Analysing Classification of Ammonium Nitrate Cargoes and Safety Issues for Ammonium Nitrate...

i

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 Oruçoğlu

Advisor

Lecturer Barış Kuleyin

2012

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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: Oruçoğlu Name: Recep

Turkish Name of The Project: Amonyum nitrat yükünün sınıflandırılması analizi ve gemi-

sahil operasyonlarında alınması 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 Name: Barış Surname: Kuleyin

English Key Words: Turkish Key Words:

1- IMDG Code 1- IMDG Kod

2- Hazardous Goods 2- Tehlikeli Yükler

3- Ammonium Nitrate 3- Amonyum Nitrat

4- Ammonium Nitrate Based Fertilizers 4- Amonyum Nitrat İçerikli Gübreler

5- Safety Precautions 5- Emniyet Önlemleri

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. Barış 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 Oruçoğlu

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TURKISH SUMMARY

Bu tez projesinin amaçları, gemi-sahil operasyonlarında amonyum nitrat (AN)

elleçlenmesinde alınması gereken emniyet tedbirlerini arttırmak, bu yükün deniz

yoluyla taşınırken alınması gereken koşulları incelemek, hangi koşullar altında bu

yükün tehlikeli olduğunu anlamak ve acil durumlarda nelerin yapılıp yapılmayacağını

açıklamaktır.

Amonyum nitratın tehlikelerini ve emniyet tedbirlerini açıklarken IMO kitapları

ile birlikte düzenleyici kanunları kullandım. Amonyum nitrata olan bakışı etkileyen ve

ilgili kuruluşların sınıralamalar getirmesine yol açan, geçmişte yaşanmış kazaları ve

terörizm olaylarını inceledim. Bununla birlikte, saha çalışması olarak Ocak 2012'de

Aliağa Ege Gübre Limanı'nda gerçekleşen bir amonyum nitrat içerikli gübre

tahliyesine nezaret ettim; bu çalışmayı gözlem yaparak ve Avrupa Gübre Üreticileri

Birliği'nin (EFMA) hazırladığı kontrol listesi şablonu ile kıyaslayarak yaptım.

Amacım, amonyum nitrat yükü elleçlenirken alınacak emniyet tedbirlerinin

artırılmasını ve deniz yoluyla taşınırken yükün tehlikelerine dikkat çekmeyi

sağlamaktır. Bu bağlamda, emniyet kontrol listeleri, depolama kuralları ve satışta

yapılan sınırlamalar hakkında önerilerde 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 i

TURKISH SUMMARY ii

ABSTRACT iii

CONTENTS iv

LIST OF ABBREVIATIONS x

LIST OF TABLES xi

LIST OF FIGURES xii

INTRODUCTION xiii

CHAPTER ONE

THE MARKET OF AMMONIUM NITRATE AND OTHER FERTILIZERS

1.1. World Fertilizer Statistics 2

1.1.1. World Fertilizer Production/Consumption Values (2000-2010) 2

1.1.2. World Fertilizer Export/Import Values (2000 - 2010) 3

1.2. World Ammonium Nitrate Statistics 4

1.2.1. Ammonium Nitrate Exports by Regions 4

1.2.2. Ammonium Nitrate Imports by Regions 6

1.3. Domestic Fertilizer Statistics 8

1.3.1. Export Statistics in Turkey 9

1.3.2. Import Statistics in Turkey 9

1.3.3. Ammonium Nitrate Based Fertilizer Statistics 2004 - 2010 10

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CHAPTER TWO

ANALYSIS AND CLASSIFICATION OF AMMONIUM NITRATE AND AMMONIUM NITRATE BASED FERTILIZERS

2.1. Classification of Ammonium Nitrate 13

2.1.1. Ammonium Nitrate UN 0222 - Class 1.1 13


2.1.3. Ammonium Nitrate Based Fertilizer UN 2067 - Class 5.1 13

2.1.4. Ammonium Nitrate Based Fertilizer UN 2071 - Class 9 14

2.1.5. Ammonium Nitrate Based Fertilizer (Non-Hazardous) 14

2.2. Logic Diagram 16

2.3. Properties of Ammonium Nitrate 20

2.4. General Hazards of Ammonium Nitrate 21

2.4.1. Fire 21

2.4.2. Explosion 21

2.4.3. Decomposition 22

2.5. Class Based Hazards of Ammonium Nitrate 23





2.6. Stowage and Segregation Requirements of Ammonium Nitrate 24




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2.7. Weather Precautions of Ammonium Nitrate 26

