Furbish, 1965). Between about pH 3 and 3.5, the more basic phase bamfordite,
FeMo2O6(OH)3·H2O, is formed but the narrow pH range associated with its stability
(Sarafian and Furbish, 1965) limits its distribution in nature; to date bamfordite is
known only from its type locality, the Bamford Hill W-Mo-Bi deposit, Bamford,
sufficiently high concentrations are reached (Baes and Mesmer, 1976) and molybdate
can be dispersed under basic conditions in ground waters. However, when molybdenite
oxidises together with bismuth or tungsten minerals, the very insoluble Aurivillius
phases koechlinite, Bi2MoO6, and russellite, Bi2WO6, are formed. These are very
common secondary minerals in the New England Bi deposits. It has hitherto been
molybdenite, MoS2, at Kingsgate, but this is not the case; most of the yellow “molybdic
understanding the geochemistry of the oxidised zone in this setting and its bearing on
Kingsgate are virtually devoid of carbonates, aside from the very insoluble Bi species
68 | P a g e
Goodwin’s Pipe, in which calcite formed the cement for fractured quartz and occurred
as crystals a few cm long lining vughs (England, 1985). Drusy films of calcite on or
filling joints between quartz crystals and fragments may still be collected on the dumps.
No other carbonate minerals have been found elsewhere on the field. Given the above
data, and the geochemical considerations below, the occurrence of bismite at Kingsgate,
and elsewhere, must be due to its crystallisation in local micro-environments that were
a rare mineral at Kingsgate (England, 1985; Sharpe and Williams, 2004). Oxidation of
acidic conditions. This is evident from an inspection of the stoichiometry of the process
hydrolysis of Fe3+(aq), will further acidify the system. In the absence of a carbonate
gangue, protons will either be flushed from the supergene zone or react with feldspars to
yield clays, which are conspicuous constituents of the upper sections of the Kingsgate
(Rankin et al., 2001, 2002). At Kingsgate, this species has not been observed, but
conditions were certainly acid enough to give rise to ferrimolybdite in the oxidised
69 | P a g e
The structure of koechlinite, Bi2MoO6, was originally reported by Zemann
(1956). This was subsequently refined by van den Elzen and Rieck (1973) and Teller et
al. (1984). The type specimen was from St Daniel mine, Neustädtel, Schneeberg
District, Saxony, Germany (Schaller, 1916), where it was discovered in a quartz vein
with bismuth and smaltite. Associated primary minerals include bismuthinite and
joseite and cassiterite are present in the associated primary assemblage. In an Australian
context, koechlinite is also common in various sites of the New England region, NSW,
Figure 4.1: Koechlinite completely replacing bismuthinite needles, FOV 10mm. From
Quartz vein outcrops, Knöttel area (Knötel; Knödel; Knödlberg), Krupka
70 | P a g e
(Graupen), Krušné Hory Mts (Erzgebirge), Ústí Region, Bohemia (Böhmen;
Boehmen), Czech Republic (Fuchs, 2012).
(2010) on the type specimen from Punta de Su Seinargiu, Sarroch, Cagliari Province,
Sardinia, Italy (Orlandi et al., 2010), at this site bismuth and molybdenite are primary
phases; and sardignaite was associated with gelosaite. Another reported occurrence is
from Elsmore Hill, Elsmore, associated with a host of secondary Bi and Mo minerals,
Figure 4.2: Elongated tabular crystals of sardignaite on quartz, with colourless fluorite
group size crystals 1mm. from Punta de Su Seinargiu, Sarroch, Cagliari Province,
Sardinia, Italy (Ambrino, 2013).
(2011) along with its structure. The type locality was the Punta de Su Seinargiu,
71 | P a g e
Sarroch, Cagliari Province, Sardinia, Italy (Orlandi et al., 2011), where bismuth and
molybdenite are primary phases and it was associated with sardignaite. In the same
report (Orlandi et al., 2011) another occurrence is mentioned from the number 25 Pipe,
Kingsgate, New South Wales, Australia where it was associated with a host of
secondary Mo and Bi minerals, and intimate associates are bismutite and bismite, but it
Figure 4.3: Cluster of gelosaite crystals 2mm across. Colour varies from greyish green
to deep blue-green. from Old 25 Pipe, Kingsgate, Gough Co., New South Wales,
Australia (Haupt, 2011)
The structure of russellite, Bi2WO6, (Figure 4.4) was re-determined from a
neutron powder diffraction study of synthetic Bi2WO6 and reported by Knight (1992).
Cornwall, UK, where wolframite is listed as a primary phase and chrysocolla is the only
72 | P a g e
Figure 4.4: Yellow microcrystalline masses of russellite in cavities in quartz vein.
Specimen size is 9.5x6x3 cm from Kara-Oba W deposit, Betpakdal Desert (Bet-Pak-Dal
Desert), Karagandy Province (Qaragandy Oblysy; Karaganda Oblast'), Kazakhstan
(Pavel, 2008)
4.3 EXPERIMENTAL
ACS reagent ≥ 98%), Na2WO4∙2H2O (0.3564 g, ACS reagent ≥ 98%) and HNO3 (10
cm3, 0.1 M, ACS reagent 70%) was reacted in an acid digestion bomb at 180oC for 48
hours. The product obtained was a pale yellow, crystalline powder. The product was
suspended in aqueous 0.1 M HNO3 at room temperature for 24 hours to dissolve any
residual starting materials. It was then collected at the pump, washed with water then
73 | P a g e
Koechlinite was synthesised in a similar way. A mixture of Bi(NO3)3∙5H2O
and HNO3 (10 cm3, 0.1 M, ACS reagent 70%) was reacted in an acid digestion bomb at
180oC for 48 hours. The colour of the crystalline powder obtained was off-white to
(NH4)6Mo7O24∙4H2O (0.1999 g,) and HNO3 (20 cm3, 0.1 M, ACS reagent 70%). The
mixture was placed in an acid digestion bomb at 180oC for 48 hours. The product
obtained was off-white in colour, and a crystalline powder was isolated as described
above.
Powder X-ray diffraction studies of the products were carried-out using a Philips
30 mA). Traces were produced between 5-70o 2θ, with a step size of 0.02 o and a rate of
1.2 o min–1. Diffraction Technology Data processing software (Traces Version 6) and
JCPDS-ICDD data base files were used to identify the phases produced.
Solubility studies were undertaken using sealed 250 cm3 conical QuickfitR flasks
ION450 apparatus fitted with a combination electrode. Subsequent analyses showed that
all three minerals dissolve congruently in aqueous HNO3. The minerals (ca 0.1 g) were
added to a series of conical flasks containing 100 cm3 of standardised HNO3; 0.09928
M for koechlinite and russellite and 0.0981 M for sardignaite. The flasks were left for
74 | P a g e
10 weeks, during which time the pH of paired flasks was monitored periodically until
no change was detected. In all cases, equilibrium was achieved after 6 weeks. Resulting
solutions were filtered through a WhatmanR GF/F fibreglass filter and collected in clean
PET bottles. Dissolved Bi/Mo and Bi/W concentrations were determined using ICP-MS
4.4 RESULTS
essentially quantitative yield. Powder X-ray diffraction did not give any evidence for
any contaminating phase. Unit cell parameters were refined using the program LAPOD
c = 6.357(7) Å for sardignaite. These results are in excellent agreement with those
reported elsewhere (Teller et al., 1984; Knight, 1992; and Orlandi et al., 2010).
75 | P a g e
140
130
120
110
100
90
Lin (Counts)
80
70
60
50
40
30
20
10
11 20 30 40 50 60
2-Theta - Scale
Figure 4.5: Powder XRD trace of russellite with peak positions of the ‘type’ pattern from JCPDS file 00-039-0256 (red).
76 | P a g e
220
210
200
190
180
170
160
150
140
130
Lin (Counts)
120
110
100
90
80
70
60
50
40
30
20
10
5 10 20 30 40 50 60 70
2-Theta - Scale
Figure 4.6: Powder XRD trace of koechlinite with peak positions of the ‘type’ pattern from JCPDS file 01-072-1524 (red).
77 | P a g e
160
150
140
130
120
110
100
Lin (Counts)
90
80
70
60
50
40
30
20
10
14 20 30 40 50
2-Theta - Scale
Figure 4.7: Powder XRD trace of sardignaite with peak positions of the ‘type’ pattern from JCPDS file 01-072-1524 (red).
