T.C.

DOKUZ EYLUL UNIVERSITY Maritime Faculty Department of Marine Transportation Engineering DIPLOMA PROJECT

ANALYZING CLASSIFICATION OF THE AMMONIUM NITRATE CARGOES AND SAFETY ISSUES FOR AMMONIUM NITRATE SHIP-SHORE OPERATIONS

Recep Oruolu

Advisor Lecturer Bar Kuleyin

2012

Dokuz Eylul University Maritime Faculty Diploma Project Data Form Project No: Subject Code: Department Code:

Note: This Place Will Be Filled By The School.

Surname: Oruolu

Name: Recep

Turkish Name of The Project: Amonyum nitrat yknn snflandrlmas analizi ve gemisahil operasyonlarnda alnmas gereken emniyet tedbirleri. English Name of The Project: Analyzing classification of the ammonium nitrate cargoes and safety issues for ammonium nitrate ship-shore operations.

Year: 2012 Language: English Number of Pages: 124 Number of References: 60 ... of Advisor: Title: Lecturer
English Key Words: 1- IMDG Code 2- Hazardous Goods 3- Ammonium Nitrate 4- Ammonium Nitrate Based Fertilizers 5- Safety Precautions

Name: Bar

Surname: Kuleyin

Turkish Key Words: 1- IMDG Kod 2- Tehlikeli Ykler 3- Amonyum Nitrat 4- Amonyum Nitrat erikli Gbreler 5- Emniyet nlemleri

Date: 02/05/2012 Signature:

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PREFACE One of the most traded inorganic, chemical fertilizer and blasting agent ammonium nitrate, examined by the angle on sea transport, safety, IMDG Code, UN Regulations and Country Regulations. This thesis will help improving safety issues and briefing what to do in an emergency situation while handling ammonium nitrate and ammonium nitrate based fertilizers. I am greatful to Lec. Bar Kuleyin for sharing his dear opinions and leading me to finish this project. I appriciate Ege Gubre Sanayi A.S. for allowing to visit M/V Sultan Atasoy and also officers, crew and company DPA Mr. Burak Atasoy, for sharing information. I want to thank who I enqired information or documents via e-mail. Fertilizers Europe (EFMA); Baltic and International Maritime Council (BIMCO); The Department for Environment, Food and Rural Affairs (DEFRA); Government of Western Australia, Director of Dangerous Goods Safety Mr. Philip Hine; Fertilizers Europe Technical Director Mr. Dr. Antoine Hoxha.

Izmir, May 2012

Recep Oruolu

TURKISH SUMMARY Bu tez projesinin amalar, gemi-sahil operasyonlarnda amonyum nitrat (AN) ellelenmesinde alnmas gereken emniyet tedbirlerini arttrmak, bu ykn deniz yoluyla tanrken alnmas gereken koullar incelemek, hangi koullar altnda bu ykn tehlikeli olduunu anlamak ve acil durumlarda nelerin yaplp yaplmayacan aklamaktr. Amonyum nitratn tehlikelerini ve emniyet tedbirlerini aklarken IMO kitaplar ile birlikte dzenleyici kanunlar kullandm. Amonyum nitrata olan bak etkileyen ve ilgili kurulularn snralamalar getirmesine yol aan, gemite yaanm kazalar ve terrizm olaylarn inceledim. Bununla birlikte, saha almas olarak Ocak 2012'de Aliaa Ege Gbre Liman'nda gerekleen bir amonyum nitrat ierikli gbre tahliyesine nezaret ettim; bu almay gzlem yaparak ve Avrupa Gbre reticileri Birlii'nin (EFMA) hazrlad kontrol listesi ablonu ile kyaslayarak yaptm. Amacm, amonyum nitrat yk ellelenirken alnacak emniyet tedbirlerinin artrlmasn ve deniz yoluyla tanrken ykn tehlikelerine dikkat ekmeyi salamaktr. Bu balamda, emniyet kontrol listeleri, depolama kurallar ve satta yaplan snrlamalar hakknda nerilerde bulundum.

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ABSTRACT The purposes of my project were improving safety precautions while handling ammonium nitrate (AN) in ship-shore operations, learning sea transportation requirements, determining under which conditions the cargo can be dangerous, and what are the do's/don'ts in an emergency situation. I have used regulatory articles, IMO books for decribing what were the hazards and safety precautions of AN. I have studied past accidends and terrorism incidents that affected the worlds outlook and made the related organizations to do restrictions. Besides, I had inspected an ammonium nitrate based fertilizer discharge operation as a case study in January 2012 at Aliaga Ege Gubre Port, by observing visually and controlling my template checklists which was prepared by EFMA. According to accidents, my point is to carry out improving safety at ammonium nitrate ship-shore operations and attract awareness while sea transport of AN. I proposed that checklists and regulations about storage and restrictions of sales.

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CONTENTS PREFACE TURKISH SUMMARY ABSTRACT CONTENTS LIST OF ABBREVIATIONS LIST OF TABLES LIST OF FIGURES INTRODUCTION i ii iii iv x xi xii xiii

CHAPTER ONE THE MARKET OF AMMONIUM NITRATE AND OTHER FERTILIZERS 1.1. World Fertilizer Statistics 1.1.1. World Fertilizer Production/Consumption Values (2000-2010) 1.1.2. World Fertilizer Export/Import Values (2000 - 2010) 1.2. World Ammonium Nitrate Statistics 1.2.1. Ammonium Nitrate Exports by Regions 1.2.2. Ammonium Nitrate Imports by Regions 1.3. Domestic Fertilizer Statistics 1.3.1. Export Statistics in Turkey 1.3.2. Import Statistics in Turkey 1.3.3. Ammonium Nitrate Based Fertilizer Statistics 2004 - 2010 2 2 3 4 4 6 8 9 9 10

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CHAPTER TWO ANALYSIS AND CLASSIFICATION OF AMMONIUM NITRATE AND AMMONIUM NITRATE BASED FERTILIZERS 2.1. Classification of Ammonium Nitrate 2.1.1. Ammonium Nitrate UN 0222 - Class 1.1 2.1.2. Ammonium Nitrate UN 1942 - Class 5.1 2.1.3. Ammonium Nitrate Based Fertilizer UN 2067 - Class 5.1 2.1.4. Ammonium Nitrate Based Fertilizer UN 2071 - Class 9 2.1.5. Ammonium Nitrate Based Fertilizer (Non-Hazardous) 2.2. Logic Diagram 2.3. Properties of Ammonium Nitrate 2.4. General Hazards of Ammonium Nitrate 2.4.1. Fire 2.4.2. Explosion 2.4.3. Decomposition 2.5. Class Based Hazards of Ammonium Nitrate 2.5.1. Ammonium Nitrate UN 1942 - Class 5.1 2.5.2. Ammonium Nitrate Based Fertilizer UN 2067 - Class 5.1 2.5.3. Ammonium Nitrate Based Fertilizer UN 2071 - Class 9 2.5.4. Ammonium Nitrate Based Fertilizer (Non-Hazardous) 2.6. Stowage and Segregation Requirements of Ammonium Nitrate 2.6.1. Ammonium Nitrate UN 1942 - Class 5.1 2.6.2. Ammonium Nitrate Based Fertilizer UN 2067 - Class 5.1 2.6.3. Ammonium Nitrate Based Fertilizer UN 2071 - Class 9 13 13 13 13 14 14 16 20 21 21 21 22 23 23 23 24 24 24 24 25 25

2.6.4. Ammonium Nitrate Based Fertilizer (Non-Hazardous) 2.7. Weather Precautions of Ammonium Nitrate 2.8. Loading 2.8.1. Ammonium Nitrate UN 1942 - Class 5.1 2.8.2. Ammonium Nitrate Based Fertilizer UN 2067 - Class 5.1 2.8.3. Ammonium Nitrate Based Fertilizer UN 2071 - Class 9 2.8.4. Ammonium Nitrate Based Fertilizer (Non-Hazardous)

25 26 26 26 27 28 29

CHAPTER THREE AMMONIUM NITRATE ACCIDENTS, TERROR INCIDENTS AND EFFECTS 3.1. Accidents 3.1.1. 1921 Oppau - Germany 3.1.2. 1942 Tessenderloo - Belgium 3.1.3. 1947 Texas City - USA 3.1.4. 1947 Brest - France 3.1.5. 1953 SS Tirrenia Wreck 3.1.6. 1959 Roseburg, Oregon - USA 3.1.7. 1988 Kansas City, Missouri - USA 3.1.8. 1994 Port Neal, Iowa - USA 3.1.9. 2001 Toulouse - France 3.1.10. 2004 Barracas - Spain 3.1.11. 2004 Mihailesti - Romania 30 30 31 31 33 33 34 34 34 35 36 36

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3.2. Near Misses 3.2.1. 2007 M/V Ostedijk - Spain 3.2.2. 2009 M/V Lady Juliet - Dardanelles - Turkey 3.3. Terror Incidents 3.3.1. 1995 Oklahoma City - USA 3.3.2. 2002 Bali - Indonesia 3.3.3. 2003 Istanbul - Turkey 3.3.4. 2006 Mumbai - India 3.3.5. Oslo - Norway 3.4. Effects Around World 3.4.1. European Union and Turkey 3.4.2. Australia 3.4.3. United Kingdom 3.4.4. United States of America, Oklahoma State

37 37 38 40 40 42 42 44 44 44 45 46 46 47

CHAPTER FOUR SAFETY PRECAUTIONS OF AMMONIUM NITRATE AND A CASE STUDY AT ALIAGA EGE GUBRE PORT 4.1. Safety Precautions of AN 4.1.1. Ammonium Nitrate UN 1942 - Class 5.1 (IMSBC Code) 4.1.2. Ammonium Nitrate UN 2067 - Class 5.1 (IMSBC Code) 4.1.3. Ammonium Nitrate UN 2071 - Class 9 (IMSBC Code) 4.1.4. Emergency Procedures (IMSBC Code) 48 48 49 49 49

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4.2. Risk Assessment 4.3. Material Safety Data Sheet 4.4. Case Study at Aliaga Ege Gubre Port 4.4.1.Purpose and Scope 4.4.2. Observations 4.4.3. Checklist Proposal

50 53 54 55 55 58

CONCLUSIONS REFERANCES APPENDICES APPENDIX 1: UN MANUAL OF TESTS AND CRITERIA APPENDIX 2: CLASSIFICATION PROCEDURES, TEST METHODS AND CRITERIA RELATING TO CLASS 9 APPENDIX 3: A-60 CLASS BULKHEAD CERTIFICATE APPENDIX 4: RESISTANCE TO DETONATION TEST APPENDIX 5: RESISTANCE TO DETONATION CERTIFICATE APPENDIX 6: MATERIAL SAFETY DATA SHEET EXAMPLE

59 60 65 66

79 84 86 90 91

APPENDIX 7: DECISION No 1348/2008/EC OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL APPENDIX 8: SAFE STORAGE OF AMMONIUM NITRATE APPENDIX 9: ISM PROCEDURES OF M/V SULTAN ATASOY APPENDIX 10: LETTER TO PERMISSION APPENDIX 11: Ykleme ncesi Ambarlarn Durumunu Kontrol Listesi APPENDIX 12: Gemi - Sahil Emniyet Kontrol Listesi (UN 2067) 100 102 115 118 119 120

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APPENDIX 13: Gemi - Sahil Emniyet Kontrol Listesi (UN 2071) APPENDIX 14: Gemi - Sahil Emniyet Kontrol Listesi (Tm Gbre Tipleri in) APPENDIX 15: Amonyum Nitrat Yklemesinde/Tahliyesinde Ve Seferde ken Personelin Is Yayacak Kaynaklar Kullanmaktan Kanmalar Uyars

121 122

123

APPENDIX 16: Amonyum Nitratn Kimyasal Bozunmaya Uramas Durumunda Acil Olarak Gemi Personelinin Yapmas Gerekenler 124

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LIST OF ABBREVIATIONS AN: Ammonium Nitrate ANFO: Ammonium Nitrate Fuel Oil AS: Ammonium Sulphate CAN: Calcium Ammonium Nitrate CAS: Chemical Abstracts Service COAG: Council of Australian Governments DAP: Diammonium Phosphate EmS: Emergency Responce Procedures Guide EPA: The United States Environmental Protection Agency EU: European Union IFA: International Fertilizer Industry Association IMDG: International Maritime Dangerous Goods IMO: International Maritime Organization IMSBC: International Maritime Solid Bulk Cargoes MAP: Monoammonium Phosphate N: Nitrogen N-P-K: Nitrogen-Phosphorus-Potassium RDX: Royal Demolition Explosive (cyclotrimethylene-trinitraamine) TSP: Triple Super Phosphate UN: United Nations

LIST OF TABLES Table 1.1.: World Fertilizer Production Table 1.2.: Production Percentages Table 1.3.: Global Export/Import Values Table 1.4.: Export/Import Percentages Table 1.5.: World AN Export Values by Regions Table 1.6.: World AN Import Values by Regions Table 1.7.: Production Quantities of Turkey Table 1.8.: Consumption Quantities of Turkey Table 1.9.: Export Quantities of Turkey Table 1.10.: Import Quantities of Turkey Table 1.11.: Turkish Ports Statistics of AN Table 4.1.: Emergency Procedures Table 4.2.: Risk Assessment 2 3 4 4 5 7 8 8 9 9 10 50 51

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LIST OF FIGURES Figure 1.1.: From Raw Material to Fertilizer Flow Diagram Figure 2.1.: Logic Diagram 1 Figure 2.2.: Logic Diagram 2 Figure 2.3.: General Properties of AN Figure 3.1.: Photo of Oppau Accident Figure 3.2.: SS Grandcamp Figure 3.3.: View from Galveston Figure 3.4.: After the Explosion of Terra AN Plant Figure 3.5.: Explosion of Plant Near Toulouse City Figure 3.6.: 18th February 2007 the Ostedijk Figure 3.7.: 21st February 2007 the Ostedijk Figure 3.8: M/V Lady Juliet Figure 3.9.: After the terrorist attack, Oklahoma City Figure 3.10.: The Daily Oklahoman Newspaper Figure 3.11.: 15th and 20th November 2003, Istanbul Figure 4.1.: M/V SULTAN ATASOY Figure 4.2.: M/V SULTAN ATASOY Hold No 1 Figure 4.3.: M/V SULTAN ATASOY Hold No 2 Figure 4.4.: UN 2067 AN Based Fertilizer Sample Sack 1 17 18 21 31 32 32 35 36 37 38 39 40 41 43 54 56 57 58

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INTRODUCTION The text is divided into four chapters; the market, classification and hazards, accidents and terror incidents, and safety precautions to be held. First chapter gives information about the global and domestic ammonium nitrate with other fertilizers trade statistics. In the second chapter, I worked for explaining the sections while categorizing and classification of AN according to UN Regulations and IMDG Code. Also test procedures and certificates are given in appendices. I was influenced while searching the third chapter of this thesis, learned how the accidents occured. Also starting with 1995 U.S. Oklahoma City terrorism incident, there were lots of terrorist attacks which include bomb of AN. What is the world's decisions about preventing AN usage for terrorism? Restrictions, bans and the effects of terrorism incidents are discussed too. The last chapter which includes a case study of AN discharge operation in January 2012 that gave me an observation chance, Besides this chapter inludes what are the safety precautions while handling and transporting AN. To improving safety at ship-shore operations and ship officers and crew awareness for hazards of AN; I have proposed checklists which are in appendices in Turkish format.