2.8. Loading 26





CHAPTER THREE

AMMONIUM NITRATE ACCIDENTS, TERROR INCIDENTS AND EFFECTS

3.1. Accidents 30

3.1.1. 1921 Oppau - Germany 30

3.1.2. 1942 Tessenderloo - Belgium 31

3.1.3. 1947 Texas City - USA 31

3.1.4. 1947 Brest - France 33

3.1.5. 1953 SS Tirrenia Wreck 33

3.1.6. 1959 Roseburg, Oregon - USA 34

3.1.7. 1988 Kansas City, Missouri - USA 34

3.1.8. 1994 Port Neal, Iowa - USA 34

3.1.9. 2001 Toulouse - France 35

3.1.10. 2004 Barracas - Spain 36

3.1.11. 2004 Mihailesti - Romania 36

vii

3.2. Near Misses 37

3.2.1. 2007 M/V Ostedijk - Spain 37

3.2.2. 2009 M/V Lady Juliet - Dardanelles - Turkey 38

3.3. Terror Incidents 40

3.3.1. 1995 Oklahoma City - USA 40

3.3.2. 2002 Bali - Indonesia 42

3.3.3. 2003 Istanbul - Turkey 42

3.3.4. 2006 Mumbai - India 44

3.3.5. Oslo - Norway 44

3.4. Effects Around World 44

3.4.1. European Union and Turkey 45

3.4.2. Australia 46

3.4.3. United Kingdom 46

3.4.4. United States of America, Oklahoma State 47

CHAPTER FOUR

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

4.1. Safety Precautions of AN 48

4.1.1. Ammonium Nitrate UN 1942 - Class 5.1 (IMSBC Code) 48

4.1.2. Ammonium Nitrate UN 2067 - Class 5.1 (IMSBC Code) 49

4.1.3. Ammonium Nitrate UN 2071 - Class 9 (IMSBC Code) 49

4.1.4. Emergency Procedures (IMSBC Code) 49

viii

4.2. Risk Assessment 50

4.3. Material Safety Data Sheet 53

4.4. Case Study at Aliaga Ege Gubre Port 54

4.4.1.Purpose and Scope 55

4.4.2. Observations 55

4.4.3. Checklist Proposal 58

CONCLUSIONS 59

REFERANCES 60

APPENDICES 65

APPENDIX 1: UN MANUAL OF TESTS AND CRITERIA 66

APPENDIX 2: CLASSIFICATION PROCEDURES, TEST METHODS AND

CRITERIA RELATING TO CLASS 9 79

APPENDIX 3: A-60 CLASS BULKHEAD CERTIFICATE 84

APPENDIX 4: RESISTANCE TO DETONATION TEST 86

APPENDIX 5: RESISTANCE TO DETONATION CERTIFICATE 90

APPENDIX 6: MATERIAL SAFETY DATA SHEET EXAMPLE 91

APPENDIX 7: DECISION No 1348/2008/EC OF THE EUROPEAN PARLIAMENT

AND OF THE COUNCIL 100

APPENDIX 8: SAFE STORAGE OF AMMONIUM NITRATE 102

APPENDIX 9: ISM PROCEDURES OF M/V SULTAN ATASOY 115

APPENDIX 10: LETTER TO PERMISSION 118

APPENDIX 11: Yükleme Öncesi Ambarların Durumunu Kontrol Listesi 119

APPENDIX 12: Gemi - Sahil Emniyet Kontrol Listesi (UN 2067) 120

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APPENDIX 13: Gemi - Sahil Emniyet Kontrol Listesi (UN 2071) 121

APPENDIX 14: Gemi - Sahil Emniyet Kontrol Listesi (Tüm Gübre Tipleri İçin) 122

APPENDIX 15: Amonyum Nitrat Yüklemesinde/Tahliyesinde Ve Seferde İken

Personelin Isı Yayacak Kaynakları Kullanmaktan Kaçınmaları Uyarısı 123

APPENDIX 16: Amonyum Nitratın Kimyasal Bozunmaya Uğraması Durumunda Acil

Olarak Gemi Personelinin Yapması 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