78 | P a g e
4.4.2 Solution studies
Solubility data for the three minerals are reported in Tables 4.1, 4.2, and 4.3. All
three phases are comparatively insoluble and dissolve congruently in aqueous HNO3.
was used in the determination of ion speciation patterns using the program COMICS
(Perrin and Sayce, 1967). Individual ion activity coefficients were calculated using the
0.5085z2((I/(1+I)-0.3I), for russellite I = 0.090 mol.dm–3, 3 = 0.042 and 2 = 0.245,
for koechlinite I = 0.092 mol.dm–3, 3 = 0.041 and 2 = 0.242, and for sardignaite I =
0.090 mol.dm–3, 3 = 0.043 and 2 = 0.2460, In all instances, o is taken to be unity.
The activity of H+(aq), a(H+), in HNO3; 0.0981 M was then calculated and
corresponding activities a(Bi3+), a(WO42-) and a (MoO42-), were calculated from the
79 | P a g e
Table 4.1 Dissolved metal concentrations for russellite
Solution [Bi] ppm [Bi] mol dm-3 [Mo] ppm [Mo] mol dm-3
1 10 4.8 x 10-5 1.5 1.6 x 10-5
Solution [Bi] ppm [Bi] mol dm-3 [Mo] ppm [Mo] mol dm-3
1 0.59 2.8 x 10-6 1.8 2.4 x 10-5
2 0.52 2.5 x 10-6 2.1 2.8 x 10-5
3 0.58 2.8 x 10-6 1.9 2.5 x 10-5
4 0.61 2.9 x 10-6 1.7 2.3 x 10-5
Mean 0.58 2.75 x 10-6 1.9 2.5 x 10-5
Error 0.16 7.4 x 10-7 0.2 3.0 x 10-6
80 | P a g e
The pH at equilibrium for russellite was used in the determination of individual
ion speciation using COMICS (Perrin and Sayce, 1967). Reliable lg K values for the
equations (6), (8), (10), (12), (14), (16), and (18) at I = 0 mol dm–3 were reported by van
Der Lee and Lomenech (2004) and Baes and Mesmer (1976). Correction to I = 0.090,
mol dm–3 yields lg K(298.15 K) = –2.63, –5.74, –10.97, –11.42, and –7.12, using the
relationships shown by equations (7), (9), (11), (13), and (15). This gave the
(aq) as 3.7 x 10-8, 3.5 x 10-10 2.6 x 10-14, 2.00 x 10-19, and 3.30 x 10-16 mol.dm–3
respectively.
81 | P a g e
MoO42-(aq) + 2H+(aq) ⇋ H2MoO4- (aq) (18)
Correction to I = 0.092, mol dm–3 for koechlinite by the method of Baes and
Mesmer (1976), yields lg K(298.15 K) = –1.63, –4.13, –9.14, –9.3 and –7.56, using the
relationships shown by equations (7), (9), (11), (13), and (15). This gave the
(aq) as 5.10 x 10-7, 1.9 x 10-8, 2.2 x 10--12, 6.10 x 10-17, and 2.90 x 10-16 mol.dm–3
respectively.
Correction to I = 0.090, mol dm–3 for sardignaite by the method of Baes and
Mesmer (1976), yields lg K(298.15 K) = –1.87, –4.52, –9.58, –9.45 and –7.76, using the
relationships shown by equations (7), (9), (11), (13), and (15). This gave the
(aq) as 3.00 x 10-7, 8.10 x 10-9, 8.7 x 10--13, 7.50 x 10-17, and 3.00 x 10-16 mol.dm–3
respectively.
24.83±1.5 and sardignaite–20.59±1.50, equations (2), (3) and (4) respectively and the
kJ mol–1
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The estimated error takes into account the analytical error of the solubility
83 | P a g e
4.5 REFERENCES
http://www.mindat.org/photo-566105.html>.
Angio, E.E. and Long, D.T. (Eds) (1979) Geochemistry of Bismuth. Dowden,
Anthony, J.W., Bideaux, R.A., Bladh, K.W. and Nichols, M.C. (1990) Handbook of
Tucson, Arizona.
Anthony, J.W., Bideaux, R.A., Bladh, K.W. and Nichols, M.C. (1995) Handbook of
Anthony, J.W., Bideaux, R.A., Bladh, K.W. and Nichols, M.C. (1997) Handbook of
Tucson, Arizona.
Anthony, J.W., Bideaux, R.A., Bladh, K.W. and Nichols, M.C. (2000) Handbook of
84 | P a g e
Anthony, J.W., Bideaux, R.A., Bladh, K.W. and Nichols, M.C. (2003) Handbook of
Tucson, Arizona.
Baes, C.F. Jr and Mesmer, R.E. (1976) The Hydrolysis of Cations. Plenum Press, New
York.
Baker, T., Pollard, P.J., Mustard, R., Mark, G. and Graham, J.L. (2005) A comparison
Birch, W.D., Pring, A., McBriar, E.M. Gatehouse, B.M. and McCammon, C.A. (1998)
Clissold, M.E. (2007) Aspects of the supergene geochemistry of copper nickel and
Cox, J.D., Wagman, D.D. and Medvedev, V.A. (1989) CODATA Key Values for
Thermodynamics. Hemisphere Press, New York.
England, B.M. (1985) Famous mineral localities: the Kingsgate mines. The
Fuchs, P., (2012) Koechlinite: Bi2MoO6 Quartz vein outcrops, Knöttel area (Knötel;
85 | P a g e
Region, Bohemia (Böhmen; Boehmen), Czech Republic, photograph, viewed 10
Gaines, R.V., Skinner, H.C.W., Foord, E.E., Mason, B. and Rosenzweig, A. (1997)
Dana’s New Mineralogy. Eight edition, John Wiley and Sons, New York.
Hey, M.H. and Bannister, F.A. (1938) Russellite, a new British mineral, with a note on
Knight, K.S. (1992) The crystal structure of russellite; a re-determination using neutron
Lang, J.R. and Baker, T. 2001: Intrusion-related gold systems: the present level of
Lovreček, B., Mekjavić, I. and Metikoš-Huković, M. (1985) Bismuth. In: Bard, A.J.,
International Union of Pure and Applied Chemistry and Marcel Dekker, New York,
180-187.
86 | P a g e
Martell , A. E. And Smith, R. M. (1982) Critical Stability Constants Volume 5: First
Orlandi, P., Demartin, F., Pasero, M., Leverett, P., Williams, P.A. and Hibbs, D.E.
Su Senargiu (Ca), Sardinia, Italy, and a second occurrence from Kingsgate, New
http://www.mindat.org/photo-148658.html>.
Perrin, D.D. and Sayce, I.G. (1967) Computer calculation of equilibrium concentrations
Rankin, J., Lawrence, L.J., Sharpe, J.L. and Williams, P.A. (2002) Rare secondary
bismuth, tungsten and molybdenum minerals from Elsmore, New England district
Rankin, J., Sharpe, J.L. and Williams, P.A. (2001) Betpakdalite from the tin deposits of
Mineralogy, 7, 15-17.
Rankin, J., Sharpe, J.L. and Williams, P.A. (2013) Unpublished survey of secondary Bi,
87 | P a g e
Robie, R.A. and Hemingway, B.S. (1995) Thermodynamic properties of minerals and
related substances at 298.15K and 1 bar (105 Pascals) pressure and at higher
Sharpe, J.L. and Williams (2004) Secondary bismuth and molybdenum minerals from
Sarafian, P.G. and Furbish, W.J. (1965) Solubilities of natural and synthetic
Schaller, W.T. (1916) Koechlinite (bismuth molybdate), a new mineral. United States
Teller, R.G., Brazdil, J.F., Grasselli, R.K. and Jorgensen, J.D. (1984) The structure of
van den Elzen, A.F. and Rieck, G.D. (1973) Redetermination of the structure of
van der Lee, J. and Lomenech, C. (2004) Towards a common thermodynamic database
for speciation models. Radiochimica Acta, 92, 811-818.
88 | P a g e
Zemann, J. (1956) Die Kristallstruktur von Koechlinit, Bi2MoO6. Contributions to
89 | P a g e
CHAPTER 5
90 | P a g e
5.1 ABSTRACT
geochemistry due to the association of Bi-Te with precious metal deposits (McPhail,
1995). Syntheses and stability studies of the two minerals have been undertaken.