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CHAPTER ONE THE MARKET OF AMMONIUM NITRATE AND OTHER FERTILIZERS World is becoming more and more populous every year. In 1950, grain production was 1000 million tons in one year to feed 4.5 billions of people. This fact has changed to 2500 million tons to feed 7 billions of people in 2000's. (http://faostat.fao.org) When you consider that every field of crops in the world is made up of individual growing plants, each in need of nutrients, the fertilizer industry has a distribution and economic challenge unrivaled in almost any other business. The most important components of fertilizer for plant nutrition are known as the primary nutrients. These primary nutrients are nitrogen, phosphorus, and potassium. The flow diagram which shown below that explains production of fertilizers. Figure 1.1: From Raw Material to Fertilizer Flow Diagram

Source: http://www.fertilizer101.org

1.1. World Fertilizer Statistics Fertilizer demand has been influenced by population, economic growth, agricultural production and government policies. So that production rates are changing with fertilizer demand. 1.1.1. World Fertilizer Production/Consumption Values (2000-2010) "Table 1.1." shows that the production of all fertilizers by all the countries in one year. 505070 thousand metric tons of fertilizer produced in 2000, 642923 thousand metric tons of fertilizer produced in 2010. The appearent consumption values are nearly the same as the production values. Note: In all general fertilizer tables, the examined fertilizer types are: Ammonium, Ammonium Nitrate (AN), Ammonium Sulphate (AS), Calcium Ammonium Nitrate (CAN), Diammonium Phosphate (DAP), Monoammonium Phosphate (MAP), Triple Super Phosphate (TSP), Phosphate, Phosphoric Acid, Potash, Sulphur and Urea. Table 1.1.: World Fertilizer Production Fertilizer Production
700000 650000

Thousand Metric Tons

600000 550000 500000 450000 400000 350000 300000 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010

Source: IFA, (2011)

AN based fertilizers production values are %9 and N based fertilizers production values are %68 of all fertilizers. (Average values between 2000 and 2010). Table 1.2.: Production Percentages Production Percentages

TSP 1% POTASH 8%

UREA 23%

AMMONIA 25%

SULPHUR 8%

PHOSPHATE 9% CAN DAP 2% 5%

AN 7% AS 3%

PHOSPHORIC ACID 6%

MAP 3%

Source: IFA, (2011) 1.1.2. World Fertilizer Export/Import Values (2000 - 2010) Statistics which given in this section are transported goods with all transportation options like road, rail and sea transport. Ammonia and AN based fertilizers are frequently transporting between South America and Canada to U.S. Also big producers like Russian Federation, Poland and Ukraine export to West Europe this fertilizers. Urea and potash are mostly transported to India, China and South America. Biggest exporters of potash are Canada and Russian Federation. Urea exporters are S.Arabia, Egypt, Ukraine and Canada. Phosphate Rock exporters generally are Russian Federation, Morocco, Lebanon, Syria and Egypt. DAP fertilizer trade usually transporting from U.S. to India. Most of the transportation between countries continental, as explained that the mostly selected transportation way between countries is shipping.

"Table 1.3." shows that the total export/import quantity which transported between countries in one year. Table 1.3.: Global Export/Import Values Global Export/Import Values
220000 200000

Thousand metric tons

180000 160000 140000 120000 100000 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010

Source: IFA, 2011 AN based fertilizers export/import values are %9 and N based fertilizers are %42 of all fertilizers. (Average values between 2000 and 2010). Table 1.4.: Export / Import Percentages Export / Import Percentages
AN 5% TSP 2% UREA 18% AMMONIA; %10 AS 5% CAN 4% SULPHUR 15% DAP 7%

POTASH 22% MAP 3% PHOSPHORIC ACID 3% PHOSPHATE 6%

Source: IFA, 2011

1.2. World Ammonium Nitrate Statistics This section provides general information of importers and exporters with their quantities. 1.2.1. Ammonium Nitrate Exports by Regions Supplier countries of the world by regions are shown below, they are exporting nearly all of the AN. West Europe: France, Spain, Sweden Central Europe: Bulgaria, Hungary, Romania East Europe & Central Asia: Lithuania, Poland, Russian Federation, Ukraine North America: Canada Latin America: Brazil, Chile Africa: Algeria, Egypt, South Africa Oceania: Australia

Source: http://faostat.fao.org/ Table 1.5.: World AN Export Values by Regions

Source: IFA, 2011 1.2.2. Ammonium Nitrate Imports by Regions Demander countries of the world by regions are shown below. In fact, most of the countries demand AN but here written which country import plenty of it. West Europe: Denmark, France, Spain, United Kingdom Central Europe: Hungary, Serbia, Italy, Poland East Europe & Central Asia: Ukraine, Romania North America: Mexico, U.S. Latin America: Argentina, Brazil, Ecuador, Colombia, Peru Africa: Morocco, Tunusia West Asia: Turkey, Syria, Azerbaijan South Asia: India East Asia: Indonesia, Malaysia Oceania: Australia, New Zealand, Papua New Guinea.

Source: http://faostat.fao.org/

Table 1.6.: World AN Import Values by Regions

Source: IFA, 2011

1.3. Domestic Fertilizer Statistics Turkey produced 3160 thousand tons of fertilizer and consumpted 5175 thousand tons of fertilizer in year 2004. In each year the demand of fertilizer increase, however domestic production do not supply. The fertilizer factories are under their capacities because of the energy costs and raw material prices. The transportation of fertilizers to Turkey generally from Ukraine and Russian Federation via Black Sea. Tables which are shown below, point that the production and consumption quantities of different kinds of fertilizers, average in between years. Table 1.7.: Production Quantities of Turkey
Fertilizer (1000 Tons) AS AN %26 AN %33 Urea TSP DAP Composite Total
1985-1989 1990-1995 1996-2000 2001-2005

2006 141 1131 94 147 114 192 1312 3131

2007 219 942 225 121 226 1379 3112

2008 108 847 293 145 119 143 1304 2959

299 1028 455 458 416 986 3642

215 1201 32 551 159 286 1365 3809

139 1149 42 363 104 229 1542 3568

147 930 72 345 85 114 1459 3152

Source: TK, 2010 Table 1.8.: Consumption Quantities of Turkey

Fertilizer (1000 Tons) AS AN %26 AN %33 Urea TSP DAP Composite Total
1985-1989 1990-1995 1996-2000 2001-2005

2006 388 973 896 807 53 637 1571 5325

2007 360 1006 889 772 40 428 1614 5109

2008 292 809 744 770 19 149 1313 4096

440 1584 2 517 264 432 1171 4410

342 1401 132 650 128 659 1395 4707

310 1228 401 838 60 633 1627 5097

305 933 752 781 39 501 1509 4820

Source: TK, 2010

1.3.1. Export Statistics in Turkey Export amount of Turkey depends on prices, interior market conditions and demands of other countries. However, Turkey exports less than 10% of all produced fertilizers in one year. Generally export regions are West Europe, North Africa and Middle East. Table 1.9.: Export Quantities of Turkey
Fertilizer (1000 Tons) AS AN %26 AN %33 Urea TSP DAP Composite Total
1985-1989 1990-1995 1996-2000 2001-2005

2006 6 72 7 17 32 39 173

2007 69 6 29 123 47 274

2008 5 20 7 32 95 45 204

2 28 146 285 222 13 696

13 46 8 76 47 5 27 222

1 2 1 8 3 10 25

33 26 11 45 20 66 201

Source: TK, 2010 1.3.2. Import Statistics in Turkey Turkey generally imports nitrogen based fertilizers rather than phosphate or sulphur based fertilizers. 85% of fertilizers that Turkey imported in year 2004 are urea and ammonium nitrate based fertilizers. Table 1.10.: Import Quantities of Turkey
Fertilizer (1000 Tons) AS AN %26 AN %33 Urea TSP DAP Composite Total
1985-1989 1990-1995 1996-2000 2001-2005

2006 250 860 812 32 414 260 2628

2007 231 42 560 943 3 310 55 2144

2008 253 8 555 789 9 164 265 2043

168 532 2 220 22 223 234 1401

141 245 137 258 4 365 70 1220

192 81 450 557 6 351 64 1701

233 21 723 546 14 424 181 2142

Source: TK, 2010

1.3.3. Ammonium Nitrate Based Fertilizer Statistics 2004 - 2010 This section brings information and statistics of AN based fertilizers' handling quantities which handled at Turkish ports. The table shown below displays quantities. Difference between loaded and exported is traded in Turkish Coasts. Difference between discharged and imported is the transit shipment value. Table 1.11.: Turkish Ports Statistics of AN (ton) Year 2004 2005 2006 2007 2008 2009 2010 Loaded 13200 5068 90499 40275 30007 Discharged 720288 664751 789463 634797 585182 936052 670439 Handled 735925 668750 793963 639869 675681 976327 700446 Imported 720288 664751 788460 634797 508172 914395 657818 Exported 10500 5068 37689 28142 18897

Source: TK, 2011

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CHAPTER TWO ANALYSIS AND CLASSIFICATION OF AMMONIUM NITRATE AND AMMONIUM NITRATE BASED FERTILIZERS The classification of AN and AN based fertilizers were explained according to IMDG Code, IMSBC Code and UN Recommendations on the Transport of Dangerous Goods Model Regulations in this chapter. IMDG Code contains relevant information for hazard class, subsidiary risk(s) (if any), packing group (where assigned), packing and tank transport provisions, EmS, segregation and stowage, properties and observations. In the IMDG Code, substances are divided into 9 classes. A substance with multiple hazards has one 'Primary Class' and one or more 'Subsidiary Risks'. Some substances in the various classes have also been identified as substances harmful to the marine environment. (IMDG Code, 2010; 35-40) (Zorba, 2009; 91-95) IMDG Classes are given below: Class 1: Explosives Division 1.1: substances and articles which have a mass explosion hazard Division 1.2: substances and articles which have a projection hazard but not a mass explosion hazard Division 1.3: substances and articles which have a fire hazard and either a minor blast hazard or a minor projection hazard or both, but not a mass explosion hazard Division 1.4: substances and articles which present no significant hazard Division 1.5: very insensitive substances which have a mass explosion hazard Division 1.6: extremely insensitive articles which do not have a mass explosion hazard Class 2: Gases Class 2.1: flammable gases

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Class 2.2: non-flammable, non-toxic gases Class 2.3: toxic gases

Class 3: Flammable liquids Class 4: Flammable solids; substances liable to spontaneous combustion; substances which, in contact with water, emit flammable gases Class 4.1: flammable solids, self-reactive substances and desensitized explosives Class 4.2: substances liable to spontaneous combustion Class 4.3: substances which, in contact with water, emit flammable gases Class 5: Oxidizing substances and organic peroxides Class 5.1: oxidizing substances Class 5.2: organic peroxides

Class 6: Toxic and infectious substances Class 6.1: toxic substances Class 6.2: infectious substances

Class 7: Radioactive material Class 8: Corrosive substances Class 9: Miscellaneous dangerous substances and articles Many of the substances assigned to classes 1 to 9 are deemed as being marine pollutants. Certain marine pollutants have an extreme pollution potential and are identified as severe marine pollutants. Dangerous goods are assigned to UN Numbers and Proper Shipping Names according to their hazard classification and their composition. Goods of all classes other than 1, 2, 6.2 and 7 have also been assigned packaging groups according to the degree of danger they present; I - great danger, II - medium danger, or III - minor danger. (IMDG Code, 2010; 37-40)

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2.1. Classification of Ammonium Nitrate There are five types classification of AN, which are generally transported by bulk carriers. Products considered here are listed below with their UN numbers, shipping names, class numbers. 2.1.1. Ammonium Nitrate UN 0222 - Class 1.1 White crystals, prills or granules. Wholly or partly soluble in water. Odorless. AN with more than 0.2% combustible material, including any organic substance, calculated as carbon to the exclusion of any other added substance is described UN number 0222 and Class 1.1D. (IMSBC Code, 2010; 66) 2.1.2. Ammonium Nitrate UN 1942 - Class 5.1 White crystals, prills or granules. Wholly or partly soluble in water. Oxidizer, supports combustion. Odorless. AN with not more than 0.2% total combustible material, including any organic substance, calculated as carbon to the exclusion of any other added substance is described UN number 1942 and Class 5.1. (IMSBC Code, 2010; 67-68) 2.1.3. Ammonium Nitrate Based Fertilizer UN 2067 - Class 5.1 Crystals, granules or prills. Wholly or partly soluble in water. Hygroscopic. Odorless. AN based fertilizers classified as UN 2067 are uniform mixtures containing ammonium nitrate as the main ingredient within the following composition limits: i) not less than 90% ammonium nitrate with not more than 0.2% total combustible/organic material calculated as carbon and with added matter, if any, which is inorganic and inert towards ammonium nitrate; or ii) less than 90% but more than 80% ammonium nitrate with other inorganic materals; or iii) less than 90% but more than 70% ammonium nitrate mixed with calcium carbonate and/or dolomite (calcium magnesium carbonate) and not more than 0.4% total combustible/organic material calculated as carbon; or