xi

LIST OF TABLES

Table 1.1.: World Fertilizer Production 2

Table 1.2.: Production Percentages 3

Table 1.3.: Global Export/Import Values 4

Table 1.4.: Export/Import Percentages 4

Table 1.5.: World AN Export Values by Regions 5

Table 1.6.: World AN Import Values by Regions 7

Table 1.7.: Production Quantities of Turkey 8

Table 1.8.: Consumption Quantities of Turkey 8

Table 1.9.: Export Quantities of Turkey 9

Table 1.10.: Import Quantities of Turkey 9

Table 1.11.: Turkish Ports Statistics of AN 10

Table 4.1.: Emergency Procedures 50

Table 4.2.: Risk Assessment 51

xii

LIST OF FIGURES

Figure 1.1.: From Raw Material to Fertilizer Flow Diagram 1

Figure 2.1.: Logic Diagram 1 17

Figure 2.2.: Logic Diagram 2 18

Figure 2.3.: General Properties of AN 21

Figure 3.1.: Photo of Oppau Accident 31

Figure 3.2.: SS Grandcamp 32

Figure 3.3.: View from Galveston 32

Figure 3.4.: After the Explosion of Terra AN Plant 35

Figure 3.5.: Explosion of Plant Near Toulouse City 36

Figure 3.6.: 18th February 2007 the Ostedijk 37

Figure 3.7.: 21st February 2007 the Ostedijk 38

Figure 3.8: M/V Lady Juliet 39

Figure 3.9.: After the terrorist attack, Oklahoma City 40

Figure 3.10.: The Daily Oklahoman Newspaper 41

Figure 3.11.: 15th and 20th November 2003, Istanbul 43

Figure 4.1.: M/V SULTAN ATASOY 54

Figure 4.2.: M/V SULTAN ATASOY Hold No 1 56

Figure 4.3.: M/V SULTAN ATASOY Hold No 2 57

Figure 4.4.: UN 2067 AN Based Fertilizer Sample Sack 58

xiii

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.

1

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

2

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

Source: IFA, (2011)

300000

350000

400000

450000

500000

550000

600000

650000

700000

2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010

Thou

sand

Met

ric T

ons

Fertilizer Production

3

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

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.

AMMONIA25%

AN7%

AS3%CAN

2%DAP5%MAP

3%

PHOSPHATE9%

PHOSPHORIC ACID6%

POTASH8%SULPHUR

8%

TSP1%

UREA23%

Production Percentages

4

"Table 1.3." shows that the total export/import quantity which transported

between countries in one year.

Table 1.3.: Global Export/Import Values

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

Source: IFA, 2011

100000

120000

140000

160000

180000

200000

220000

2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010

Thou

sand

met

ric to

ns

Global Export/Import Values

AMMONIA; %10

AN5%

AS5%

CAN4%

DAP7%

MAP3%

PHOSPHATE6%

PHOSPHORIC ACID3%

POTASH22%

SULPHUR15%

TSP2%

UREA18%

Export / Import Percentages

5

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

6

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/

7

Table 1.6.: World AN Import Values by Regions

Source: IFA, 2011

8

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) 1985-1989 1990-1995 1996-2000 2001-2005 2006 2007 2008

AS

AN %26

AN %33

Urea

TSP

DAP

Composite

299

1028

-

455

458

416

986

215

1201

32

551

159

286

1365

139

1149

42

363

104

229

1542

147

930

72

345

85

114

1459

141

1131

94

147

114

192

1312

219

942

225

-

121

226

1379

108

847

293

145

119

143

1304

Total 3642 3809 3568 3152 3131 3112 2959

Source: TÜİK, 2010

Table 1.8.: Consumption Quantities of Turkey

Fertilizer

(1000 Tons) 1985-1989 1990-1995 1996-2000 2001-2005 2006 2007 2008

AS

AN %26

AN %33

Urea

TSP

DAP

Composite

440

1584

2

517

264

432

1171

342

1401

132

650

128

659

1395

310

1228

401

838

60

633

1627

305

933

752

781

39

501

1509

388

973

896

807

53

637

1571

360

1006

889

772

40

428

1614

292

809

744

770

19

149

1313

Total 4410 4707 5097 4820 5325 5109 4096


9

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) 1985-1989 1990-1995 1996-2000 2001-2005 2006 2007 2008

AS

AN %26

AN %33

Urea

TSP

DAP

Composite

2

28

-

146

285

222

13

13

46

8

76

47

5

27

1

2

1

-

8

3

10

33

26

11

45

-

20

66

6

72

7

17

-

32

39

69

-

6

-

29

123

47

5

20

7

32

-

95

45

Total 696 222 25 201 173 274 204


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) 1985-1989 1990-1995 1996-2000 2001-2005 2006 2007 2008

AS

AN %26

AN %33

Urea

TSP

DAP

Composite

168

532

2

220

22

223

234

141

245

137

258

4

365

70

192

81

450

557

6

351

64

233

21

723

546

14

424

181

250

-

860

812

32

414

260

231

42

560

943

3

310

55

253

8

555

789

9

164

265

Total 1401 1220 1701 2142 2628 2144 2043


10

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 Loaded Discharged Handled Imported Exported

2004 13200 720288 735925 720288 10500

2005 - 664751 668750 664751 -

2006 - 789463 793963 788460 -

2007 5068 634797 639869 634797 5068

2008 90499 585182 675681 508172 37689

2009 40275 936052 976327 914395 28142

2010 30007 670439 700446 657818 18897


11

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

12

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)

13

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)


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

14

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;

15

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.