Solubilities in aqueous HNO3 were determined at 298.2 K and the data obtained used to
calculate values of ΔGfө at the same temperature. The derived ΔGfө (298.2 K) values for
chekhovichite, (–1457.23 ± 0.5 kJ mol–1), and smirnite (–820.92 ± 1.0 kJ mol–1) have
been used in subsequent calculations to determine their relative stabilities to each other
5.2 INTRODUCTION
commonly occurs in precious metal and sulfosalt minerals (Afifi et al., 1988; Jaireth,
1991). Of the known secondary species containing essential Bi and Te (Chapter 2, Table
1), the only phases that have any reasonable distribution include chekhovichite,
Bi2Te4O11, smirnite Bi2TeO5, and to a lesser extent pingguite Bi6Te2O13. These three
where it was found at the Zod Mine (Sotk deposit), Vardenis, Gelark’unik’, Armenia,
reported that chekhovicihite was associated with a number of Bi and Te sulfosalts and
91 | P a g e
Figure 5.1: Chekhovichite from the Zod Mine (Sotk deposit), Vardenis, Gelark'unik'
Province (Geghark'unik'), Specimen size 3.5 x 3.5 x 3 mm (Bosi, 2012)
“emmonsite” and tripuhyite. Rossell et al. (1992) have reported a structure for
chekhovichite, and a synthesis was reported by Szaller et al. (1996). The crystal
structure of smirnite, Bi2TeO5, was reported in Mercurio et al. (1983) and was found
from the same type locality as chekhovichite (Spiridonov et al., 1987). Smirnite is
associated with tellurobismuthite, tetradymite and volynskite and also has a known
92 | P a g e
Figure 5.2: Greyish to olive-green crusts of smirnite over quartz and metallic-grey
tsumoite from the Shilovo-Isetskii mine, Ekaterinburg, Sverdlovskaya Oblast', Middle
Urals, Urals Region, Russia. FOV is ~12x10 mm (Pavel, 2007).
There are other known bismuth tellurite minerals. The mineral “montanite”,
Kazachenko et al., 1980). Another species which contains essential molybdenum is the
mineral chiluite, Bi6Te2Mo2O21, discovered from the Chilu deposit, Fu’an County,
Ningde Prefecture, China (Yang et al., 1989; Deng and Yang, 1993). The mineral is rare
93 | P a g e
koechlinite, with molybdenite reported to be present in the primary assemblage. Despite
a known type locality, the mineral’s structure is uncertain. The synthetic analogue was
prepared, but the mineral requires further study as the cell constants are not well-
defined. The mineral was originally supposed to be hexagonal (Yang et al., 1989), but
Yang, 1993).
5.3 EXPERIMENTAL
reported by Szaller et al. (1996). Bi2O3 and TeO3 were both initially annealed in air
(450oC) and then ground and sieved (-63 μm), the smaller fraction was used. A Bi2O3:
4TeO3 mixture was sealed in a quartz tube and heated at 720oC for 2 hours. The charge
was cooled slowly (50oC/hour) to ambient temperature then heated again (500oC) for
two days.
The synthesis of smirnite, Bi2TeO5, was adapted from the method reported by
Ok et al. (2001). A stoichiometric mixture of Bi2O3 (1.72 mmol) and TeO2 (1.72 mmol)
was thoroughly ground and sealed in a quartz tube and placed in a furnace (690oC) for
36 hours. The mixture was cooled to ambient temperature and the product collected as
above.
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5.3.2 Solubility Studies
Solubility studies of the Te minerals were undertaken using sealed 250 cm3
conical QuickfitR flasks maintained at 25.0 0.2oC in a thermostatted water bath inside
using a Radiometer ION450 apparatus fitted with a combination electrode. The minerals
(ca 0.1 g) were added to a series of conical flasks containing 100 cm3 of standardised
HNO3; 0.1065 M. The flasks were left for a period of time until the pH of a paired flask,
which was monitored periodically, reached stability. Resulting solutions were filtered
through a WhatmanR GF/F fibreglass filter and collected in clean PET bottles.
5.4 RESULTS
High purity, single phase samples of chekhovichite and smirnite were obtained by the
solid state methods mentioned above and were characterised by powder X-ray
diffraction. Unit cell parameters were refined in LAPOD (Langford, 1973) and obtained
agree well with those reported by Rossell et al. (1992) and Mercurio et al. (1983).
95 | P a g e
600
500
400
Lin (Counts)
300
200
100
5 10 20 30 40 50 60 70
2-Theta - Scale
Figure 5.3: Powder XRD trace of checkhovichite with peak positions of the ‘type’ pattern from JCPDS file 01-081-1330 (red).
96 | P a g e
1000
900
800
700
600
Lin (Counts)
500
400
300
200
100
5 10 20 30 40 50 60 70
2-Theta - Scale
Figure 5.4: Powder XRD trace of smirnite with peak positions of the ‘type’ pattern from JCPDS file 00-038-04200 (red).
97 | P a g e
5.4.2 Solubility Studies
The dissolution of chekhovichite, and smirnite are described in equations (1) and (2)
respectively.
Individual ion activity coefficients were calculated using the Davis extension of
chekhovichite, I = 0.1069 mol dm–3, 3 = 0.1045 2 = 0.3665 and = 0.778. For
smirnite I = 0.1068 mol dm–3, 3 = 0.1046, 2 = 0.3666 and = 0.7781. In all
instances, o is taken to be unity. The activity of H+(aq), a(H+), in HNO3; 0.1065 M was
then calculated and corresponding activities a(Bi3+) and a(H3TeO3+) calculated from the
individual ion speciation using COMICS (Perrin and Sayce, 1967). A reliable lg K value
for equation (3) of lg K(298.15 K) = –2.83 and for equation (5) of lg K(298.15 K) = –
9.21 at I = 0 mol dm–3 was reported by McPhail (1995). Correction to I = 0.1069, mol
dm–3 by the method of Baes and Mesmer (1976), yields lg K(298.15 K) = –2.94 and –
9.21 respectively. Using the relation shown in equation (4), the concentration of
98 | P a g e
Table 5.1. Dissolved metal concentrations for chekhovichite
Solution [Bi] ppm [Bi] mol dm-3
1 18 8.613 x 10-5
2 19 9.092 x 10-5
3 18 8.613 x 10-5
4 19 9.092 x 10-5
5 19 9.092 x 10-5
6 18 8.613 x 10-5
Mean 18.5 8.853 x 10-5
Error ±0.5 ±2.393 x 10-5
99 | P a g e
Bi3+(aq) + H2O(l) ⇋ Bi(OH)2+(aq) + H+(aq) (7)
[Bi(OH)2+].[H+]/[Bi3+] (8)
[Bi(OH)2+].2[H+]/[Bi3+] (10)
[Bi(OH)30].3[H+]/[Bi3+] (12)
Reliable lg K values for equation (7), (9) and (11) of lg K(298.15 K) = –1.11, –
3.30 and –8.21 at I = 0 mol dm–3 were reported by van Der Lee and Lomenech (2004).
Correction to I = 0.1069, mol dm–3 by the method of Baes and Mesmer (1976), yields lg
K(298.15 K) = –1.65, –4.17 and –9.19. Using the relationships shown by equations (8),
(10) and (12), the concentration of Bi(OH)2+(aq), Bi(OH)2+(aq) and Bi(OH)3o(aq) are
1.886 x 10-5, 6.958 x 10-7 and 8.12 x 10-11 mol dm–3, respectively.
individual ion speciation using COMICS (Perrin and Sayce, 1967). Correction to I =
0.1068, mol dm–3 by the method of Baes and Mesmer (1976), yields lg K(298.15 K) = –
2.94 for equation (3) and lg K(298.15 K) = –9.21 for equation (4). Using the relation
shown in equation (4), the concentration of H2TeO3o(aq) is 1.047 x 10-8 and HTeO3-(aq)
= 4.466 x 10–16 mol dm–3. Correction to I = 0.1068, mol dm–3 by the method of Baes and
Mesmer (1976) for equations (8), (10) and (12), yields lg K(298.15 K) = –1.66, –4.17
and –9.19. Using the relationships shown by equations (8), (10) and (12), the
100 | P a g e
concentration of Bi(OH)2+(aq), Bi(OH)2+(aq) and Bi(OH)3o(aq) are 1.23 x 10-5, 4.784 x
The activity of H+(aq), a(H+), in 0.1084 and 0.0104 M HNO3 was then
a(Bi(OH)2+), a(Bi(OH)2+), and a(Bi(OH)3o), were calculated from the solubility data.
This yields values of lg K for equations (1) and (2) of –14.86 ± 0.10 and -6.95 ± 0.12
respectively. Use of the appropriate data in Table 5.3 yields corresponding values for
1457.23 ± 0.5 kJ mol–1 and ΔGfө(Bi2TeO5, s, 298.15 K) = –820.92 ± 1.0 kJ mol–1. The
101 | P a g e
estimated error takes into account the analytical error of the solubility experiments and
5.5 REFERENCES
Afifi, A., Kelly, M., and Essene, E.J. (1988) Phase relationships among tellurides,
Baes, C.F. Jr and Mesmer, R.E. (1976) The Hydrolysis of Cations. Plenum Press, New
York.
Cox, J.D., Wagman, D.D. and Medvedev, V.A. (1989) CODATA Key Values for
Deng, M. and Yang, X. (1993) Bi6Te2Mo2O21 - a new synthetic crystal and its physical
precious metal deposits. Economic Geology, 37. James Cook University of North
Queensland, Australia.