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iv) ammonium nitrate based fertilizers containing mixtures of ammonium nitrate and ammonium sulphate with more than 45% but less than 70% ammonium nitrate and more than 0.4% total combustible/organic material calculated as carbon such that the sum of the percentage compositions of ammonium nitrate and ammonium sulphate exceeds 70%. (IMSBC Code, 2010; 69-71) Note: This entry may only be used for substances that do not exhibit explosive properties of class 1 when tested in accordance to Test Series 1 and 2 of class 1 (see Appendix 1; UN Manual of Tests and Criteria, Part I) 2.1.4. Ammonium Nitrate Based Fertilizer UN 2071 - Class 9 Usually granules, wholly or partly soluble in water. Hygroscopic. Ammonium nitrate based fertilizers classified as UN 2071 are uniform ammonium nitrate based fertilizer mixtures of nitrogen, phosphate and potash, containing not more than 70% ammonium nitrate and not more than 0.4% total combustible organic material calculated as carbon or with not more than 45% ammonium nitrate and unrestricted combustible material. Fertilizers within these composition limits are not subject to the provisions of this schedule when shown by a trough test (see Appendix 2; UN Manual of Tests and Criteria, Part III, subsection 38.2) they are not liable to self-sustaining decomposition. (IMSBC Code, 2010; 72-73) 2.1.5. Ammonium Nitrate Based Fertilizer (Non-Hazardous) Crystals, granules or prills. Non-cohesive when dry. Wholly or partly soluble in water. Ammonium nitrate based fertilizers transported in conditions mentioned in this schedule are uniform mixtures containing ammonium nitrate as the main ingredient within the following composition limits: not more than 70% ammonium nitrate with other inorganic materials;

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not more than 80% ammonium nitrate mixed with calcium carbonate and/or dolomite and not more than 0.4% total combustible organic material calculated as carbon;

nitrogen type ammonium nitrate ammonium nitrate based fertilizers containing mixtures of ammonium nitrate and ammonium sulphate with not more than 45% ammonium nitrate and not more than 0.4% total combustible organic material calculated as carbon; and

uniform ammonium nitrate based fertilizer mixtures of nitrogen, phosphate or potash, containing not more than 70% ammonium nitrate and not more than 0.4% total combustible organic material calculated as carbon or with not more than 45% ammonium nitrate and unrestricted combustible material. Fertilizers within these composition limits are not subject to the provisions of the schedule when shown by a trough test (see Appendix 2) that they are liable to self-sustaining decomposition or if they contain an excess of nitrate greater than 10% by mass. (IMSBC Code, 2010; 75-77)

Note: "Non-hazardous" may only be used if the chemical or physical properties of an ammonium nitrate based fertilizer are such that, when tested (in accordance to Appendix 1 and Appendix 2), it does not meet the established defining criteria of any IMDG class.

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2.2. Logic Diagram The logic diagram explains that classification of ammonium nitrate in accordance with UN Regulations, and EU Regulations. The logic diagram is split into two, "Diagram 1" and "Diagram 2" on next pages. It uses the AN content as the main parameter. The second level parameter is based on the nature and concentration of the other ingredients. The fertilizers are categorised as compounds** (i.e. NP, NK or NPKs) or straight*-N types (i.e. those containing only nitrogen as the nutrient). The main source of nitrogen here is AN but other nitrates such as potassium nitrate, sodium nitrate and calcium nitrate can also be potential sources. *Straight fertilizer Qualification generally given to a nitrogenous, phosphatic or potassic fertilizer having a declarable content of only one of theprimary nutrients **Compound fertilizer Fertilizer, obtained chemically or by blending or both, having adeclarable content of at least two of the primary nutrients. It is important to note that the EU Detonation Test is not part of the UN classification system. In the EU the Fertilizer Regulations require most high AN fertilizers to satisfy the EU Detonation Test. (see Appendix 4 and Appendix 5) (EFMA, 2012; 1-20) Figure 2.1.: Logic Diagram Part 1 Figure 2.2.: Logic Diagram Part 2

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Source: (EFMA, 2012; 1-20)

17

Source: (EFMA, 2012; 1-20)

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2.2.1. Examples Classification of three fertilizer compositions are shown below according to logic diagrams based on the source material content. It is assumed that the organic/combustible material content is within the specified limits. Example 1: Fertilizer composition by weight % Ammonium nitrate 75 Calcium carbonate or dolomite 21 Ammonium sulphate 4

Answer: The fertilizer is not classified. Clearly, the addition of ammonium sulphate is quite small and is to improve quality. The fertilizer can be regarded as a mixture of AN and dolomite. Example 2: Fertilizer composition by weight % Ammonium nitrate 75 Calcium carbonate or dolomite 10 Inert e.g. calcium sulphate or gypsum 15

Answer: The fertilizer is classified as an oxidiser, class 5.1. Example 3: Fertilizer composition by weight % Ammonium nitrate 69 MOP (KCl) 9 Ammonium sulphate 22 Trough test shows it to be not capable of self-sustaining

decomposition. Answer: The fertilizer is not classified. Source: (EFMA, 2012; 1-20)

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2.3. Properties of Ammonium Nitrate Ammonium nitrate (AN) is a major chemical product. It is most frequently produced by neutralisation of nitric acid with ammonia and is mainly processed into high quality fertilisers. As a straight fertilizer, in 2005 it accounted for 20% of world consumption of nitrogen fertilisers, and is present in many blended and compound fertilisers. AN is primarily used as a fertiliser; however it is better known for its use as an ingredient in explosives, especially in mining. (Kiiski, 2009; 6-7) (W.Aus.Gov., 2008; 20) AN is produced from ammonia and nitric acid with the highly exothermic reaction: NH3 (g) + HNO3 (l) NH4NO3(s) ; H = - 146 kJ/mol AN melts at 169C and decomposes above 2100C. It is not in itself combustible but as it is an oxidising agent, it can assist other materials to burn. It cakes readily; particularly when handled in bulk and exposed to atmosphere. (Gerhartz, 1985; 243-247) The transition at 32C is accompanied by a significant volume change; consequently repeated thermal cycling across this temperature causes physical breakdown of the prills/granules, unless they have been treated for thermal stability. (IFA, 2007; 3-8) AN dissolves readily in water. In addition the salt is hygroscopic. When the salt is dissolved in water, heat is absorbed. Therefore AN can be used in freezing mixtures. The heat of solution in an almost infinite quantity of water is +26.4 kJ/mol at 18C, the integral heat of solution to saturation is +16.75 kJ/mol and the heat of solution in a saturated solution is +15 kJ/mol. (Kiiski, 2009; 8)

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Figure 2.3.: General properties of AN (Kiiski, 2009; 6) 2.4. General Hazards of Ammonium Nitrate 2.4.1. Fire AN itself does not burn. Being an oxidising agent, it can facilitate the initiation of fire and intensify fires in combustible materials. Hot AN solutions can initiate fires when coming into contact with rags, wooden articles and clothing. Other combustible materials impregnated with AN have been known to startburning spontaneously when left on hot surfaces. Similarly, AN products contaminated with oil or combustible materials can start a fire when hot. (W.Aus.Gov., 2008; 18) 2.4.2. Explosion An explosion of pure AN can be initiated with high explosives under ambient conditions, and explosives must never be used to break up or loosen caked AN. Under ambient conditions, it is not possible to initiate AN by means of a bullet. However, the shock sensitivity of molten AN increases significantly with temperature, and severe mechanical impact under extreme conditions of temperature may lead to detonation in certain circumstances. AN can also explode without shock if heated sufficiently, but only if contaminated, underconfinement, or both. Under these circumstances, the

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temperature will quickly rise above 300C, giving off other gases including brown vapours of toxic nitrogen dioxide (NO2). The temperature will continue to rise through self-accelerating reactions, and a detonation may occur. In a fire, for example, pools of molten AN may be formed and if the molten mass becomes confined, such as in drains, pipes, plant or machinery, it could explode, particularly if it becomes contaminated. Fires involving AN have caused many explosions in the past. It is also true that there have been many more fires involving AN that did not lead to explosions. The potential for an explosion is always pres ent when the AN melt is contaminated and the following explosion reaction is catalysed: NH4NO3 N2 + 2H2O + O2 (+ 1580 kJ/kg) An explosion is favoured by the increased heat of explosion and increased sensitivity when further mixed with the optimum amount of fuel (such as diesel fuel, a hydrocarbon represented by CH2) so that the following oxygen-balanced reaction (as in the explosion of ANFO) occurs: 3(NH4NO3) + CH2 3N2 + 7H2O + CO2 (+ 4017 kJ/kg) AN is ideally set up as an explosive substance, since it carries the oxidising nitrate ion in intimate contact with the fuel element, the ammonium ion. All that is required are small amounts of contaminants to act as a catalyst, explaining the unpredictability of AN under fire conditions. (W.Aus.Gov., 2008; 19-20) 2.4.3. Decomposition Molten AN decomposes at about 210C to give off toxic gases. If AN is heated in an open and unconfined situation, it will decompose completely to give gaseous products in a steady controlled way with white fumes and vapours. The primary reaction is irreversible, exothermic and produces nitrous oxide (N2O), a medical anaesthetic, and water. NH4NO3 N2O + 2H2O (+ 450 kJ/kg) If the reaction temperature is allowed to exceed 250C then it is accompanied by an endothermic reaction producing ammonia (NH3) and nitric acid (HNO3).

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NH4NO3 HNO3 + NH3 (- 2200 kJ/kg) Providing gases can escape freely, this combination of exothermic and endothermic reactions can provide a temperature limiting mechanism so that the temperature does not rise above 300C, even with the input of a considerable amount of external heating. (W.Aus.Gov., 2008; 19-20) 2.5. Class Based Hazards of Ammonium Nitrate Five classes show different hazards as explained below. 2.5.1. Ammonium Nitrate UN 1942 - Class 5.1 A major fire aboard a ship carrying these materials may involve a risk of explosion, in the event of contamination with fuel oil. An adjacent detonation may also involve a risk of explosion. If heated strongly, this cargo decomposes giving of toxic gases and gases which support combustion. Ammonium nitrate dust might be irritating to skin and mucous membranes. This cargo is hygroscopic (absorbs water, water vapor or moisture) and will cake if wet. (IMSBC Code, 2010; 67) 2.5.2. Ammonium Nitrate Based Fertilizer UN 2067 - Class 5.1 Supports combustion. A major fire aboard a ship carrying these materials may involve a risk of explosion, in the event of contamination with fuel oil. An adjacent detonation may also involve a risk of explosion. If heated strongly decomposes, risk of toxic fumes and gases which support combustion, in the cargo space and on deck. Fertilizer dust might be irritating to skin and mucous membranes. This cargo is hygroscopic (absorbs water, water vapor or moisture) and will cake if wet. (IMSBC Code, 2010; 69)

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2.5.3. Ammonium Nitrate Based Fertilizer UN 2071 - Class 9 These mixtures may be subject to self-sustaining decomposition if heated. The temperature in such a reaction can reach 500C. Decompostion, once initiated, may spread through the remainder, producing gases which are toxic. None of these mixtures is subject to the explosion hazard. Fertilizer dust might be irritating to skin and mucous membranes. This cargo is hygroscopic (absorbs water, water vapor or moisture) and will cake if wet. (IMSBC Code, 2010; 71) 2.5.4. Ammonium Nitrate Based Fertilizer (Non-Hazardous) This cargo is non-combustible or with low fire risk. Even though this cargo is classified as non-hazardous, it will behave in the same way as the ammonium nitrate based fertilizers classified in class 9 under UN 2071 when heated strongly, by decomposing and giving off toxic gases. (IMSBC Code, 2010; 74) 2.6. Stowage and Segregation Requirements of Ammonium Nitrate Stowage and segregation requirements of ammonium nitrate cargoes shown below. 2.6.1. Ammonium Nitrate UN 1942 - Class 5.1 There should be no sources of heat or ignition in the cargo space. "Seperated by a complete compartment or hold from" combustible materials, chlorates, chlorides, chlorites, hypochlorites, nitrites, permanganates and fibrous materials (e.g. cotton, jute, sisal). "Seperated from" all other goods. If the bulkhead between the cargo space and the engine room is not insulated to class A-60 standart (see Appendix 3; A-60 Class Bulkhead Certificate), this cargo shall be stowed "away from" the bulkhead. (IMSBC Code, 2010; 67)

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2.6.2. Ammonium Nitrate Based Fertilizer UN 2067 - Class 5.1 "Seperated by a complete compartment or hold from" combustible materials, bromates, chlorates, chlorites, hypochlorites, nitrites, perchlorates, permanganates, powdered metals and vegetable fibres. "Seperated from" all other goods. "Seperated from" sources of heat or ignition. Not to be stowed immediately adjacent to any tank or double bottom tank containing fuel oil heated to more than 50C. If the bulkhead between the cargo space and the engine room is not insulated to class A-60 standart this cargo shall be stowed "away from" the bulkhead. (IMSBC Code, 2010; 70) 2.6.3. Ammonium Nitrate Based Fertilizer UN 2071 - Class 9 Stowage and segregation requirements are the same as 2.4.2. (IMSBC Code, 2010; 71) 2.6.4. Ammonium Nitrate Based Fertilizer (Non-Hazardous) The compatibility of non-hazardous ammonium nitrate based fertilizers with other materials which may be stowed in the same cargo space should be considered before loading. "Seperated from" sources of heat or ignition. Not to be stowed immediately adjacent to any tank or double bottom tank containing fuel oil heated to more than 50C. Fertilizers of this type should be stowed out of direct contact with a metal engine room boundary. This may be done, for example, by using flame-retardant bags containing inert materials or by any equivalent barrier approved by the competent authority. This requirement need not apply to short international voyages. (IMSBC Code, 2010; 75)

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2.7. Weather Precautions of Ammonium Nitrate This cargo shall be kept as dry as practicable. This cargo shall not be handled during precipitation. During handling of this cargo, all non-working hatches of the cargo spaces which this cargo is loaded or to be loaded shall be closed. Weather precautions are same for all classes of ammonium nitrate and ammonium nitrate based fertilizers. (IMSBC Code, 2010; 66-77) 2.8. Loading This subsection explains what shall be done at before loading and during loading. 2.8.1. Ammonium Nitrate UN 1942 - Class 5.1
Angle of Repose 27 to 42 Size 1 to 4 mm Bulk Density (kg/m) 1000 Class 5.1 Stowage Factor (m/t) 1.0 Group B

Prior to loading, the following provisions shall be complied with: This cargo shall not be accepted for loading when the temperature of the cargo above 40C. Prior to loading, the shipper shall provide the master with a certificate signed by the shipper stating that all the relevant conditions of the cargo. The fuel tanks situated under the cargo spaces to be used for the transport of this cargo shall be pressure tested to ensure that there is no leakage of manholes and piping systems leading to the tanks. All electrical equipment, other than those of approved intrinsically safe type, in the cargo spaces to be used for this cargo shall be electrically disconnected from the power source, by appropriate means other than a fuse, at a point external to the space. This situation shall be maintained while the cargo is on board.