102 | P a g e
Kazachenko, V.T., Fat’yanov, I.I. and Chubanov. (1980) Discovery of a lead-containing
Langford, J.I. (1973) Least-squares refinement of cell dimensions from powder data by
Mercurio, D., El Farissi, M., Frit, B. and Goursat, P. (1983) Etude structurale et
Ok, K.M., Bhucanesh, N.S.P. and Halasyamani, P.S. (2001) Bi2TeO5: synthesis,
40, 1978-1980.
Palache, C., Berman, H. and Frondel, C. (1951) Dana’s System of Mineralogy, 2, 636-
637
103 | P a g e
Perrin, D.D. and Sayce, I.G. (1967) Computer calculation of equilibrium concentrations
Robie, R.A. and Hemingway, B.S. (1995) Thermodynamic properties of minerals and
related substances at 298.15K and 1 bar (105 Pascals) pressure and at higher
Rossell, H.J., Leblanc, M., F´erey, G., Bevan, D.J.M., Simpson, D.J. and Taylor, M.R.
1415-1425.
Spiridonov, E.M., Petrova, I.V., Demina, L.A., Dolgikh, V.I. and Antonyan, G.M.
Szaller, Z., Pöppl, L., Lovas, G., and Dódony, I. (1996) Study of the formation of
van der Lee, J. and Lomenech, C. (2004) Towards a common thermodynamic database
Yang, X., Li, D., Wang, G., Deng, M., Chen, N. and Wang, S. (1989) A study of
chiluite - a new mineral found in Chilu, Fujian, China. Acta Mineralogica Sinica, 9,
104 | P a g e
CHAPTER 6
Conclusions
105 | P a g e
6.1 ABSTRACT
A model of the dispersion of bismuth in the supergene zone has been developed
in this work. This was done by using the free energy of formation values and equations
derived in this thesis for cannonite, rooseveltite, koechlinite, russellite and smirnite
were compared to the two most common bismuth minerals bismoclite and bismutite. To
make this determination and provide a clear and reasonable understanding of the
dispersion of bismuth, an assessment of the Cobar region and Kingsgate region of NSW
was undertaken. This was done by reviewing the respective environments, the known
mineralogy and the reported geochemical data, as well as drawing upon previous
chapter’s data and conclusions to develop a reverse water solubility model, which has
6.2 INTRODUCTION
characteristics may be displayed over extensive regions, either generically, for many
understanding of the chemical as well as physical controls that govern this dispersion.
Therefore, in the case of this study to draw conclusions on a proper understanding of the
106 | P a g e
dispersion of Bi in the environment will depend on appreciation of its low-temperature
aqueous chemistry and knowledge of the secondary Bi minerals that serve to buffer the
primary ore deposits and the dispersion of ore and pathfinder elements in the
some deposits and promote the formation of secondary orebodies. To understand the
history and potential mechanisms and pathways of migration of ore and pathfinder
parameters can be estimated, and with an assumption that the mineral phases of interest
This approach can be used to calculate the volume of proxy groundwater solution
required to dissolve one kilogram of bismutite (for example) at various pH values. This
the total dissolved concentration of bismuth at any particular pH. The same calculation
can be used for other mineral species and the calculated volumes are estimated, as
required for each system to reach equilibrium, and even variations in temperature will
serve to alter them. Even with these factors considered, the magnitude of differences in
107 | P a g e
results implies that some species are relatively resistant to chemical weathering, while
The work completed in chapter two can be used to determine the relationships
which control bismuth dispersion. The two basic carbonates bismutite, Bi2O2CO3, and a
al. (1984) determined thermochemical data for both of these phases, relative to that of
bismite, α-Bi2O3. ΔGfө values have been recalculated using values for H2O(l), CO2(g)
and Bi2O3(s) at 298.2 K taken from Robie and Hemingway (1995) in order to establish
consistency and to eliminate error between data sets. This yields values of
forms only at p(CO2) values below ambient (10-3.5) and that bismite is
when H2O is present or with respect to bismutite whenever p(CO2) > 10-5.5. Bismutite is
thus the stable phase under ambient conditions with respect both to Bi4O4CO3(OH)2 and
bismite. This is in line with the observation that Bi2O3, when exposed to air, undergoes
surface carbonation and that the preparation of pure Bi2O3 requires heating the samples
in an air stream at elevated temperatures (Barreca et al., 2001; Levin and Roth, 1964). A
can be based on bismutite, the most common secondary Bi mineral, bismoclite, BiOCl
and cannonite (Figure 6.1). A value for ΔGfө (BiOCl, bismoclite, 298.2 K), of -322.1 kJ
108 | P a g e
mol-1, was taken from Kaye and Laby (1995). The equilibrium conditions for equation
(1), (3) and (5) was then calculated using the data listed above, with ΔGfө (Cl-(aq), 298.2
744.0± 0.4 kJ mol-1 (Cox et al., 1989) this gives equation (2), (4) and (6) which are used
in Figure 6.1.
pH
0 1 2 3 4 5 6 7 8 9 10 11
0
-1
-2
log activit of Cl-
-3 Bismoclite
-4
-5
Bismutite
-6
-7
Cannonite
-8
109 | P a g e
Figure 6.1: Relationship of cannonite, with common bismutite and bismoclite. a(SO42-)
= 10-2. Dashed and solid lines represent p(CO2) = 10-3.5 and p(CO2) = 10-2.5 (solid line),
respectively.
It is apparent that bismoclite dominates the stability field even at high a(SO42-),
thus for cannonite to persist in natural settings requires the depletion of the [Cl-] and
low pH. The formation of bismutite also requires almost complete exhaustion of both
Cl-(aq) as shown by Figure 6.1. It is clear that cannonite has a contribution to the
immobilisation of Bi, but not as great as that of bismoclite. Thus, the possibility for the
reflects the persistent acidic conditions at localities where the a(Cl-) is slow enough or
limited to the minerals’ contact time with ground waters due to it being metastable.
conditions for equation (7, 9 and 11) were calculated using the data listed in Table 3.4,
110 | P a g e
ΔGrө= +38.69 Thus, Log K = –6.777
The relative stability of the three phases depends only on the a(H3AsO40). Thus
environments, despite having fewer reported localities than preisingerite and atelestite.
As previously stated, the numerical values reported from mindat.org are only a guide.
Below are the equations for the relationship between rooseveltite and bismoclite, which
are shown in equations (13) and (14) where ΔGrө = -3.64 and log K = 0.64; therefore
This work has determined the conditions under which the rare minerals
rooseveltite, preisingerite and atelestite can form under ambient conditions in the
H3AsO40 must be observed for the formation and stability of the basic Bi-As minerals.
111 | P a g e
conclusion is significant as it provides a more refined focus on other secondary Bi
6.3.3Chapter 4 Discussion
Figure 6.2 and Figure 6.3 describe the relationships which are considered to
control the stability of koechlinite and russellite with bismoclite and bismutite. The
equilibrium conditions were calculated using the data listed in Table 4.4, with respect to
the various speciation of MoO42- and WO42- across the range of pH 0-11. It is apparent
from this work that we can conclude that the dominant bismuth secondaries are
koechlinite and russellite. Even when the activity of either MoO42- or WO42- is low, in
this case 10-6 both koechlinite and russellite dominate the stability field.
pH
0 1 2 3 4 5 6 7 8 9 10 11
0
-1
-2
bismoclite
Log activity of Cl-
-3
-4
-5
-6 bismutite
-7
-8 koechlinite
-9
-10
112 | P a g e
to those points where a(MoO42-) = a(HMoO4-) at about pH 5 and where a(HMoO4-) =
a(H2MoO4O) at about pH 2.
pH
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
0
-1 bismoclite
-2
Log activity of Cl-
-3
-4 bismutite
-5
-6
-7 russellite
-8
-9
-10
Figure 6.3: Stability relationships of russellite with other common Bi minerals. The
activity of total dissolved W(VI) = 10-6 and pCO2 = 10-3.5 (dashed line) and 10-2.5 (solid
line). The break in the boundary between russellite and bismoclite corresponds to the
points where a(WO42-) = a(H2WO4O) at about pH 3. No data exist in the literature for
the first ionisation constant of H2WO40(aq).