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Due consideration shall be paid to the possible need to open hatches in case of fire to provide maximum ventilation and to apply water in an emergency, and the consequent risk to the stability of the ship through fluidization of the cargo. During loading, the following provisions shall be complied with: Smoking shall not be allowed on deck and in the cargo spaces and "NO SMOKING" signs shall be displayed while this cargo is on board. Bunkering of fuel oil shall not be allowed. Pumping of fuel oil in spaces adjacent to the cargo spaces, other than the engine room, shall not be allowed. As far as reasonably practicable, combustible securing and protecting materials shall not be used. When wooden dunnage is necessary, only a minimum shall be used. (IMSBC Code, 2010; 66-69) 2.8.2. Ammonium Nitrate Based Fertilizer UN 2067 - Class 5.1
Angle of Repose 27 to 42 Size 1 to 5 mm Bulk Density (kg/m) 900 to 1200 Class 5.1 Stowage Factor (m/t) 0.83 to 1.11 Group B

Prior to loading, the following provisions shall be complied with: This cargo shall not be accepted for loading when the temperature of the cargo above 40C. Prior to loading, the shipper shall provide the master with a certificate signed by the shipper stating that all the relevant conditions of the cargo. The fuel tanks situated under the cargo spaces to be used for the transport of this cargo shall be pressure tested to ensure that there is no leakage of manholes and piping systems leading to the tanks. All electrical equipment, other than those of approved intrinsically safe type, in the cargo spaces to be used for this cargo shall be electrically disconnected from the power source, by appropriate means other than a fuse, at a point external to the space. This situation shall be maintained while the cargo is on board.

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Due consideration shall be paid to the possible need to open hatches in case of fire to provide maximum ventilation and to apply water in an emergency, and the consequent risk to the stability of the ship through fluidization of the cargo. During loading, the following provisions shall be complied with: Bunkering of fuel oil shall not be allowed. Pumping of fuel oil in spaces adjacent to the cargo spaces, other than the engine room, shall not be allowed. As far as reasonably practicable, combustible securing and protecting materials shall not be used. When wooden dunnage is necessary, only a minimum shall be used. (IMSBC Code, 2010; 69-73) 2.8.3. Ammonium Nitrate Based Fertilizer UN 2071 - Class 9
Angle of Repose 27 to 42 Size 1 to 5 mm Bulk Density (kg/m) 900 to 1200 Class 9 Stowage Factor (m/t) 0.83 to 1.11 Group B

Prior to loading, the following provisions shall be complied with: All electrical equipment, other than those of approved intrinsically safe type, in the cargo spaces to be used for this cargo shall be electrically disconnected from the power source, by appropriate means other than a fuse, at a point external to the space. This situation shall be maintained while the cargo is on board. Due consideration shall be paid to the possible need to open hatches in case of fire to provide maximum ventilation and to apply water in an emergency, and the consequent risk to the stability of the ship through fluidization of the cargo. In addition, if decomposition occurs, the residue left after decomposition may have only half the mass of the original cargo. Due considetation shall be paid to the effect of the loss of mass on the stability of the ship. During loading, the following provisions shall be complied with:

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Bunkering of fuel oil shall not be allowed. Pumping of fuel oil in spaces adjacent to the cargo spaces, other than the engine room, shall not be allowed. (IMSBC Code, 2010; 72-74) 2.8.4. Ammonium Nitrate Based Fertilizer (Non-Hazardous)
Angle of Repose 27 to 42 Size 1 to 4 mm Bulk Density (kg/m) 1000 to 1200 Class Not applicable Stowage Factor (m/t) 0.83 to 1.0 Group C

Prior to loading, the following provisions shall be complied with: All electrical equipment, other than those of approved intrinsically safe type, in the cargo spaces to be used for this cargo shall be electrically disconnected from the power source, by appropriate means other than a fuse, at a point external to the space. This situation shall be maintained while the cargo is on board. Due consideration shall be paid to the possible need to open hatches in case of fire to provide maximum ventilation and to apply water in an emergency, and the consequent risk to the stability of the ship through fluidization of the cargo. In addition, if decomposition occurs, the residue left after decomposition may have only half the mass of the original cargo. Due considetation shall be paid to the effect of the loss of mass on the stability of the ship. During loading, the following provisions shall be complied with: Bunkering of fuel oil shall not be allowed. Pumping of fuel oil in spaces adjacent to the cargo spaces, other than the engine room, shall not be allowed. (IMSBC Code, 2010; 73-77)

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CHAPTER THREE AMMONIUM NITRATE ACCIDENTS, TERROR INCIDENTS AND EFFECTS 3.1. Accidents Although ammonium nitrate generally is used safely and normally is stable and unlikely to explode accidentally, accidental explosions of ammonium nitrate have resulted in loss of lives and destruction of property. These accidents rarely occur, but when they do, they have high impacts. Past accidental explosions of ammonium nitrate have included some of the most destructive on record. Several of these, including two in Germany in 1921, occurred during attempts to break up large piles of solidified or caked ammonium nitrate-ammonium sulfate mixtures using a blasting explosive. The blasting initiated explosions in the ammonium nitrate - ammonium sulfate mixtures. Other large explosions were triggered by fires involving ammonium nitrate in confined spaces, including the Texas 1947 explosion of two cargo ships. A fire in the hold, involving ammonium nitrate fertilizer coated with wax and stored in paper bags, caused the explosion of the first ship; the ammonium nitrate in the second ship exploded some time later, apparently as a result of a fire caused by the first explosion. As a result of such accidents and subsequent studies of the properties of ammonium nitrate, caked ammonium nitrate no longer is broken up with blasting agents, and wax coatings are no longer used for ammonium nitrate fertilizer. Explosions of ammonium nitrate, involving relatively small quantities, have occurred during the preparation of nitrous oxide. In these cases, the explosions of ammonium nitrate occurred as a result of excessively high temperatures and confinement during processing. 3.1.1. 1921 Oppau - Germany On 21 September 1921, when the technician was preparing the holes for the firings in the "silo 110" at 7.00 am, a very powerful explosion took place in the silo at 7.32 am, creating a 90m x 125m crater and 20m deep. According to witnesses, there were two successive explosions, the first one being weak and the second one devastating. Seismographic readings

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from Stuttgart, at 150 km from Oppau also showed two distinctive explosions that occurred at an interval of half a second. The explosion was heard in Munich, 275 km from the plant and caused panic among the masses. Material damage was reported at several dozens of kilometers away from the accident site. The official human casualty reported included 561 deaths, 1952 injured and 7500 people left homeless. Around 80% of the buildings in Oppau were destroyed. (Braun O.,1953; 33) Figure 3.1. : Photo of Oppau Accident.

Source: http://en.wikipedia.org 3.1.2. 1942 Tessenderloo - Belgium Use of blasting explosive led to a detonation in AN pile on April 29th 1942, killing 189 people at the plant and in the town. (IFA, 2002; 8-9) 3.1.3. 1947 Texas City - USA One of the worst disasters in history occurred on April 16, 1947, when the ship SS Grandcamp exploded at 9:12 A.M. at the docks in Texas City. The French owned vessel, carrying explosive ammonium nitrate, caught fire early in the

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morning, and while attempts were being made to extinguish the fire, the ship exploded. Fireballs streaked across the sky and could be seen for miles across Galveston Bay as molten ship fragments erupted out of the pier. Figure 3.2. : SS Grandcamp.

Source: http://texashistory.unt.edu Figure 3.3.: View from Galveston.

Source: http://texashistory.unt.edu The ship SS High Flyer, in dock for repairs and also carrying ammonium nitrate, was ignited by the first explosion; it was towed 100 feet from the docks before it exploded about sixteen hours later, at 1:10 A.M. on April 17. The High Flyer

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exploded in a blast, witnesses thought even more powerful than that of the Grandcamp. The precise number of dead was impossible to establish given the power of the explosions, confusion, and commuter nature of many dock workers. The anchor monument records 576 persons killed, of whom 398 were identified, while 178 are listed as missing. The number of injured is generally estimated at around 3500, which roughly equaled 25% of Texas Citys estimated population of 16000. In the 1947 the property loss amounted to about $100 million along with 1.5 million barrels of petroleum products consumed in the flames of the disaster valued at about $500 million. One-third of the towns 1519 houses were condemned, leaving an estimated 2,000 people homeless. (Stephens, 1997; 1-20), (Armistead, 1947; 1-16). 3.1.4. 1947 Brest - France On 23 July 1947, the Norwegian cargo vessel Ocean Liberty arrived in Brest after crossing the Atlantic. 5 days later, a port worker noticed smoke coming from one of the holds which had not been opened as its contents, more than 3000 tons of ammonium nitrate, were bound for Le Havre and Boulogne. The worker, remembering the Grandcamp disaster which had occurred three months earlier in Texas City, warned the captain, the fire brigade, the port authority and the Marines. A major and potentially very dangerous fire indeed then broke out onboard the Ocean Liberty and spread rapidly due to the east wind. A towing attempt was made but the vessel grounded on shoals near the port. While the team attempted to scuttle the vessel, still in the clutches of flames, to put out the fire, the cargo exploded. All the windows in the city and its surrounding area shattered into pieces. As in Texas City, a tidal wave caused by the explosion swept along the coast and sparked panic among bathers. In total, 22 people were killed in this accident, 4 went missing and hundreds were injured. (http://www.cedre.fr) 3.1.5. 1953 SS Tirrenia Wreck SS Tirrenia was a Finnish cargo steamer of 3826 grt. On the 23rd January 1953 when on route from Constanta for China with cargo of ammonium nitrate and a general cargo she suffered a fire and explosion after it. Ship sank at 145 nm east of Port Sudan. (http://www.wrecksite.eu)

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3.1.6. 1959 Roseburg, Oregon - USA On August 7, 1959 at 1:14am eight city blocks in downtown Roseburg, Oregon were leveled by the explosion of a truck containing 2 tons of dynamite and 4.5 tons of a strong oxidizer, nitro carbon nitrate. Fourteen people were killed, 125 injured, and over 100 building were destroyed or damaged. Windows nine miles from the blast were shattered. (http://www.ohs.org) 3.1.7. 1988 Kansas City, Missouri - USA One of the most common blasting agents used throughout the United States is a mixture of ammonium nitrate with fuel oil. The common name for the product is ANFO. Reportedly, of the approximately 23 tons of ammonium nitrate/fuel oil mixture involved in these explosions. On November 29, 1988, at 4:07 AM the explosion occurred. The blasts created two craters, each approximately 30 m wide and 2.4 m deep. The explosions also shattered windows within a 16 km area and could be heard 64 km away. Six firemen were killed at the accident. (http://www.kansascity.com) 3.1.8. 1994 Port Neal, Iowa - USA At approximately 0606 hours on December 13, 1994, an explosion occurred in the ammonium nitrate plant at the Terra International, Inc., Port Neal Complex. Four persons were killed as a direct result of the explosion, and 18 were injured and required hospitalization. The explosion resulted in the release of approximately 5,700 tons of anhydrous ammonia to the air and secondary containment, approximately 25,000 gallons of nitric acid to the ground and lined chemical ditches and sumps, and a large volume of liquid ammonium nitrate solution into secondary containment. (EPA Chemical Accident Investigation Report, 1995; 1-5)

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Figure 3.4.: After explosion of Terra AN Plant.

Source: http://www.exponent.com 3.1.9. 2001 Toulouse - France A terrible explosion of ammonium nitrate, killing 30 people, occurred on 21st September 2001, in Toulouse. The manufactured chemicals in the plant were mainly ammonium nitrate, ammonium nitrate-based fertilisers and other chemicals including chlorinated compounds. (Dechy, Bourdeaux, Ayrault, Kordek and Le Coze, 2004; 131-138)

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Figure 3.5.: Explosion of plant near Toulouse City.

Source: (Dechy, Bourdeaux, Ayrault, Kordek and Le Coze, 2004; 132)

3.1.10. 2004 Barracas - Spain In Barracas, a truck transporting 25 tons of ammonium nitrate exploded after a collision which resulted in two deaths and 5 people being injured. The explosion created a crater of 20m in diameter and 5m deep. (Marlair and Kordek, 2005; 13-28) 3.1.11. 2004 Mihailesti - Romania The accident in Romania followed a traffic accident where 50 kg bags caught fire and exploded 25 tons of AN. This accident resulted in 18 deaths and 10 severely injured persons. (Marlair and Kordek, 2005; 13-28)

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3.2. Near Misses One of the incidents is decomposition of AN due to fire at high temperature and the other is collision while the ship carrying AN with other explosives. 3.2.1. 2007 M/V Ostedijk - Spain The incident occurred while the Ostedijk was transporting a 6012 tons cargo of NPK fertilizer from Norway to Spain. In February 2007, the fertilizer aboard the cargo ship Ostedijk underwent a chemical reaction for seven days, destroying part of the cargo and compromising the ship. The incident took place off the coast of Galicia in Northeast Spain and generated a large plume of irritant gases easily seen from the coast. Figure 3.6.: 18th Feb 2007 the Ostedijk.

Source: Hadden, Jervis and Rein, 2009; 1-18 Thermal cameras were deployed by emergency personnel and measured surface temperatures of the fertilizer cargo in excess of 175C indicating that the inside of the cargo was at significantly higher temperature than this. Although the composition of the plume gas was not measured, it is likely that it contained the typical products of fertilizer decomposition. The fire fighting efforts began on the 20th February, when a tugboat sprayed the outside of hold 2 with a water canon. This had little or no effect and the reaction,

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deep inside the hold, continued as evidenced by the increasing size and density of the plume. On the fifth day, the plume increased in size to many times the ships length when emergency personnel sent aboard opened the cargo hold. A salvage company was then appointed on the 22nd February to provide specialized assistance and took control of the incident from the Spanish emergency services. Over the next couple of days, the fire is brought under control until it was declared extinguished on 23rd February by using 240m of water. (Hadden, Jervis and Rein, 2009; 1-18) Figure 3.7.: 21st Feb 2007 the Ostedijk.