Where ΔGrө = +63.30, therefore the formation of koechlinite is more favourable to that
of sardignaite
113 | P a g e
This chapter has established that the common yellow coloured secondary
furthermore the minerals koechlinite and russellite dominate the site (Chapter 1
Appendix A). Also established are the conditions in which russellite, koechlinite and
sardignaite can form under ambient conditions in the oxidised zones of Bi-Mo and Bi-
W deposits. Both koechlinite and russellite are stable phases and play a significant
effect, in relation to other secondary Bi species, and persist even at low [Mo] and [W],
NSW. This conclusion is important as it has refined our understanding of secondary Bi-
Mo and Bi-W phases which control the buffering dissolved Bi species in solution. This
6.3.4.Chpater 5 Discussion
114 | P a g e
pH
0 2 4 6 8 10
0
-2
Log activity of H3TeO3+
-4
smirnite
-6
-8
-10
-12
-14
-16
chekovichite
-18
-20
Equation (17) and (18) describes the relationship between smirnite and
bismoclite for the species H3TeO3+(aq) and H2TeO30(aq)where ΔGrө = –51.58 and –
35.48 respectively.
This study has established the conditions in which smirnite and chekovichite can
form under ambient conditions in the oxidised zones of Bi-Te bearing deposits. Smirnite
is the more favourable phase and plays a significant effect on the immobilisation and
115 | P a g e
dispersion of bismuth in oxidising environments as seen in Figure 6.4 even though Bi-
secondary Bi-Te phases which control the buffering dissolved Bi species in ground
water solutions and can be used with previous work and data to make a fair assessment
For the chosen conditions of the model, an equation was derived for every
conceivable complex and hydrolysed species of Bi3+ which are listed in Table 6.1
whereby state terms have been omitted for simplicity and the ΔGfө values used for the
minerals modelled are those listed in previous chapters of this thesis. Calculated
activities of dissolved species at equilibrium over the pH range from 0 to 11 for each
mineral of interest were then calculated and summed to yield a total dissolved [Bi3+] in
each case. Model conditions considered were for a(Cl–) = 10-1 (comparatively saline
conditions) and 10–4 (simulating rain water-flushed conditions), and p(CO2) = 10–3.5
(atmospheric) and 10–2.5 (simulating soil atmospheric levels) and a(SO42–)= 10-4. No
correction for ionic activity coefficients were made as this does not affect the
116 | P a g e
Table 6.1: Data used in species distributions in solutions at equilibrium with
solid phases. State terms have been omitted for simplicity. Data used in species
Equation lg K Ref
Bi + H2O ⇋ BiOH + H
3+ 2+ +
-1.11 1
Bi + 2H2O ⇋ Bi(OH)2 + 2H
3+ + +
-3.30 1
Bi + 3H2O ⇋ Bi(OH)3 + 3H
3+ 0 +
-8.21 1
Bi3+ + 4H2O ⇋ Bi(OH)4- + H+ -21.11 1
6Bi + 12H2O ⇋ Bi6(OH)22 + 12H
3+ 6+ +
-0.33 ±0.1 2
1.5Bi6(OH)22 + 2H2O ⇋ Bi9(OH)20 + 2H
6+ 7+ +
-3.5 ±0.1 2
Bi9(OH)207+ + H2O ⇋ Bi9(OH)216+ + H+ -3.2 ±0.1 2
Bi3+ + Cl- ⇋ BiCl2+ 2.4 2, 3
Bi3+ + 2Cl- ⇋ BiCl2+ 3.5 2, 3
Bi + 3Cl ⇋ BiCl3
3+ -
5.4 2, 3
Bi + 4Cl ⇋ BiCl4
3+ - -
6.1 2, 3
Bi3+ + 5Cl- ⇋ BiCl52- 6.7 2, 3
Bi + 6Cl ⇋
3+ -
BiCl63- 6.6 2, 3
3+
Bi + SO42- ⇋ BiSO4+ 2.01 4
Bi3+ + 2SO42- ⇋ Bi(SO4)- 3.41 4
3+
Bi + 3SO42- ⇋ Bi(SO4)33- 4.6 4
Bi3+ + 4SO4 ⇋ Bi(SO4)4
2- 5-
4.88 4
1: van Der Lee and Lomenech (2004); 2: Lovereček et al., (1985); 3: Smith and Martell
(1976); 4: Fedorov et al., (1971)
The Cobar region is a major metallogenic province located within the Lachlan
old Belt and has been explored and mined since the late 1800’s. Exploration in this
region is difficult due to the complex regolith, deep weathering and extensive
transported cover components, as well as by the narrow and deep style and geometry of
the deposits. Due to the large ore deposits of the region, the geology is relatively well-
117 | P a g e
known and has been reported and updated (Andrews, 1911; Rayner, 1969; McClatchie,
1971; Suppel, 1982; Gilligan and Byrnes, 1994; Stegman and Pocock, 1996; Stegman,
2001; Stegman and Reynolds, 2005). Also, the completion of CRC LEME (2001-2008)
covers much of the information on Cobar-style deposits and as such it is not assessed in
made. Berthelsen (2004) noted that there is notable gold–bismuth and gold–copper
correlation in the deposits at Cobar (i.e. New Cobar, Peak, Perseverance and the New
Gilligan and Byrnes, 1994; Stegman and Pocock, 1996; Reynolds, 1998; Stegman,
2001; Stegman and Reynolds, 2005). Native bismuth and bismuthinite have been
mineralisation in the Cobar Basin include bismutite (Bi2O2CO3), identified at the New
Cobar deposit (McKinnon, 2003) and the C.S.A. deposit (Stegman and Reynolds,
2005), as well as bismutite, bismite (Bi2O3) and bismoclite (BiOCl) from the Mount
Taking into consideration the common and rare secondary bismuth minerals and
know bismuth sulfosalts mentioned above from the Cobar region, an understanding of
the behaviour of Bi in the supergene environment can be made. If we consider the work
done in Chapter 2 which assessed the solubility and stability of the minerals bismutite,
118 | P a g e
bismoclite, and cannonite, we can determine a reasonable background concentration for
the area. For this purpose, the phase diagram shown in Chapter 2 Figure 2.1 can be
referenced.
Taking the ΔGfө(298.2 K) values for bismutite, bismoclite and cannonite, found in
Chapter 2, and modelling them in equilibrium with every conceivable dissolved species
then total dissolved Bi3+ can be evaluated. For this purpose, the equilibrium data of
Table 6.1 has been taken from the literature. In the calculations, a value for ΔGfө
(Bi3+,aq,298.2K) is needed. Lovreček et al., (1985) give the standard electrode potential,
Eө, at 298.2 K for equation (4) as 0.3172 ±0.0006 V; this corresponds to ΔGfө
(Bi3+,aq,298.2 K) = +91.8 ± 0.2 kJ.mol-1 and this is the value adopted here. It should be
noted that uncertainties in the value cancel out in calculations of dissolved Bi3+ species.
equation (1) is derived from ΔGfө data for constituent species given above and equation
119 | P a g e
Therefore, we can start to model specific sites based on the reported minerals
from specific regional or localised areas to define total dissolved bismuth values in any
given area.
Inspection of the data from Tables 6.2 to 6.5 shows that the maximum Bi
about 10-8 M (ignoring activity corrections), when negligible Cl-(aq) ion is present, and
solution Bi load of only 2.0 ppb. As a(Cl-) increases, total solution Bi is depressed
further. The presence of less soluble phases will have an impact and also serve to limit
Bi solution levels. In addition, soil gas concentrations of CO2 can reach partial pressures
an order of magnitude higher than those considered here, as the result of biological
activity (Appelo and Postma, 1993). This would result in an extension of the stability
field for bismutite and further lowering of solution Bi concentrations. Put simply, the
rate of dissolution of Bi minerals and chemical dispersion of the element in the regolith
120 | P a g e
Table 6.2: Total bismuth in solution at equilibrium with cannonite, bismoclite and bismutite Saline Water p(CO2) = 10-3.5, activity of Cl- = 10-1
and activity of SO42- = 10--3 (Saline) (absence of data refers to cases when the calculated activity is less than 10-13).
pH
Species 0 1 2 3 4 5 6 7 8 9 10 11
2+
BiOH 7.78E-09 7.78E-10 7.78E-11 7.78E-12 7.78E-13
Bi(OH)2+ 5.13E-11 5.13E-11 5.13E-11 5.13E-11 5.13E-11 5.13E-11 5.13E-11 5.13E-11 5.13E-11 5.13E-11 2.90E-12 2.90E-13
Bi(OH)3 3.57E-07 3.57E-07
-
Bi(OH)4 7.92E-13 7.92E-11 4.50E-10 4.50E-09
Bi6(OH)226+
Bi9(OH)207+
Bi9(OH)216+
BiCl2+ 2.56E-06 2.56E-08 2.56E-10 2.56E-12
+
BiCl2 3.23E-06 3.23E-08 3.23E-10 3.23E-12
BiCl3 2.57E-04 2.57E-06 2.57E-08 2.57E-10 2.57E-12
-
BiCl4 1.28E-05 1.28E-07 1.28E-09 1.28E-11 1.28E-13
2-
BiCl5 5.12E-06 5.12E-08 5.12E-10 5.12E-12
BiCl63- 4.07E-07 4.07E-09 4.07E-11 4.07E-13
BiSO4+ 1.02E-10 1.02E-12
Bi(SO4)2- 2.62E-10 2.62E-12
Bi(SO4)33- 4.15E-10 4.15E-12
Bi(SO4)45- 1.99E-11 1.99E-13
3+
Bi 1.02E-07 1.02E-09 1.02E-11 1.02E-13
Σ 2.81E-04 2.81E-06 2.82E-08 3.40E-10 5.49E-11 5.14E-11 5.13E-11 5.13E-11 5.21E-11 1.31E-10 3.58E-07 3.62E-07
121 | P a g e
Table 6.3: Total bismuth in solution at equilibrium with cannonite, bismoclite and bismutite Saline Water p(CO2) = 10-2.5, activity of Cl- = 10-1
and activity of SO42- = 10-3 (Saline) (absence of data refers to cases when the calculated activity is less than 10-13).