Source: Hadden, Jervis and Rein, 2009; 1-18 3.2.2. 2009 M/V Lady Juliet - Dardanelles - Turkey On 17 December 2009, the Saint Vincent and the Grenadines flagged cargo ship M/V Lady Juliet with lenght 162 meters and 11978grt was traveling in Dardanelles in southern direction. (http://www.denizhaber.com) At 00.30 Lady Juliet has had rudder failure. She missed the turn at Nara point and rammed into the fisher breakwater at Eceabat. She entered 6 meters in the breakwater and damaged a 10 meter wide section. (http://www.denizhaber.com) When the captain of the ship refused at first any help adamantly it raised suspicion. It turned out that the ship was not only carrying 6900 tons of ammonium nitrate. Along ammonium nitrate, 152677 kilograms of rocket warhead primers, 24600 kilograms of bomb primers and 69 tons of various goods were on board too. If an explosion has occured it could be devastating for anakkale City. That ship also passed the Bosphorus while entering the Marmara from Black Sea. The

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population of Istanbul was 13 millions estimated at that time. So it could be a disaster if this accident has occured in Bosphorus. (http://www.denizhaber.com) On 18 December 2009 at 23.00, the ship salvaged by tugboats and went to anchorage area for waiting reinspection. After the inspection she was detained. Figure 3.8.: M/V Lady Juliet

Source: http://fotogaleri.hurriyet.com.tr

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3.3. Terror Incidents The explosive of choice in several of the most spectacular terrorist bombings around the world doesn't take an army of weapons inspectors to detect. It's cheap farm fertilizer that's tightly restricted in Europe but easily available in the United States and elsewhere, despite U.S. warnings after the train bombings in Madrid, Spain, that terrorists might use ammonium nitrate explosives to strike public transportation. (Hacaolu, 2004) 3.3.1. 1995 Oklahoma City - USA The Oklahoma City bombing was a terrorist attack on a federal building on April 19, 1995. The Oklahoma blast claimed 168 lives, including 19 children under the age of 6, and injured more than 680 people and demonstrated firsthand to America how ammonium nitrate could be misused by terrorists. (USA Today, June 20, 2001) (The Daily Oklahoman, April 20, 1995) The bomb is a mixture of 2500 kg high grade ammonium nitrate based fertilizer in bags, nitro methane and diesel fuel. Terrorists loaded in a truck this mixture. The blast destroyed or damaged 324 buildings within a sixteen-block radius, destroyed or burned 86 cars, and shattered glass in 258 nearby buildings. (http://www.fbi.gov) Figure 3.9.: After the Terrorist Attack, Oklahoma City

Source: http://upload.wikimedia.org

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Figure 3.10.: The Daily Oklahoman Newspaper

Source: The Daily Oklahoman, 20 April 1995

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3.3.2. 2002 Bali - Indonesia The October 12, 2002 Bali Night Club bombings, had claimed 202 lives and had left over 240 souls precariously injured. 88 of the victims are Australian. The suicide van bomb was containg 2 tons of explosive. Attacks such as the Bali bombings on 12 October 2002, and the bombing outside the Australian Embassy in Bali on 9 September 2004 but there is no evidence that ammonium nitrate was used in either of these attacks. (Chemicals and Plastics Regulation of Australia, 269)

3.3.3. 2003 Istanbul - Turkey On 15th and 20th November 2003 there were two attacks to Istanbul. First terrorist attack is to two synagogues in Istanbul, Neve Shalom and Bet Israel. Second bombing attack is to British Consulate and HSBC Bank Headquarters. The synagogues were located in a middleclass district with shops, apartments, offices. The trucks carried 400 & 700 kgs of ammonium sulfate, ammonium nitrate, pressured fuel mixed in plastic containers. The blasts killed 25 and injured 303 people. (http://news.bbc.co.uk) Police said ammonium nitrate based explosives were used again in the construction of second attack. The explosion killed 31 people including British Consul General Roger Short and injured 480 people. (http://news.bbc.co.uk)

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Figure 3.11.: 15th and 20th November 2003, Istanbul

Source: http://gazetearsivi.milliyet.com.tr

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3.3.4. 2006 Mumbai - India On 11 July 2006, 7 bombs each have 2.5 kg of ammonium nitrate and RDX mixture, were placed on trains on the western line of the suburban train network, which forms the backbone of the city's transport network. 209 people were killed and over 700 were injured. (http://news.bbc.co.uk) 3.3.5. Oslo - Norway A massive blast shook the centre of Oslo on Friday 22 July 2011, blowing out the windows of the prime minister's offices and damaging the finance and oil ministries. Police confirmed the next day that the blast was caused by a car bomb, and that undetonated explosives remained in the area. The bomb contained an estimated 950 kg of explosives made of ammonium nitrate fertilizer. Eight people were killed. (http://www.bbc.co.uk) 3.4. Effects Around World Some countries, such as the United Kingdom, have taken a light-handed approach, emphasising education, training and information sharing rather than legislative controls. In contrast, Indonesia, South Africa, Peru and Colombia have banned the production and/or import of ammonium nitrate fertilisers. Other countries have imposed bans on the fertilisers based on their ammonium nitrate content. For example, China has banned the use of 100% ammonium nitrate fertilisers, while in the Republic of Ireland and Northern Ireland, fertilisers containing more than 79% ammonium nitrate are banned. In the United States, about half of the 1.8 million tonnes of ammonium nitrate sold each year is used for fertiliser. However, only a few states have introduced regulations for controlling the sale of ammonium nitrate fertilisers. These regulations require retailers to be licensed, obtain valid identification from the buyer, keep transaction records and report any suspicious purchases. Retailers in other US states have adopted a voluntary security campaign, Be Aware America, where they report suspicious transactions involving ammonium nitrate. (COAG, 2008; 270) In 2007, the Department of Homeland Security introduced national standards for chemical facilities of high risk. These standards, which are still being implemented, impose tight security measures, with the certification of chemicals

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stores requiring the implementation of security plans and inventory management procedures. The UK Government has taken a light-handed approach to regulation, even though it is one of the greatest users of ammonium nitrate fertilisers in the world. Specifically, it has taken a layered approach to security of ammonium nitrate fertiliser, utilising regulation and industry partnerships to achieve security outcomes. It manufactures and imports about four million tonnes of ammonium nitrate products per year. It restricts the types of ammonium nitrate fertilisers that can be sold they must be certified as detonation resistant, and must satisfy other technical requirements pertaining to porosity and particle size. Further, farmers are provided with advice regarding appropriate storage and security measures for their ammonium nitrate fertilisers. (COAG, 2008; 270-274)

3.4.1. European Union and Turkey The European Economic Community predecessor of the European Union began to regulate production of ammonium nitrate fertilizer in 1980. EU rules require that ammonium nitrate fertilizers with more than 28 percent nitrogen be produced with large, dense granules to prevent them from absorbing diesel fuel the explosive mix that has killed hundreds of people. (see Appendix 7 EU Standards Relating Fertilizers) Turkey becomes the latest country to join the European Union in regulating sales of ammonium nitrate which, when mixed with diesel fuel, forms an explosive with more than half the force of dynamite. (18/3/2004 tarihli ve 25406 sayl Resm Gazete) Also look at Turkish Chemical Fertilizer Regulation "Kimyevi Gbre Denetim Ynetmelii" (25/4/2002 tarihli ve 24736 sayl Resm Gazete) Turkish importers mix limestone or dolomite into the fertilizer to cut its concentration of nitrogen and make it safer. Reducing the nitrogen content, however, undermines its value as a fertilizer.

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3.4.2. Australia In 2004, Australian governments agreed to a set of principles for the regulation of ammonium nitrate. The proposed control measures were intended to improve national security by reducing the potential for ammonium nitrate to be obtained for illegitimate purposes but allow continued access for legitimate users primarily miners and farmers. (Chemicals and Plastics Regulation Australia, 267) Australian Government have enacted laws to regulate the movement of dangerous goods that can harm humanity, handling, storage and sale of a number of readily available chemical compounds like ammonium nitrate that are serving both mankind and the terrorists at the same time. In Australia, the Dangerous Goods Regulations had also come into effect in August 2005 to enforce licensing in dealing with such substances and licenses were only granted industries with appropriate security measures in place to prevent any misuse. (see Appendix 8) 3.4.3. United Kingdom United Kingdom, recommend farmers to secure their fertilizers from stealing. They advise a ten point plan which shown below: Do not's and Do's. (http://www.secureyourfertiliser.gov.uk) Do not store fertilizer where there is public access. Do not leave bags of fertilizer in the field overnight. Do not store fertilizer near to, or visible from, the public highway. It is an offence to sell ammonium nitrate fertilizer without the proper certification (Detonation Resistance Certificate). (See, Appendix 5)

Do retain and file all fertilizer delivery notes. Do, wherever possible, and with regard to store fertilizer inside a locked building or compound.

Do fully sheet fertilizer when stored outside and regularly check to ensure that the stack has not been tampered with.

Do carry out regular, frequent stock checks.

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Do report any unexplained stock discrepancy or loss/theft to the police immediately.

Do purchase your fertilizer from an approved supplier.

3.4.4. United States of America, Oklahoma State USA, Code of Federal Regulations states that ammonium nitrate storage shall be secured to provide reasonable protection against vandalism, theft, or unauthorized access. Fertilizer retailers shall obtain the following regarding any sale of ammonium nitrate: Date of sale; Quantity purchased; License number of the purchaser's valid state or federal drivers license, or other picture identification card number approved for purchaser identification by the Board; and The purchaser's name, current physical address, and telephone number. Records created pursuant to this rule shall be maintained for a minimum of two years on a form or using a format set forth by the Board. Any retailer of ammonium nitrate may refuse to sell to any person attempting to purchase ammonium nitrate out of season, in unusual quantities, or under suspect purchase patterns. (http://www.oda.state.ok.us)

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CHAPTER FOUR SAFETY PRECAUTIONS OF AMMONIUM NITRATE AND A CASE STUDY AT ALIAGA EGE GUBRE PORT

4.1. Safety Precautions of AN Reference points in this part are United Nations "Transport of Dangerous Goods", IMSBC Code, EFMA Guidance for Sea Transport of Ammonium Nitrate Based Fertilizers and Government of Western Australia "Handling Ammonium Nitrate at a Special Berth". 4.1.1. Ammonium Nitrate UN 1942 - Class 5.1 (IMSBC Code) This cargo shall only be accepted for loading when the competent authority is satisfied in regard to the resistance to detonation test (see Appendix 4; Resistance to Detonation Test) Prior to loading, the shipper shall provide the master with a certificate stating that the resistance to detonation of this material. (see Appendix 5; Resistance to Detonation Certificate) The master and officers shall note that a fixed gas fire extinguishing system is ineffective on the fire involving this cargo and that applying water may be necessary. Pressure on the fire mains shall be maintained for fire fighting and fire hoses shall be laid out or be in position and ready for immediate use during loading and discharging opeation. No welding, burning, cutting or other operations involving the use of fire, open flame, spark producing equipment shall be carried out in the vicinity of the cargo spaces containing this cargo except in an emergency. Precautions shall be taken to avoid the containing this cargo except in an emergency. Precautions shall be taken to avoid the penetration of this cargo into other cargo spaces, bilges or other enclosed spaces. Smoking shall not be allowed on deck and in the cargo spaces and "NO SMOKING" signs shall be displayed on deck whenever this cargo is on board.

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The hatches of the cargo spaces, whenever this cargo is on board, shall be kept free to be capable of being opened in case of an emergency. When the bulkhead between cargo space and the engine room is not insulated to class A-60 standart, this cargo shall not be accepted for loading unless the competent authority approves that the arrangement is equivalent. Appropriate precautions shall be taken to protect machinery and

accommodation spaces from the dust of the cargo. Bilge wells of the cargo spaces shall be protected from ingress of the cargo. Due consideration shall be paid to protect equipment from the dust of the cargo. Persons who may exposed to the dust of the cargo shall wear goggles or other equivalent dust eye protection and dust filter masks. Those person shall wear protective clothing as necessary. The cargo spaces carrying this cargo shall not be ventilated during voyage. Hatches of the cargo spaces carrying this cargo shall be weathertight to prevent ingress of water. The temperature of this cargo shall be monitored and recorded daily during the voyage. (IMSBC Code, 66-77,323-324) 4.1.2. Ammonium Nitrate UN 2067 - Class 5.1 (IMSBC Code) Same as 4.1.1. 4.1.3. Ammonium Nitrate UN 2071 - Class 9 (IMSBC Code) This cargo shall only be accepted for loading when, as a result of testing in the trough test, its liability to self-sustaining decomposition shows decomposition rate not greater than 0.25 m/h. Other precautions are the same as 4.1.1. except the detonation test. 4.1.4. Emergency Procedures (IMSBC Code) All of ammonium nitrate cargoes have the same procedures as defined below, in accordance with IMSBC Code.

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Table 4.1.: Emergency Procedures Special emergency equipment to be carried

Protective clothing: boots, gloves, coveralls and headgear. Self-contained breathing apparatus.

Emergency Procedures
Wear protective clothing and self-contained breathing apparatus.

Emergency action in the event of fire Fire in a cargo space containing this cargo: Open hatches to provide maximum
ventilation. Ship's fixed gas fire extinguishing will be inadequate. Use copious quantities of water. Flooding of the cargo space may be considered but due consideration should be given to stability.

Fire in an adjacent cargo space: Open hatches to provide maximum ventilation. Heat
transferred from fire in an adjacent space can cause the material to decompose with consequent evolution of toxic fumes. Dividing bulkheads should be cooled.

Medical First Aid

Refer to the Medical First Aid Guide (MFAG).

Source: IMSBC Code, 2010; 68 Also, fire, first aid etc. emergency procedures are given in MSDS example (see Appendix 6) 4.2. Risk Assessment Government of Western Australia avoids getting into debates about how much material should be allowed through a particular port and discussions about what might happen if there was an explosion. However, focuses that by adopting these controls the likelihood of an explosion is reduced to zero, so the quantity is irrelevant. The focus of risk assessments for ammonium nitrate special berth declarations is to: identify all relevant hazards and risk factors associated with the handling of this material; and implement simple but effective controls to minimise or eliminate that hazard.