pH
Species 0 1 2 3 4 5 6 7 8 9 10 11
2+
BiOH 7.78E-09 7.78E-10 7.78E-11 7.78E-12 7.78E-13
Bi(OH)2+ 5.13E-11 5.13E-11 5.13E-11 5.13E-11 5.13E-11 5.13E-11 5.13E-11 5.13E-11 5.13E-11 2.90E-11 2.90E-12 2.90E-13
Bi(OH)3 3.57E-07 3.57E-07 3.57E-07
-
Bi(OH)4 7.92E-13 4.50E-11 4.50E-10 4.50E-09
Bi6(OH)226+
Bi9(OH)207+
Bi9(OH)216+
BiCl2+ 2.56E-06 2.56E-08 2.56E-10 2.56E-12
+
BiCl2 3.23E-06 3.23E-08 3.23E-10 3.23E-12
BiCl3 2.57E-04 2.57E-06 2.57E-08 2.57E-10 2.57E-12
-
BiCl4 1.28E-05 1.28E-07 1.28E-09 1.28E-11 1.28E-13
2-
BiCl5 5.12E-06 5.12E-08 5.12E-10 5.12E-12
BiCl63- 4.07E-07 4.07E-09 4.07E-11 4.07E-13
BiSO4+ 1.02E-10 1.02E-12
-
Bi(SO4)2 2.62E-10 2.62E-12
Bi(SO4)33- 4.15E-10 4.15E-12
Bi(SO4)45- 1.99E-11 1.99E-13
3+
Bi 1.02E-07 1.02E-09 1.02E-11 1.02E-13
Σ 2.81E-04 2.81E-06 2.82E-08 3.40E-10 5.49E-11 5.14E-11 5.13E-11 5.13E-11 5.21E-11 3.57E-07 3.58E-07 3.62E-07
122 | P a g e
Table 6.4: Total bismuth in solution at equilibrium with cannonite, bismoclite and bismutite Saline Water p(CO2) = 10-3.5, activity of Cl- = 10-4
and activity of SO42- = 10-3 (fresh) (absence of data refers to cases when the calculated activity is less than 10-13).
pH
Species 0 1 2 3 4 5 6 7 8 9 10 11
BiOH2+ 7.78E-06 7.78E-07 7.78E-08 7.78E-09 7.78E-10 7.78E-11 7.78E-12 1.37E-13
+
Bi(OH)2 5.13E-08 5.13E-08 5.13E-08 5.13E-08 5.13E-08 5.13E-08 5.13E-08 9.18E-09 9.18E-10 9.18E-11 9.18E-12 9.18E-13
Bi(OH)3 6.29E-13 1.13E-06 1.13E-06 1.13E-06 1.13E-06 1.13E-06
-
Bi(OH)4 1.42E-12 1.42E-11 1.42E-10 1.42E-09 1.42E-08
Bi6(OH)226+
Bi9(OH)207+
Bi9(OH)216+
BiCl2+ 2.56E-06 2.56E-08 2.56E-10 2.56E-12
BiCl2+ 3.23E-09 3.23E-11 3.23E-13
BiCl3 2.57E-10 2.57E-12
BiCl4-
BiCl52-
BiCl63-
BiSO4+ 1.02E-07 1.02E-09 1.02E-11 1.02E-13
-
Bi(SO4)2 2.62E-07 2.62E-09 2.62E-11 2.62E-13
Bi(SO4)33- 4.15E-07 4.15E-09 4.15E-11 4.15E-13
Bi(SO4)45- 1.99E-08 1.99E-10 1.99E-12
Bi3+ 1.02E-04 1.02E-06 1.02E-08 1.02E-10 1.02E-12
Σ 1.13E-04 1.88E-06 1.40E-07 5.92E-08 5.21E-08 5.14E-08 5.13E-08 1.14E-06 1.13E-06 1.13E-06 1.13E-06 1.14E-06
123 | P a g e
Table 6.5: Total bismuth in solution at equilibrium with cannonite, bismoclite and bismutite Saline Water p(CO2) = 10-2.5, activity of Cl- = 10-4
and activity of SO42- = 10-3 (fresh) (absence of data refers to cases when the calculated activity is less than 10-13).
pH
Species 0 1 2 3 4 5 6 7 8 9 10 11
BiOH2+ 7.78E-06 7.78E-07 7.78E-08 7.78E-09 7.78E-10 7.78E-11 4.33E-12
+
Bi(OH)2 5.13E-08 5.13E-08 5.13E-08 5.13E-08 5.13E-08 5.13E-08 2.90E-08 2.90E-09 2.90E-10 2.90E-11 2.90E-12 2.90E-13
Bi(OH)3 6.29E-13 3.57E-07 3.57E-07 3.57E-07 3.57E-07 3.57E-07 3.57E-07
-
Bi(OH)4 4.50E-13 4.50E-12 4.50E-11 4.50E-10 4.50E-09
Bi6(OH)226+
Bi9(OH)207+
Bi9(OH)216+
BiCl2+ 2.56E-06 2.56E-08 2.56E-10 2.56E-12
BiCl2+ 3.23E-09 3.23E-11 3.23E-13
BiCl3 2.57E-10 2.57E-12
BiCl4-
BiCl52-
BiCl63-
BiSO4+ 1.02E-07 1.02E-09 1.02E-11 1.02E-13
-
Bi(SO4)2 2.62E-07 2.62E-09 2.62E-11 2.62E-13
3-
Bi(SO4)3 4.15E-07 4.15E-09 4.15E-11 4.15E-13
Bi(SO4)45- 1.99E-08 1.99E-10 1.99E-12
Bi3+ 1.02E-04 1.02E-06 1.02E-08 1.02E-10 1.02E-12
Σ 1.13E-04 1.88E-06 1.40E-07 5.92E-08 5.21E-08 5.14E-08 3.86E-07 3.60E-07 3.58E-07 3.57E-07 3.58E-07 3.62E-07
124 | P a g e
6.6 BISMUTH MODEL FOR THE NEW ENGLAND REGION
This thesis has previously mentioned the Kingsgate region of Northern NSW
and its reported mineralogy has been outlined in Chapter 1, Appendix A and Chapter 4.
Therefore, in this example we would need to consider and impose a number of limits to
provide an appropriate summation on the solubility of Bi3+. For the pH conditions found
in the Kingsgate regolith we find that pH is expected to vary between about 4 and 6.5,
with a median of about 5. Soils covering granites of the New England region are known
to have pH values of less than 5.5 in all horizons (Dolling et al., 2001). Also, the soils
covering mineralised areas, in this case they are predominantly shallow, with an umbric
Inspection of the data from Tables 6.6 to 6.9 shows that the maximum Bi
turn corresponds to a total solution Bi load of only 0.2 ppb. As a(Cl-) increases, total
solution Bi is depressed further at 10-11M and is limited to 2.0 ppt. Put simply, the rate
of dissolution of Bi minerals in the New England region and chemical dispersion of the
element in the regolith is predicted to be very slow in comparison with most base
metals. Therefore we can conclude that bismuth is not very mobile in the supergene
has largely been untested as the use of Bi and Mo in these environment as pathfinders
as a localised pathfinder.