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Table 4.2.: Risk Assessment

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Table 4.2.: Risk Assessment (continued)

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Table 4.2.: Risk Assessment (concluded)

Source: Gov.of W. Aus., 2009; 5-13

4.3. Material Safety Data Sheet A manufacturer of dangerous goods must prepare a material safety data sheet (MSDS) for the dangerous goods before the dangerous goods are supplied to another person. (See Appendix 6; MSDS Example)

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4.4. Case Study at Aliaga Ege Gubre Port I have attended UN 2067 ammonium nitrate based fertilizer discharge operation in Aliaga Ege Gubre Port at 4th January 2012. Letter to permission is attached to Appendix 9. Ship transported approximately 5500 tons of UN 2067 from Nikolaev Ukraine to Nemrut Bay Turkey. Ship information is below: Name: SULTAN ATASOY Type: Bulk Carrier Flag: Turkish Year Built: 2010 LOA: 106.80 m Beam: 16.83 m Draft: 7.05 m Dwt: 6400

Figure 4.1.: M/V SULTAN ATASOY.

Source: Author, 04.01.2012.

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4.4.1.Purpose and Scope The aim of this study is observing the discharging operation and stating safety measures to be taken. Besides, within ammonium nitrate handling procedures prepared by European Fertilizer Manufacturer's Association, a port operation would be observed visiually and questionned to ship officers and analyzed. 4.4.2. Observations I think this ship a very good example for my study. 2010-year-built ship was in good condition. I wish to see a bad conditioned ship to observate deficiencies. Ship has loaded two longitudinal hatches with approximately 5500 tons of UN 2067 AN based fertilizer. There was no other cargo on board. Chief officer of the vessel was aware the dangers/hazards of the cargo according our conversation. Chief officer was complied with company's ISM procedures and cargo MSDS. (see Appendix 10) The crew on the vessel was aware that no welding, burning, cutting, or other operation involving the use of fire, open flame, spark or arc producing equipment should be carried out on deck. There was no bunkering operation on board. But the ship stayed in the berth two and a half days, I have attended only one day of operation. Ship's fire hoses were not ready for immediate use, and the two firepumps with one emergency firepump, sufficient water capacity was 80m/h each of pump. The "NO SMOKING" signs were displayed on board. Also a watchman was assigned on deck to prevent smoking on board. She had have approved certificate of A-60 bulkhead. There was no electrical equipment in cargo holds. Loading at Nikolaev Port, the temperature of the cargo was 9C and middle moisture of the cargo 0.29% according to cargo manifest which they gave me. Cargo residues were cleaned carefully, in the emptied hold.

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Figure 4.2.: Sultan Atasoy Hold No 1

Source: Author, 04.01.2012

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Figure 4.3.: Sultan Atasoy Hold No 2

Source: Author, 04.01.2012

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Figure 4.4.: UN 2067 Ammonium Nitrate Based Fertilizer Sample Sack

Source: Author, 04.01.2012 4.4.3. Checklist Proposal Checklists and instructions were prepared by EFMA, very useful, simple but effective questionnaire. The approach is to focus on specific hazards that obligate these measures. Conditions of Hatches Prior to Loading (see Appendix 11) Ship/Shore Safety Checklist (UN 2067) (see Appendix 12) Ship/Shore Safety Checklist (UN 2071) (see Appendix 13) Ship/Shore Safety Checklist (All Fertilizers) (see Appendix 14) Instruction to the Ships Crew Concerning Avoidance of Heat Sources When Loading/Unloading And Carrying Ammonium Nitrate Based Fertilizers (See Appendix 15) Instruction to the Ships Crew for the Handling of Emergencies Involving the Decomposition of Ammonium Nitrate Based Fertilizers (See Appendix 16)

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CONCLUSIONS

Accidents of ammonium nitrate rarely occur but when they occur, the impacts could be devastating like 1947 Texas City Disaster and 2001 Toulouse AN Plant Disaster. It is a question that need of using AN in agriculture and a blasting agent in mining industry. This subject is ascertainable. If the ship personnel misunderstand disregard the hazards of AN, there will be risks that costs life and damage to environment. I have wished to inspect the wreck of M/V Dogu Haslaman, which ship carrying AN from Ukraine to Israel, sunk near coast of eme on 30th December 2011, but I did not allowed to reach details. In sea transport of AN, there is a risk when the ships that bearing AN, passing the narrow seas of Turkey. I think, production and importing of AN with high than 26-28% N content would be banned in Turkey, because of the higher N content, the more explosiveness of AN. Leaning to organic fertilizers from inorganic and urea -has more N content than AN- usage of urea and organic fertilizers can be a good solution, composite fertilizers can be a solution that include e.g. N-P-K percentages of 15-15-15, 20-200. There is no regulation in Turkey for securing the AN that sold to farmers, for preventing AN usage in terrorism. Furthermore, a few incidents occured lately that terrorists have been caught with ammonium nitrate before as they planned to use to make a bomb.

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REFERANCES

Armistead, G. (1947). Report to John G. Simmonds and Company, Inc. on the Ship Explosions at Texas City, Texas, on April 16 and 17, 1947 and Their Results. Washington, D.C. Braun, O.K. (1953). Hystory of Both Rhine Villages Oppau and Edigheim. COAG (Council of Ausralian Governments). (2005) Chemicals and Plastics Regulation Australia. pp 267 COAG (Council of Australian Governments). (2008). Security Sensitive Ammonium Nitrate. pp 269-280 CSBP Limited, (2011) Material Safety Data Sheets. http://www.csbp.com.au/Media/MSDS/AN/MSDS_Ammoniun_Nitrate.aspx (12.11.2011) Dechy, N. & Bourdeaux T. & Ayrault N. & Kordek M.A. & Le Coze J.C. (2004). First Lessons of the Toulouse Ammonium Nitrate Disaster, 21st September 2001, AZF plant, France. Journal of Hazardous Materials. EFMA (European Fertlizer Manufacturers' Association) (2004). Guidance for Sea Transport of Ammonium Nitrate Based Fertilizers, Belgium. EFMA (European Fertlizer Manufacturers' Association). (2007). Guidance for the Storage Handling and Transportation of Solid Mineral Fertilizers, Belgium. EFMA (European Fertlizer Manufacturers' Association). (2012). Guidance for UN Classification of Ammonium Nitrate Based Substances, Belgium. EPA (Environmental Protection Agency). (1995). Report of the Investigation Committee, "The Terra Port Neal Explosion. December 13, 1994". FAO (Food and Agriculture Organization of United Nations). (2012). World fertilizer statistics from FAOSTATS website. http://faostat.fao.org/site/575/default.aspx#ancor (15.04.2012)

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Gerhartz, W. (1985). Ullmann's Encyclopedia of Industrial Chemistry 5th ed., Vol. 2, p 243-252. Government of South Australia. (2004). Regulatory Impact Statement in Relation to the Regulation and Control of Ammonium Nitrate. Government of Western Australia. (2008). Safe Storage Of Solid Ammonium Nitrate Code Of Practice. Government of Western Australia. (2009). DGS Guidance Note P01/09 Handling Ammonium Nitrate At Special Berth. Government of Western Australia. (2010). Storage And Handling Of Dangerous Goods Code of Practice, 2nd Edition. Hacaolu S. (2004). USA Today Associated Press. Newspaper Article, 14 April 2004. Hadden R. & Jervis F.X. & Rein G. (2007). Investigation of the Fertilizer Fire aboard the Ostedijk. HSE (Health and Security Executive). (2000). Code of Practice for Storage, Handling and Transportation of Solid Ammonium Nitrate Based Fertilisers, Peterborough 2000, UK. HSE (Health and Security Executive). (2001). Storing And Handling Ammonium Nitrate, Revised Edition. HSE (Health and Security Executive). (2004). Guidance Note CS18: Storage and Handling of Ammonium Nitrate. http://en.wikipedia.org/wiki/File:Oppau_Explosion_1921.JPG (15.04.2012) http://faostat.fao.org/site/575/default.aspx#ancor (15.04.2012) http://fotogaleri.hurriyet.com.tr/galeridetay.aspx?cid=30026 (15.04.2012) http://gazetearsivi.milliyet.com.tr/%C4%B0stanbul%20Sald%C4%B1r%C4%B1lar% C4%B1/ (15.04.2012)

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http://news.bbc.co.uk/2/hi/south_asia/5179014.stm (15.04.2012) http://news.bbc.co.uk/2/hi/uk_news/england/3584009.stm (15.04.2012) http://news.bbc.co.uk/2/hi/uk_news/england/manchester/3227876.stm (15.04.2012) http://texashistory.unt.edu/ark:/67531/metapth11803/?q=texas%201947 (15.04.2012) http://texashistory.unt.edu/ark:/67531/metapth11825/?q=texas%201947 (15.04.2012) http://upload.wikimedia.org/wikipedia/commons/thumb/c/cb/OklahomacitybombingDF-ST-98-01356.jpg/408px-Oklahomacitybombing-DF-ST-98-01356.jpg (15.04.2012) http://www.bbc.co.uk/news/world-europe-14260297 (15.04.2012) http://www.cedre.fr/en/spill/ocean_liberty/ocean_liberty.php (20.04.2012) http://www.denizhaber.com/index.php?sayfa=arama&aranan=Lady%20Juliet&basla =0&bitir=50 (10.04.2012) http://www.exponent.com/process_plant_explosion (15.04.2012) http://www.fbi.gov/about-us/history/famous-cases/oklahoma-city-bombing (15.04.2012) http://www.kansascity.com/2009/04/25/1162352/report-surfaces-in-1988explosion.html (20.04.2012) http://www.oda.state.ok.us/forms/cps/faar.pdf (15.04.2012) http://www.ohs.org/education/oregonhistory/historical_records/dspDocument.cfm?do c_ID=B5F03F96-E94E-A4A6-290AB607EF449F4D (20.02.2012) http://www.wrecksite.eu/wreck.aspx?160318 (19.02.2012)

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IFA (International Fertilizer Industy Association). (2012). World Fertilizer Trade Statistics. http://www.fertilizer.org/ifa/HomePage/STATISTICS/Production-and-trade (12.04.2012) IMO (International Maritime Organisation). (2010). The IMDG Code as adopted by the Maritime Safety Committee of the Organization by resolution MSC.122(75) IMO (International Maritime Organisation). (2010). International Maritime Solid Bulk Cargoes (IMSBC) Code as adopted by the Maritime Safety Committee of the Organization by resolution MSC.89/25/Add 1. Kiiski, H. (2000). The Self-Sustaining Decomposition of Ammonium Nitrate Containing Fertilisers, International Fertiliser Association Technical Conference, New Orleans. Kiiski, H. (2009). Properties of Ammonium Nitrate Based Fertilisers, (English) University of Helsinki, Finland. Kintz, G.M. & Jones, G.W. & Carpenter, C.B. (1948). Report of Investigations Explosions of Ammonium Nitrate Fertiliser on board the S.S. Grandcamp and S.S. Highflyer at Texas City, April 16-17, 1947. Marlair, G. & Kordek, M. A. & Michot, C. (2010). High Challange Warehousing: Ammonium Nitrate as a Typical Case Study. 16-19 February 2010 Orlando USA. Marlair, G. & Kordek, M. A. (2005). Safety And Security Issues Relating to Low Capacity Storage Of AN-Based Fertilizers. Journal of Hazardous Materials. Perbal, G. (1971). The Thermal Stability of Fertilisers Containing Ammonium Nitrate, Proceedings of the International Fertiliser Industry, vol. 124, York, UK. Shah, K.D. & Roberts, A.G. (1985). Properties of Ammonium Nitrate in Nitric Acid and Fertilizer Nitrates, Keleti, C. (ed.), Dekker Inc., New York. Shah, K.D. (2001). Safety of Ammonium Nitrate Fertilisers, Proceedings of the International Fertiliser Society, vol. 384, York, UK. Shah, K.D. (2003). Toxic Fumes Hazards from Fires Involving Ammonium Nitrates, Congress ANNA October 2003, Tunica, MS, USA.

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Stephens, H.W. (1997). The Texas City Disaster 1947. Austin: University of Texas Press. T.C. (Trkiye Cumhuriyeti) Tarm ve Ky leri Bakanl. (2002) Kimyevi Gbre Denetim Ynetmelii 25/4/2002 tarihli ve 24736 sayl Resm Gazete T.C. (Trkiye Cumhuriyeti) Tarm ve Ky leri Bakanl. (2004). Tarmda Kullanlan Kimyevi Gbrelere Dair Ynetmelikte Deiiklik Yaplmasna Dair Ynetmelik 18/3/2004 tarihli ve 25406 sayl Resm Gazete The Daily Oklahoman Newspaper. (1995) 20 April 1995. TK (Trkiye statistik Kurumu). (2011) Deniz Ticaret statistikleri. 2004-2010 http://www.denizcilik.gov.tr/dm/yayinlar/istatistik.pdf (10.11.2011) UN (United Nations). (2005). Recommendations on the Transport of Dangerous Goods. Model Regulations, Fourteenth edition. USA Today Newspaper. (2001) "Victims of the Oklahoma City bombing". Associated Press. 20 June 2001. Zorba, Y. (2009). Uluslararas Deniz Ticaretinde Tehlikeli Yklere ilikin Gvenlik Ynetimi: Uluslararas Denizde Tehlikeli Yk Tasmacl Standartlar (IMDG Code) ve Trkiye Uygulamalar (Trke) Dokuz Eyll niversitesi Sosyal Bilimler Enstits.

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APPENDICES

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APPENDIX 1 UN MANUAL OF TESTS AND CRITERIA Purpose of the test is the United Nations scheme for the classification of explosives. It includes a description of the procedures and test criteria considered to be the most useful for providing competent authorities with the necessary information to arrive at a proper classification of explosive substances and articles for transport. The test procedures allow assessment of the hazard of explosive substances and articles so that an appropriate classification for transport can be made by the competent authority. 1. Acceptance Procedure The acceptance procedure is used to determine whether or not a product as offered for transport is a candidate for Class 1. This is decided by determining whether a substance provisionally accepted for Class 1 is either too insensitive for inclusion in Class 1 or too dangerous for transport; or whether article(s) or packaged article(s) are too dangerous for transport. 2. Test types The question "Is it an explosive substance?" is answered on the basis of national and international definitions of an explosive substance and the results of three types of Series 1 tests to assess possible explosive effects. The three types of test used are: Type 1(a): a shock test with defined booster and confinement to determine the ability of the substance to propagate a detonation; Type 1(b): a test to determine the effect of heating under confinement; and Type 1(c): a test to determine the effect of ignition under confinement.