125 | P a g e
Table 6.6: Total bismuth in solution at equilibrium with koechlinite, bismoclite and bismutite Saline Water p(CO2) = 10-2.5, activity of Cl- = 10-1
activity of SO42- = 10-4 and activity of WO42- = 10-6 (absence of data refers to cases when the calculated activity is less than 10-13).
pH
Species 0 1 2 3 4 5 6 7 8 9 10 11
2+
BiOH 7.78E-09 7.78E-10 7.78E-11 7.78E-12 7.78E-13
+
Bi(OH)2 5.13E-11 5.13E-11 5.13E-11 5.13E-11 5.13E-11 5.13E-11 5.13E-11 5.13E-11 5.13E-11 2.90E-11 2.90E-12 2.90E-13
Bi(OH)3 3.57E-07 3.57E-07 3.57E-07
Bi(OH)4- 7.92E-13 4.50E-11 4.50E-10 4.50E-09
6+
Bi6(OH)22
Bi9(OH)207+
Bi9(OH)216+
BiCl2+ 2.56E-06 2.56E-08 2.56E-10 2.56E-12
BiCl2+ 3.23E-06 3.23E-08 3.23E-10 3.23E-12
BiCl3 2.57E-04 2.57E-06 2.57E-08 2.57E-10 2.57E-12
BiCl4- 1.28E-05 1.28E-07 1.28E-09 1.28E-11 1.28E-13
BiCl52- 5.12E-06 5.12E-08 5.12E-10 5.12E-12
BiCl63- 4.07E-07 4.07E-09 4.07E-11 4.07E-13
BiSO4+ 1.02E-10 1.02E-12
126 | P a g e
Table 6.7: Total bismuth in solution at equilibrium with koechlinite, bismoclite and bismutite Saline Water p(CO2) = 10-3.5, activity of Cl- = 10-1
activity of SO42- = 10-4 and activity of WO42- = 10-6(absence of data refers to cases when the calculated activity is less than 10-13).
pH
Species 0 1 2 3 4 5 6 7 8 9 10 11
BiOH2+ 7.78E-09 7.78E-10 7.78E-11 7.78E-12 7.78E-13
+
Bi(OH)2 5.13E-11 5.13E-11 5.13E-11 5.13E-11 5.13E-11 5.13E-11 5.13E-11 5.13E-11 5.13E-11 5.13E-11 9.18E-12 9.18E-13
Bi(OH)3 1.13E-06 1.13E-06
-
Bi(OH)4 7.92E-13 7.92E-11 1.42E-09 1.42E-08
Bi6(OH)226+
Bi9(OH)207+
Bi9(OH)216+
BiCl2+ 2.56E-06 2.56E-08 2.56E-10 2.56E-12
BiCl2+ 3.23E-06 3.23E-08 3.23E-10 3.23E-12
BiCl3 2.57E-04 2.57E-06 2.57E-08 2.57E-10 2.57E-12
BiCl4- 1.28E-05 1.28E-07 1.28E-09 1.28E-11 1.28E-13
2-
BiCl5 5.12E-06 5.12E-08 5.12E-10 5.12E-12
BiCl63- 4.07E-07 4.07E-09 4.07E-11 4.07E-13
BiSO4+ 1.02E-10 1.02E-12
-
Bi(SO4)2 2.62E-10 2.62E-12
3-
Bi(SO4)3 4.15E-10 4.15E-12
Bi(SO4)45- 1.99E-11 1.99E-13
Bi3+ 1.02E-07 1.02E-09 1.02E-11 1.02E-13
Σ 2.81E-04 2.81E-06 2.82E-08 3.40E-10 5.49E-11 5.14E-11 5.13E-11 5.13E-11 5.21E-11 1.31E-10 1.13E-06 1.14E-06
127 | P a g e
Table 6.8: Total bismuth in solution at equilibrium with koechlinite, bismoclite and bismutite Fresh Water p(CO2) = 10-2.5, activity of Cl- = 10-4
activity of SO42- = 10-4 and activity of WO42- = 10-6 (absence of data refers to cases when the calculated activity is less than 10-13).
pH
Species 0 1 2 3 4 5 6 7 8 9 10 11
BiOH2+ 7.78E-06 7.78E-07 7.78E-08 5.60951E-09 1.77388E-10 5.54607E-12 5.54607E-13
+
Bi(OH)2 5.13E-08 5.13E-08 5.13E-08 3.68383E-08 1.16493E-08 3.64216E-09 3.64216E-09 2.90E-09 2.90E-10 2.90E-11 2.90E-12 2.90E-13
Bi(OH)3 6.29E-13 1.43307E-11 1.43307E-11 4.48051E-09 4.48051E-08 3.57E-07 3.57E-07 3.57E-07 3.57E-07 3.57E-07
-
Bi(OH)4 4.50E-13 4.50E-12 4.50E-11 4.50E-10 4.50E-09
Bi6(OH)226+
Bi9(OH)207+
Bi9(OH)216+
BiCl2+ 2.56E-06 2.56E-08 2.56E-10 1.84651E-12
BiCl2+ 3.23E-09 3.23E-11 3.23E-13
BiCl3 2.57E-10 2.57E-12
BiCl4-
BiCl52-
BiCl63-
BiSO4+ 1.02E-07 1.02E-09 1.02E-11 2.37531E-13
-
Bi(SO4)2 2.62E-07 2.62E-09 2.62E-11 1.8851E-13
3-
Bi(SO4)3 4.15E-07 4.15E-09 4.15E-11 2.9902E-13
Bi(SO4)45- 1.99E-08 1.99E-10 1.99E-12
Bi3+ 1.02E-04 1.02E-06 1.02E-08 7.35383E-11 2.32548E-13
Σ 1.13E-04 1.88E-06 1.40E-07 4.25382E-08 1.18412E-08 8.12822E-09 4.84478E-08 3.60E-07 3.58E-07 3.57E-07 3.58E-07 3.62E-07
128 | P a g e
Table 6.9: Total bismuth in solution at equilibrium with koechlinite, bismoclite and bismutite Fresh Water p(CO2) = 10-.3.5, activity of Cl- = 10-4
activity of SO42- = 10-4 and activity of WO42- = 10-6 (absence of data refers to cases when the calculated activity is less than 10-13).
pH
Species 0 1 2 3 4 5 6 7 8 9 10 11
2+
BiOH 7.78E-06 7.78E-07 7.78E-08 2.49041E-10 2.49041E-11 2.49041E-12 2.49041E-13
Bi(OH)2+ 5.13E-08 5.13E-08 5.13E-08 1.60931E-09 1.60931E-09 1.60931E-09 1.60931E-09 1.60931E-09 9.18E-10 9.18E-11 9.18E-12 9.18E-13
Bi(OH)3 6.29E-13 1.97973E-11 1.97973E-10 1.97973E-09 1.97973E-08 1.97973E-07 1.13E-06 1.13E-06 1.13E-06 1.13E-06
Bi6(OH)226+
Bi9(OH)207+
Bi9(OH)216+
BiCl2+ 2.56E-06 2.56E-08 2.56E-10
BiCl4-
BiCl52-
BiCl63-
BiSO4+ 1.02E-07 1.02E-09 1.02E-11 3.28141E-13
-
Bi(SO4)2 2.62E-07 2.62E-09 2.62E-11
Σ 1.13E-04 1.88E-06 1.40E-07 1.87858E-09 1.83219E-09 3.59153E-09 2.14069E-08 1.99583E-07 1.13E-06 1.13E-06 1.13E-06 1.14E-06
129 | P a g e
6.7 CONCLUSION
can be understood in the weathering environment. This work explains the differential
leaching and mobility of Bi the Kingsgate and Cobar deposits. The model outlined above
explains the limited mobility at Kingsgate and suggests that much of the New England
Orogen remains untested as the values obtained in this work are found to be lower than the
reported arbitrary values found in the literature (MacDuff and Snow, 1971; MacDuff and
Zerwick 1971a; MacDuff and Zerwick 1971b; MacDuff and Zerwick 1972; Siegal, 1974;
Rose et al., 1979; Levinson, 1980; Plant et al., 1989; Plant et al.,1991; Filella, 2010). Also,
the use of conventional Atomic Absorption Spectroscopy (AAS) is not a useful analytical
method for the determination of Bi at low levels. This is important given the data above
concerning the distribution of the element in rocks, soils and natural waters. Even though
modern ICP-OES or ICP-MS and other methods are both accurate and precise to much lower
levels (Filella, 2010; Gholivand and Romiani, 2006) and hydride generation methods have
greatly increased the sensitivity of Bi determinations using AAS (Campbell, 1992) these
This work also highlights the persistence of secondary Bi minerals in the highly
weathered gossans of Cobar-style ores (Leverett et al., 2003, 2004, 2005a,b). The model
provides the confidence that Bi can be successfully used as a localised pathfinder element in
2005). Refractory elements such as Sn in these deposits have been suggested as being useful
exploration guides (Leverett et al., 2004); Bi may also be useful, especially in Au-poor
deposits such as Elura, to the north of Cobar. Stable isotope measurements of some ground
130 | P a g e
waters in the region (Leverett et al., 2003, 2004) indicate that they are quite old and serve
well as proxies for those that had an input to the oxidised zones, despite a very long
weathering history (Pillans et al., 1999). This conclusion applies to exploration programs
carried-out in the past with the same kinds of analytical constraints. The model developed
above requires that the results be revaluated and this model should be taken into
6.7 REFERENCES
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of Mines, Sydney.