Series 2 tests are used to answer the question "Is the substance too insensitive for acceptance into Class 1?". In general the basic apparatus used is the same as that for Test Series 1.

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Type 2 (a): a shock test with defined initiation system and confinement to determine sensitivity to shock;

Type 2 (b): confinement; and

a test to determine the effect of heating under

Type 2 (c): a test to determine the effect of ignition under confinement.

2.1 Test Series 1 and 2 2.1.1 Test Methods Type 1(a): UN gap test Type 1(b): Koenen test Type 1(c): Time/pressure test

2.1.1.1 UN Gap Test This test is used to measure the ability of a substance, under confinement in a steel tube, to propagate a detonation by subjecting it to the detonation from a booster charge. 2.1.1.1.1. Procedure The sample is loaded to the top of the steel tube. Solid samples are loaded to the density attained by tapping the tube until further settling becomes imperceptible. The sample mass is determined and, if solid, the apparent density calculated using the measured internal volume of the tube. The density should be as close as possible to the shipping density. The tube is placed in a vertical position and the booster charge is placed in direct contact with the sheet which seals the bottom of the tube. The detonator is fixed in place against the booster charge and initiated. Two tests should be performed unless detonation of the substance is observed. 2.1.1.1.2. Test criteria and method of assessing results The test results are assessed on the basis of the type of fragmentation of the tube and on whether a hole is punched through the witness plate. The test giving the most severe assessment should be used for classification. The test result is considered "+" and the substance to propagate detonation if:

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The tube is fragmented completely; or A hole is punched through the witness plate.

Any other result is considered "" and the substance not to propagate detonation. 2.1.1.1.3. Test Apparatus The apparatus for solids is shown in Figure 1. The test sample is contained in a cold-drawn, seamless, carbon steel tube with an external diameter of 48 2 mm, a wall thickness of 4.0 0.1 mm and a length of 400 5 mm. 2.1.1.1.4 Examples of Results

(Source: United Nations)

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Figure 1: UN Gap Test Apparatus

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2.1.1.2. Koenen Test This test is used to determine the sensitiveness of solid and liquid substances to the effect of intense heat under high confinement. 2.1.1.2.1 Procedure Normally substances are tested as received, although in certain cases it may be necessary to test the substance after crushing it. For solids, the mass of material to be used in each test is determined using a two-stage dry run procedure. A tared tube is filled with 9 cm3 of substance and the substance tamped with 80 N force applied to the total cross-section of the tube. If the material is compressible then more is added and tamped until the tube is filled to 55 mm from the top. The total mass used to fill the tube to the 55 mm level is determined and two further increments, each tamped with 80 N force, are added. Material is then either added, with tamping, or taken out as required to leave the tube filled to a level 15 mm from the top. A second dry run is performed, starting with a tamped increment a third of the total mass found in the first dry run. Two more of these increments are added with 80 N tamping and the level of the substance in the tube adjusted to 15 mm from the top by addition or subtraction of material as required. With orifice plates from 1.0 mm to 8.0 mm diameter, nuts with an orifice of 10.0 mm diameter should be used; if the diameter of the orifice is above 8.0 mm, that of the nut should be 20.0 mm. Each tube is used for one trial only. The orifice plates, threaded collars and nuts may be used again provided they are undamaged. The tube is placed in a rigidly mounted vice and the nut tightened with a spanner. The tube is then suspended between the two rods in the protective box. The test area is vacated, the gas supply turned on and the burners lit. The time to reaction and duration of reaction can provide additional information useful in interpreting the results. If rupture of the tube does not occur, heating is to be continued for at least five minutes before the trial is finished. After each trial the fragments of the tube, if any, should be collected and weighed.

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2.1.1.2.2. Test criteria and method of assessing results The result is considered "+" and the substance to show some effect on heating under confinement if the limiting diameter is 1.0 mm or more. The result is considered "" and the substance to show no effect on heating under confinement if the limiting diameter is less than 1.0 mm. The following effects are differentiated: "O": Tube unchanged; "A": Bottom of tube bulged out; "B": Bottom and wall of the tube bulged out; "C": Bottom of tube split; "D": Wall of tube split; "E": Tube split into two fragments; "F": Tube fragmented into three or more mainly large pieces which in some cases may be connected with each other by a narrow strip; "G": Tube fragmented into many mainly small pieces, closing device undamaged; and "H": Tube fragmented into many very small pieces, closing device

bulged out or fragmented. Examples for the effect types "D", "E" and "F" are shown in Figure 4. If a trial results in any of the effects "O" to "E", the result is regarded as "no explosion". If a trial gives the effect "F", "G" or "H", the result is evaluated as "explosion".

2.1.1.2.3. Test Apparatus The apparatus consists of a non-reusable steel tube, with its re-usable closing device, installed in a heating and protective device. The tube is deep drawn from sheet steel of suitable quality. The mass of the tube is 25.5 1.0 g. The open end of the tube is flanged. The closing plate with an orifice, through which the gases from the decomposition of the test substance escape, is made from heat-resisting chrome steel. (Figure 2)

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Heating is provided by propane, from an industrial cylinder fitted with a pressure regulator, via a flow meter and distributed by a manifold to the four burners. (Figure 3) 2.1.1.2.4. Examples of Results

(Source: United Nations)

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Figure 2: Koenen Test Tube Assembly

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Figure 3: Koenen Test Heating and Protective Device

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Figure 4: Examples for the effect types "D", "E" and "F"

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2.1.1.3. Time/Pressure Test This test is used to determine the effects of igniting the substance under confinement in order to determine if ignition leads to a deflagration with explosive violence at pressures which can be attained with substances in normal commercial packages. 2.1.1.3.1 Procedure The apparatus, assembled complete with pressure transducer but without the aluminium bursting disk in position, is supported firing plug end down. 5.0 g of the substance is introduced into the apparatus so as to be in contact with the ignition system. Normally no tamping is carried out when filling the apparatus unless it is necessary to use light tamping in order to get the 5.0 g charge into the vessel. If, even with light tamping, it is impossible to get all the 5.0 g of sample in, then the charge is fired after filling the vessel to capacity. The test is carried out three times. The time taken for the pressure to rise from 690 kPa to 2070 kPa above atmospheric is noted. The shortest time interval should be used for classification. 2.1.1.3.2. Test criteria and method of assessing results The test results are interpreted in terms of whether a gauge pressure of 2070 kPa is reached and, if so, the time taken for the pressure to rise from 690 kPa to 2070 kPa gauge. The result is considered "+" and the substance to show the ability to deflagrate if the maximum pressure reached is greater than or equal to 2070 kPa. The result is considered "" and the substance to show no likelihood of deflagration if the maximum pressure reached in any one test is less than 2070 kPa gauge. Failure to ignite does not necessarily indicate that the substance has no explosive properties. 2.1.1.3.3. Test Apparatus The time/pressure apparatus consists of a cylindrical steel pressure vessel 89 mm in length and 60 mm in external diameter. (Figure 5)

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2.1.1.3.4. Example of Results

Source: (United Nations)

77

Figure 5: Time/Pressure Test Apparatus

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APPENDIX 2 CLASSIFICATION PROCEDURES, TEST METHODS AND CRITERIA RELATING TO CLASS 9 1. Ammonium Nitrate Fertilizers Capable of Self-Sustaining Decomposition This section contains classification procedures, test methods and criteria relating to substances and articles of Class 9. New products offered for transport should be subjected to the classification procedure if the composition is covered by the definition for UN 2071. The classification procedure should be undertaken before a new product is offered for transport. The test method should be performed to de termine if a decomposition initiated in a localised area will spread throughout the mass. The recommended test method is given in below. Whether the substance is an ammonium nitrate fertilizer of Class 9, or not, is decided on the basis of the test result. Packing group III is assigned to all Class 9 ammonium nitrate fertilisers. Ammonium nitrate fertilizers with the composition given for UN 2071 may be regarded as not subject to the Model Regulations if shown not to be liable to selfsustaining decomposition and provided that they do not contain an excess of nitrate greater than 10% by mass (calculated as potassium nitrate). 2. Trough Test For Determination of the Self-Sustaining Exothermic Decomposition of Fertilizers Containing Nitrates A fertilizer capable of self-sustaining decomposition is defined as one in which decomposition initiated in a localized area will spread throughout the mass. The tendency of a fertilizer, to be offered for transport, to undergo this type of decomposition can be determined by means of the Trough test. In this test localized decomposition is initiated in a bed of the fertilizer contained in a horizontally mounted trough. The amount of propagation, after removal of the initiating heat source, of decomposition through the mass is measured.

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2.1. Test Apparatus The apparatus (Figure 1) consists of a trough of internal dimensions 150 150 500 mm, open at the top. The trough is constructed of square meshed gauze (preferably stainless steel) with a mesh width of about 1.5 mm and wire thickness of 1 mm, supported on a frame made from, for example, 15 mm wide, 2 mm thick steel bars. The gauze at each end of the trough may be replaced by 1.5 mm thick, 150 150 mm stainless steel plates. The trough should be rested on a suitable support. Fertilizers with a particle size distribution such that a significant amount falls through the mesh of the trough should be tested in a trough of smaller mesh gauze, or alternatively in a trough lined with gauze of a smaller mesh. During initiation, sufficient heat should be provided and maintained to establish a uniform decomposition front. Two alternative heating methods are recommended. They are: Electrical heating (Figure 2). An electrical heating element (capacity 250 watts) enclosed in a stainless steel box, placed inside and at one end of the trough. The dimensions of the stainless steel box are 145 145 10 mm, and the wall thickness about 3 mm. The side of the box which is not in contact with the fertilizer should be protected with a heat shield (insulation plate 5 mm thick). The heating side of the box may be protected with aluminium foil or a stainless steel plate. Gas burners. A steel plate (thickness 1-3 mm) is placed inside one end of the trough and in contact with the wire gauze. The plate is heated by means of two burners which are fixed to the trough support and are capable of maintaining the plate at temperatures between 400-600 C, i.e. dull red heat. 2.2. Procedure The apparatus should be set up under a fume hood to remove toxic decomposition gases or in an open area where the fumes can be readily dispersed. Although there is no explosion risk when performing the test, it is advisable to have a protective shield, e.g. of suitable transparent plastic, between the observer and the apparatus. The trough is filled with the fertilizer in the form to be offered for transport and decomposition is initiated at one end, either electrically or by means of gas burners

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as described above. Heating should be continued until decomposition of the fertilizer is well established and propagation of the front (over approximately 3-5 cm) is observed. In the case of products of high thermal stability, it may be necessary to continue heating for two hours. If fertilizers show a tendency to melt, the heating should be done with care, i.e. using a small flame. About 20 minutes after the heating has been discontinued, the position of the decomposition front is noted. The position of the reaction front can be determined by differences in colour. 2.3. Test Criteria and Method of Assessing Results If propagation of the decomposition continues throughout the substance, the fertilizer is considered capable of showing selfsustaining decomposition. If propagation does not continue throughout the substance, the fertilizer is considered to be free from the hazard of self-sustaining decomposition.

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Figure 1: Gauze trough with support burners

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Figure 2: Electrical heating device

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APPENDIX 3 A-60 CLASS BULKHEAD CERTIFICATE

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APPENDIX 4 RESISTANCE TO DETONATION TEST 1. Principle The test sample is confined in a steel tube and subjected to detonation shock from an explosive booster charge. Propagation of the detonation is determined from the degree of compression of lead cylinders on which the tube rests horizotally during the test. 2. Sample Preparation The test must be carried out on a representative sample of material. Before being tested for resistance to detonation, the whole mass of the sample is to be thermally cycled five times between 25C and 50C in sealed tubes. The sample shall be maintained at the extreme temperatures, measured at the centre of the sample, for at least 1 hour during each thermal cycle and at 20C after complete cycling until tested. 3. Materials Seamless steel tube to ISO 65-1981-Heavy or equivalent Tube lenght: 1000 mm Nominal external diameter: 114 mm Nominal wall thickness: 5 to 6.5 mm

Bottom plate (160 x 160 mm) of good weldable quality steel, thickness 5 to 6 mm to be butt-welded to one end of the tube around the entire circumference. Initiation system and booster Electrical blasting cap or detonating cord with non-metallic sleeve Compressed pellet of secondary explosive with a central recess to take the detonator. 500 g plastic explosive containing 83 to 86% penthrite, formed into a cylinder in a cardboard or plastic tube. Detonation velocity 7300-7700 m/s Six witness cylinders of refined, cast lead for detecting detonation.

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4. Procedure Test temperature is 15 to 20C. Figures 1 and 2 show the test arrangement. Fill the tube about one-third of its height with the test sample and drop it 10 cm vertically five times on the floor. Improve the compression by striking the side wall with a hammer between drops. A further addition shall be made such that, after compaction or by raising and dropping the tube 20 times and a total of 20 intermittent hammer blows, the charge fills the tube to a distance of 70 mm from its orifice. Insert the plastic explosive into the tube and press it down with a wooden die. Place the compressed pellet centrally in the recess within the plastic explosive. Close it with a wooden disc so that it remais in contact with the test sample. Lay the test tube horizontally on the 6 lead cylinders placed at 150 mm intervals, with the centre of the last cylinder 75 mm from the bottom plate, on a firm, level, solid surface that is resistant to deformation or displacement. Insert the electrical blasting cap or the detonating cord. Ensure that all necessary safety precautions are taken, connect and detonate the explosive. Record, for each of the lead cylinders, the degree of compression expressed as a percentage of the original height of 100 mm. For oblique compression, the deformation is taken as the average of the maximum and minimum deformation. 5. Results The test is to be carried out twice. If in each test one or more of the supporting lead cylinders are crushed by less than 5%, the sample is deemed to satisfy the resistance to detonation requirements.

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Figure 1: Test Arrangement

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Figure 2: Test Arrangement

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APPENDIX 5 RESISTANCE TO DETONATION CERTIFICATE

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APPENDIX 6 MATERIAL SAFETY DATA SHEET EXAMPLE

91

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APPENDIX 7 DECISION No 1348/2008/EC OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL 16 December 2008 Ammonium nitrate, which is widely used throughout the Community as a fertiliser, can act as an oxidising agent. In particular, it has the ability to explode when mixed with certain other substances. Ammonium nitrate fertilisers should therefore meet certain requirements when placed on the market to ensure that they are safe against accidental detonation. Regulation (EC) No 2003/2003 of the European Parliament and of the Council of 13 October 2003 relating to fertilisers provides for harmonised requirements, including safety requirements, for ammonium nitrate fertilisers. Fertilisers complying with those requirements may be labelled EC fertiliser and may circulate freely within the internal market. Annex III to Regulation (EC) No 2003/2003 specifies a test of resistance to detonation for ammonium nitrate fertilisers containing more than 28 % by mass of nitrogen in relation to ammonium nitrate. It also specifies a number of physical characteristics and limits on the chemical impurity content for such fertilisers in order to minimise the risk of detonation. Ammonium nitrate fertilisers that comply with those requirements, or that contain less than 28 % by mass of nitrogen, are accepted by all Member States as being safe for use in agriculture. Ammonium Nitrate; Shall not be placed on the market for the first time after 27 June 2010 as a substance, or in preparations that contain more than 28 % by mass of nitrogen in relation to ammonium nitrate, for use as a solid fertiliser, straight or compound, unless the fertiliser complies with the technical provisions for ammonium nitrate fertilisers of high nitrogen content set out in Annex III to Regulation (EC) No 2003/2003 of the European Parliament and of the Council of 13 October 2003 relating to fertilisers.

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Shall not be placed on the market after 27 June 2010 as a substance, or in preparations that contain 16 % or more by mass of nitrogen in relation to ammonium nitrate except for supply to: 1. downstream users and distributors, including natural or legal persons licensed or authorised in accordance with Council Directive 93/15/EEC of 5 April 1993 on the harmonisation of the provisions relating to the placing on the market and supervision of explosives for civil use; 2. farmers for use in agricultural activities, either full time or part time and notnecessarily related to the size of the land area. For the purposes of this subparagraph: farmer shall mean a natural or legal person, or a group of natural or legal persons, whatever legal status is granted to the group and its members by national law, whose holding is situated within Community territory, as referred to in Article 299 of the Treaty, and who exercises an agricultural activity, agricultural activity shall mean the production, rearing or growing of agricultural products including harvesting, milking, breeding animals and keeping animals for farming purposes, or maintaining the land in good agricultural and environmental condition as established under Article 5 of Council Regulation (EC) No 1782/2003 of 29 September 2003 establishing common rules for direct support schemes under the common agricultural policy and establishing certain support schemes for farmers; 3. natural or legal persons engaged in professional activities such as horticulture, plant growing in greenhouses, maintenance of parks, gardens or sport pitches, forestry or other similar activities. However, for the restrictions in paragraph 2, Member States may until 1 July 2014, for socioeconomic reasons, apply a limit of up to 20 % by mass of nitrogen in relation to ammonium nitrate for substances and preparations placed on the market within their territories. They shall inform the Commission and other Member States thereof.

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APPENDIX 8

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APPENDIX 9 ISM PROCEDURES OF M/V SULTAN ATASOY

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APPENDIX 10 LETTER TO PERMISSION

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APPENDIX 11 Ykleme ncesi Ambarlarn Durumunu Kontrol Listesi (Amonyum nitrat ve amonyum nitrat ierikli gbreler iin rnektir)
Gemi Ad naa Yl Gross Tonaj nceki Yk Ambar zellikleri Ambar Kapaklar Ambar Taban Tek Gverteli elik Katlanan elik Yk Tipi UN No/IMDG Class Ykleme Liman Tahliye Liman Gladoral elik Ponton Dier Kutu eklinde Dier:

Aadaki maddeler kontrol edilmitir A B C D E F G H I J K L M N O P Ambar lastiklerinin salamlnn kontrol Ambar kapak yan bask siillerinin durumu Ambar drenaj delik/boru/kanallarnn durumu Kastanyola ve ko boynuzlarnn durumu Ambar kapaklarnn durumu Ambar kapaklarndaki trimming deliklerinin durumu Ambar mezarnalarnn durumu Ambar iinin genel durumu Ambar iindeki hareket edebilecek perdelerin kontrol Ambar havalandrmalar kapal m? Ambara giri k yaplan merdivenlerin durumu Ambar sintineleri bo mu? Is yayabilecek maddeler uzaklatrld m? Liman iilerinin kullanabilecei platform gibi yerler var m? Ambar ii aydnlatma veya elektrik devresi varsa kapatld m? Ultrasound Leak Detector testi (ULD)

sim ve Soyisim Enspektr Kaptan Yklemeye uygun grlen ambarlar HAZIRLAYAN: RECEP ORUOLU

mza

Tarih

Saat

ONAYLAYAN: . GR. BARI KULEYN

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APPENDIX 13 Gemi - Sahil Emniyet Kontrol Listesi (Amonyum nitrat ierikli UN 2071 gbreler iin)
Gemi Ad Liman Var Tarihi Ykleme/Tahliye edilecek yk Rhtm Var Zaman Var draft Var air draft Yk miktar Kalk draft Kalk air draft

Talimatlar Liman operasyonlarnn emniyetli bir ekilde yaplabilmesi iin aada verilen tm sorular, gemi ve liman temsilcileri tarafndan kesin ve olumlu ise kutulara iaretlenmelidir. Eer uygun bir cevap verilemiyor ise bir neden belirtilmeli, gemi ve liman arasnda uygun nlemler iin karar verilmeli ve uygulanmaldr. Eer sorularda uygunsuzluk varsa aklamalar stununa sebepler yazlmaldr.

No 1 2 3

Kontrol Edilecekler Yanabilecek veya organik bileikli maddeler ile birlikte gbre yk beraber tanyorsa, sz konusu ykler ayr blmlerde -ambarlardatanacak ekilde yklendi mi? Eer iinde UN 2071 gbre olan ambara baka bir yk alnacak ise bu iki yk birbiriyle kimyasal deiim geirmeyecek ekilde uyumlu mu? Gemi personeli, amonyum nitrat ierikli gbre gemideyken; her trl ate ve kvlcm karabilecek kesim, kaynak veya dier ilerle uralmayacann farknda m? Ambarlar tam olarak kapatlmadan veya yk operasyonu devam ederken herhangi bir yakt ikmali veya transferi ii yaplmadndan emin oldunuz mu? Yangn pompalarnz dakikada tercihen en az 1 m veya daha fazla su basabilecek kapasitede mi? Yangn hortumlarnz acil bir durumda kullanlmak zere serilip hazrland m? Gemi personeli, amonyum nitrat ierikli gbre gemideyken gverte zerinde ve ambar iinde sigara iilmeyeceinin bilincinde mi? "Sigara ilmez" tabelalar, amonyum nitrat ierikli gbre gemideyken srekli asl ve grnr durumda m? Ykleme / Tahliye operasyonunda yangn vardiyas tutuluyor mu? Ambarlarda duman dedektr yok ise, en az her 4 saatte bir ambarlarn iinde bulunan ykn kontrol yaplyor mu? (rnek alma kanalndan koklama ile) Yk bulunan ambar ile makine dairesi ayrm yangn nleyici uvallar ile veya yeterli otorite tarafndan edeer grlen ayn ii yapacak madde ile korunuyor mu? Gemide amonyum nitrat ierikli gbreleri tayabileceini gsteren klas onayl sertifikas bulunuyor mu? Yklenecek ambarlar, tutuabilecek herhangi bir maddeden arndrld m? Ambarlara teet bulunan yakt tanklarndaki fuel oil 50C yi gemeyecek ekilde tutuluyor mu? Yklemede/Tahliyede/Sefer boyunca, ambarlardaki elektrikli lambalar, kablolar ve elektrik sigortalar almayacak ekilde yerlerinden alnd m? Ambar iinde veya yzeylerinde s yayan devreler bulunuyorsa bunlar kapal tutuluyor mu? Ambarlarda saatte 6 kez ierideki havay deitirebilme kapasitesi olan havalandrma fanlar var m? Gemi sim ve nvan mza Tarih - Saat

Gemi

Terminal

Aklamalar

4 5 6 7 8 9 10

11 12 13 14 15

16 17

Liman sim ve nvan mza Tarih - Saat

HAZIRLAYAN: RECEP ORUOLU

ONAYLAYAN: . GR. BARI KULEYN

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APPENDIX 14 Gemi - Sahil Emniyet Kontrol Listesi (Tm gbre eitleri iin)
Gemi Ad Liman Var Tarihi Ykleme/Tahliye edilecek yk Rhtm Var Zaman Var draft Var air draft Yk miktar Kalk draft Kalk air draft

Talimatlar Liman operasyonlarnn emniyetli bir ekilde yaplabilmesi iin aada verilen tm sorular, gemi ve liman temsilcileri tarafndan kesin ve olumlu ise kutulara iaretlenmelidir. Eer uygun bir cevap verilemiyor ise bir neden belirtilmeli, gemi ve liman arasnda uygun nlemler iin karar verilmeli ve uygulanmaldr. Eer sorularda uygunsuzluk varsa aklamalar stununa sebepler yazlmaldr.

No 1 2 3 4 5 6 7 8 9 10 11

Kontrol Edilecekler Ykleme veya tahliye operasyonu ncesi rhtmdaki su derinlii ile air draft emniyetli seviyelerde mi? (air draft kpr geii, kreyn alma ykseklii vs var ise) Yerel aknt, gelgit, hava etkilerine geminin palamarlama ekipmanlar yeterli mi? Acil bir durumda gemi hemen liman dna kabilecek durumda m? Rhtm ile gemi arasndaki giri k emniyetli mi? Liman-gemi haberlemesi iin uygun grlen; Metod: Kanal/Tel No: Dil:

Gemi

Terminal

Aklamalar

Acil durumlar iin gemideki ve limandaki personel yeterli mi? Amonyum nitrat gemiden tahliye edilirken veya gemiye yklenirken, yakt/ya alm operasyonu yaplacak m? Amonyum nitrat gemiden tahliye edilirken veya gemiye yklenirken, gemi gvertesine veya rhtma yaplmas planlanan bir tamir ii/scak i var m? Yk operasyonlar srasnda gelebilecek hasarlarn kayd ve raporlanmas prosedr konusunda anlald m? Liman ve rhtmn emniyet, evre koruma ve dier ynetmelikleri kopyalar ile acil durum servisleri bilgileri gemiye liman tarafndan verildi mi? Ykn zellikleri, SOLAS Blm 6 gereklilikleri altnda tatan tarafndan gemi kaptanna saland m? Ambar iinin ve girilmesi gerekebilecek kapal mahallerin atmosferi emniyetli mi? Fmigasyon yaplan kargolarda girilecek mahalin atmosferinin llmesi gereklilii gemi - liman arasnda kararlatrld m? Ykleme/tahliye yapacak olan kreynlerin yk elleleme kapasiteleri istenenleri karlyor mu? Kreyn No: Hz: ton/saat Kreyn No: Hz: ton/saat Ykleme/tahliye plannn ve balast operasyonlarnn tm admlar hesaplanm m? Ykleme/tahliye plannda allacak ambarlarn sras ve miktar hesaplanp verilmi mi? Liman verilen plan uyguluyor mu? Trimming operasyonu olup olmayaca, olacaksa yntemi tartld m? Balast alma/basma plannda bir aksaklk olursa ykleme/tahliye operasyonunun kesintiye urayaca gemi ve liman tarafndan kabul ediliyor mu? Tahliye operasyonunda ykn kalntlarnn nasl alnaca konusundaki prosedr gemiye anlatlp, kabul grd m? Yklenen geminin kalk trimini ayarlamada nasl bir prosedr izleneceine karar verildi mi? Gemi, liman ykleme/tahliye operasyonundan ne kadar sonra denize kmaya hazr olaca konusunda bilgilendirdi mi? Gemi seferi boyunca tayaca gbre ykn korumak iin alaca nlemler hakknda bilgilendirildi mi? Gemi yklemeden nce aadaki evraklar ald m? - MSDS - Amonyum nitrat ykleme/tama/tahliyesi srasnda herhangi bir s kaynan uzak tutma hakknda gemi personelinin uyaca talimat - Amonyum nitratn kimyevi bozunuma uramas durumunda yaplcaklar hakknda gemi personelinin uyaca talimat ONAYLAYAN: . GR. BARI KULEYN

12 13

14 15 16 17

18 19 20 21 22

HAZIRLAYAN: RECEP ORUOLU

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AMONYUM NTRAT YKLEMESNDE/TAHLYESNDE VE SEFERDE KEN PERSONELN ISI YAYACAK KAYNAKLARI KULLANMAKTAN KAINMALARI UYARISI

Klasna baklmakszn, tm amonyum nitrat gbrelerinde tm s yayan kaynaklar ykten uzak tutulmaldr. Potansiyel s kaynaklar unlardr: ampuller, stc sistemler, buhar (stim) borular, elektrikli kaynak ve kesim makineleri, elektrik kablolar, tm plak ate kaynaklar. Dolaysyla: Sefer boyunca ambarlarn iindeki tm klar ve s yayacak kaynaklar kapatn. Ambar iindeki tm elektrik sigortalarn skn ve ykn tahliyesine kadar takmayn. Scak i kategorisine giren herhangi kesim, kaynak vb. veya kvlcm kartabilecek kesim, raspa vb. ilerin gvertede yaplmasna izin vermeyin. "Sigara ilmez" levhalarn asl tutun.

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AMONYUM NTRATIN KMYASAL BOZUNMAYA URAMASI DURUMUNDA ACL OLARAK GEM PERSONELNN YAPMASI GEREKENLER

Gemi limanda ise, yerel acil yardm servisleriyle irtibata gein. Gemi seyirde ise, gemi acentesine, irketinize veya yk sahibiyle irtibata gein.

MSDS te bulunan talimatlar uygulayn. Yangn durumunda, eer mmknse s kaynan ortadan kaldrmaya aln. Yangn ve kimyasal bozunmada su ile sndrme almas yapn.

Sadece kimyasal bozunma var ise, ykn kimyasal deiime uram blmn salam olan blmnden mmknse ayrn ve su ile slanmasn salayn. (tatl veya tuzlu su)

Yk zarar grmemi ksmdan ayrmanz mmkn deilse, ambar iindeki ykn tamamn su ile slatn. Suyun, ykn iine kadar ilemesi iin tazyikli su kullann.

Yangna veya kimyasal bozunmaya kar kpk, CO2, kum veya ykn kalan ksmn kesinlikle kullanmayn.

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