Barreca, D., Morazzoni, F., Rizzi, G.A, Scotti, R. and Tondello, E. (2001) Molecular oxygen
Berthelsen, R.R., (2004) Exploration in the Cobar Gold Field: A 2004 Perspective. In:
McQueen, K.G. and Scott, K.M. (2004) Exploration Field Workshop Cobar Region
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Cox, J.D., Wagman, D.D. and Medvedev, V.A. (1989) CODATA Key Values for
Dolling, P.J., Moody, P., Noble, A., Helyar, K., Hughes, B., Reuter, D. and Sparrow, L.
(2001) Soil Acidity and Acidification. Final report to National Land and Water Resources
Fedorov, V.A., Kalosh, T.N., Chernikova, G.E. and Mironov, V.E. (1971) Sulphato-
Filella, M. (2010) How reliable are environmental data on 'orphan' elements? The case of
109.
Gholivand, M.B. and Romiani, A.A. (2006) Highly sensitive and selective measurement of
Gilligan, L.B. & Byrnes, J.G. (1994) Cobar 1:250 000 Metallogenic Map SH/55-14: Metal
Study and Mineral Deposit Data Sheets. Geological Survey of New South Wales,
Sydney
Kaye, G.W.C. and Laby, T.H. (1995) Tables of Physical and Chemical Constants. 16th
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Leverett, P., McKinnon, A.R. and Williams, P.A. (2003) Mineralogy of the oxidised zone of
the New Cobar orebody. In: I.C. Roach (Ed.) Advances in Regolith, CRC LEME,
Canberra, 267-270.
Leverett, P., McKinnon, A.R. and Williams, P.A. (2004) A supergene exploration model for
Cobar style deposits. In: McQueen, K.G. and Scott, K.M. (Eds.) Exploration Field
Leverett, P., McKinnon, A.R. and Williams, P.A. (2005a) Supergene geochemistry of the
Endeavor ore body, Cobar, NSW, and relationships to other deposits in the Cobar Basin.
In: I.C. Roach (Ed.) Regolith 2005 – Ten Years of CRC LEME, CRC LEME, 191-194.
Leverett, P., McKinnon, A.R., Sharpe, J.L. and Williams, P.A. (2005b) Secondary minerals
from the central Cobar mines. Australian Journal of Mineralogy, 11, 75-82.
Levin, E.M. and Roth, R.S. (1964) Polymorphism of bismuth sesquioxide. I. Pure Bi 2O3.
Lovreček, B., Mekjavić, I. and Metikoš-Huković, M. (1985) Bismuth. In: Bard, A.J., Parsons,
Pure and Applied Chemistry and Marcel Dekker, New York, 180-187.
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Pillans, B., Tonui, E. and Indurm, M. (1999) Paleomagnetic dating and weathered regolith.
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Plant, J.A., Breward, N., Forrest, M.D. and Smith, R.T. (1989) The gold pathfinder elements
As, Sb and Bi - their distribution and significance in the southwest Highlands of Scotland.
Plant, J.A., Cooper, D.C., Green, P.M., Reedman, A.J. and Simpson, P.R. (1991) Regional
distribution of As, Sb and Bi in the Grampian Highlands of Scotland and English Lake
District: implications for gold metallogeny. Transactions of the Institution of Mining and
MacDuff, R. and Snow, A. (1971) Quarterly Report Period to 8th January 1971, EL208,
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AOG Minerals PL. New South Wales Department of Primary Industries (Mineral
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McKinnon, A.R., Sharpe, J.L. & Williams, P.A. (2005) Other notable mineral occurrences in
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136 | P a g e
Appendix A
Bald Nob
D30997b Bismutite
Captains Flat
M15216 Tetragonal bismuth oxide (new mineral) with bismutite, koechlinite,
russellite
Duckmaloi
D30994 Bismutite
Deepwater
D21997 Bismutite, koechlinite, chekhovichite (Bi2Te4O11)
D22221 Koechlinite, bismutite
D22232 Bismutite, koechlinite.
D28072 Bismutite
D37006 Koechlinite
Dundee
D24224 Koechlinite
D28509 Koechlinite, quartz
D28510 Bismite, bismutite
D28511 Koechlinite, bismutite
D28512 As for D28511
D35450 Zavaritskite, bismite, bismutite, koechlinite
D35450 Bismutite.
Elsmore
D15631 Bismoclite
D28050 Bismoclite
Emmaville
D18210 Russellite, bismutite
137 | P a g e
Glen Eden
D35884 Bismutite, koechlinite
Glen Elgin
D31404 Koechlinite, bismutite
Gumble Flat
D31051 Bismutite
Kingsgate
D2969 Bismutite, koechlinite
D2970 Koechlinite
D2971 Bismutite, koechlinite.
D2973 Koechlinite
D2974 Bismutite, bismite, koechlinite
D2975 Preisingerite, bismutite.
D7194 Koechlinite, bismutite
D22004 Bismutite
D30956 Bismutite, koechlinite.
D31339 Koechlinite
D31340 Wulfenite, koechlinite, bismutite
D31341 Wulfenite, koechlinite, bismutite
D31343 Bismutite, preisingerite
D31420 Bismutite.
D38036 Bismutite, chekhovichite, smrkovecite
M30035 Bismutite, bismite
M47205 Ferrimolybdite
Nanima
D18931 Bismutite
D25033 Bismutite.
Mt Gipps
D15637 Bismutite, kettnerite
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Mt Razorback
D35482 Bismutite
Murrumbateman
D30998 Bismutite
Torrington
D18209 Bismutite, russellite
D28513 Bismutite
D29744 Bismutite, russellite
D29745 Bismutite, russellite
D29746 Russellite
Whipstick
D18930 Koechlinite
D31052 Koechlinite
Unknown
D36340 Bismutite, russellite
NORTHERN TERRITORY
Alice Springs
D30600 Bismutite
Hatches Creek
M18636 Bismutite
Tennant Creek
M48721 Bismutite; XRDMV
M49700 Bismutite, bismite
Wolfram Hill
D51120 Bismutite, russellite
QUEENSLAND
Bamford
D30972 Bismutite
D30991 Koechlinite
139 | P a g e
M7425 Ferrimolybdite; XRDMV
Biggenden
D31014 Bismutite, preisingerite
D31016 Bismutite, preisingerite
Chillagoe
D18284 Bismutite
D18284 Bismutite
D18285 Bismutite
D31026 Bismutite, preisingerite
D31027 Bismutite
M49613 Russellite; XRDMV
Ukalunda
D31017 Bismutite
Halifax Bay
D31012 Bismutite, koechlinite
D31013 Bismutite, minor bismoclite
Kaboonga
D31045 Bismutite
Malbon
D30593 Bismutite
Mt Hastings
D31454 Bismutite
Mt Shamrock
D31048 Bismoclite
Mt Wyatt
D31035 Bismutite with minor quartz and amorphous iron oxides.
Wolfram Camp
D31451 Koechlinite
D31452 Koechlinite, bismutite
140 | P a g e
D31453 Russellite
D51077 Bismutite, koechlinite
M40932 Russellite
SOUTH AUSTRALIA
Balhanna mine
M30249 Bismutite
TASMANIA
Beechworth
M15403 Bismutite; XRDMV
M43565 Bismutite; XRDMV
Bendoc
D21624 Bismutite, zairite
Everton
M38367 Ferrimolybdite
M40860 Ferrimolybdite; XRDMV
M42790 Ferrimolybdite
M47686 Mendozavilite
Gombianbar Creek
M274 Bismutite
Maldon
141 | P a g e
M7552 Bismutite
M15402 Bismutite
Mt Moliagul
M39540 Ferrimolybdite
M40723 As for M39540
Mt Stanley
M41176 Ferrimolybdite
Pittong
M47373 Koechlinite, bismoclite; XRDMV
M47621 Koechlinite; XRDMV
M47622 Bismoclite; XRDMV
Thologolong
M48714 Koechlinite; XRDMV
Wangrabell
M46176 Ferrimolybdite; XRDMV
WESTERN AUSTRALIA
Leinster
M47710 Bismoclite
Mt Magnet
D36109 Bismutite
D36110 Bismutite
Poona
M49672 Russellite, bismutite; XRDMV
Warriedar
M35505 Ferrimolybdite
a
These were determined by XRD during the course of this study and are in addition to
those previously reported by Rankin (2001, 2002) Sharpe and Williams (2004).
b
Specimen numbers beginning with D are from the Australian Museum and those with
M from Museum Victoria. With respect to the latter, the note XRDMV refers to
identification by powder XRD by W.D. Birch (personal communication).
142 | P a g e