16

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

17

Source: (EFMA, 2012; 1-20)

18

Source: (EFMA, 2012; 1-20)

19

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:


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:


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)

20

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 169°C 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 32°C 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 18°C, 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)

21

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

22

temperature will quickly rise above 300°C, 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 + ½ 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 210°C 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 250°C then it is accompanied

by an endothermic reaction producing ammonia (NH3) and nitric acid (HNO3).

23

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 300°C, 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.


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)


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.



24


These mixtures may be subject to self-sustaining decomposition if heated. The

temperature in such a reaction can reach 500°C. 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 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.


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)

25


"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 50°C.

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)


Stowage and segregation requirements are the same as 2.4.2. (IMSBC Code,

2010; 71)


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 50°C.

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)

26

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.


Angle of Repose Bulk Density (kg/m³) Stowage Factor (m³/t)

27° to 42° 1000 1.0

Size Class Group

1 to 4 mm 5.1 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 40°C.

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.

27

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)



27° to 42° 900 to 1200 0.83 to 1.11

Size Class Group

1 to 5 mm 5.1 B


This cargo shall not be accepted for loading when the temperature of the

cargo above 40°C.

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.





28







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)



27° to 42° 900 to 1200 0.83 to 1.11

Size Class Group

1 to 5 mm 9 B









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.


29



(IMSBC Code, 2010; 72-74)



27° to 42° 1000 to 1200 0.83 to 1.0

Size Class Group

1 to 4 mm Not applicable C









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.




(IMSBC Code, 2010; 73-77)

30

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

31

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

32

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

33

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 City’s 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 town’s 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)

34

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)

35

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)

36

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)

37

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 175°C 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,

38

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 240m³ 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 Çanakkale City. That ship

also passed the Bosphorus while entering the Marmara from Black Sea. The

39

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

40

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. (Hacaoğlu, 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

41

Figure 3.10.: The Daily Oklahoman Newspaper

Source: The Daily Oklahoman, 20 April 1995

42

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)

43

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

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

44

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

45

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 sayılı Resmî

Gazete)

Also look at Turkish Chemical Fertilizer Regulation "Kimyevi Gübre Denetim

Yönetmeliği" (25/4/2002 tarihli ve 24736 sayılı Resmî 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.

46

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.

47

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 driver’s

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)

48

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.

49

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.

50

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.

51

Table 4.2.: Risk Assessment

52

Table 4.2.: Risk Assessment (continued)

53

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)

54

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.

55

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 80m³/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 9°C 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.

56

Figure 4.2.: Sultan Atasoy Hold No 1

Source: Author, 04.01.2012

57

Figure 4.3.: Sultan Atasoy Hold No 2


58

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


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 Ship’s Crew Concerning Avoidance of Heat Sources When

Loading/Unloading And Carrying Ammonium Nitrate Based Fertilizers (See Appendix 15)

Instruction to the Ship’s Crew for the Handling of Emergencies Involving the

Decomposition of Ammonium Nitrate Based Fertilizers (See Appendix 16)

59

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 Çeşme 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, 20-20-

0.

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.

60

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)

61

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.

Hacaoğlu 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)

62

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/Oklahomacitybombing-

DF-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-1988-

explosion.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)

63

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.

64

Stephens, H.W. (1997). The Texas City Disaster 1947. Austin: University of Texas

Press.

T.C. (Türkiye Cumhuriyeti) Tarım ve Köy İşleri Bakanlığı. (2002) Kimyevi Gübre

Denetim Yönetmeliği 25/4/2002 tarihli ve 24736 sayılı Resmî Gazete

T.C. (Türkiye Cumhuriyeti) Tarım ve Köy İşleri Bakanlığı. (2004). Tarımda Kullanılan

Kimyevi Gübrelere Dair Yönetmelikte Değişiklik Yapılmasına Dair Yönetmelik

18/3/2004 tarihli ve 25406 sayılı Resmî Gazete

The Daily Oklahoman Newspaper. (1995) 20 April 1995.

TÜİK (Türkiye İstatistik Kurumu). (2011) Deniz Ticaret İstatistikleri. 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). Uluslararası Deniz Ticaretinde Tehlikeli Yüklere ilişkin Güvenlik

Yönetimi: Uluslararası Denizde Tehlikeli Yük Tasımacılığı Standartları (IMDG Code)

ve Türkiye Uygulamaları (Türkçe) Dokuz Eylül Üniversitesi Sosyal Bilimler Enstitüsü.

65

APPENDICES

66

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.

67

Type 2 (a): a shock test with defined initiation system and confinement

to determine sensitivity to shock;

Type 2 (b): a test to determine the effect of heating under

confinement; and

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:

68

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)

69

Figure 1: UN Gap Test Apparatus

70

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.

71


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".


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)

72

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)

73

Figure 2: Koenen Test Tube Assembly

74

Figure 3: Koenen Test Heating and Protective Device

75

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

76

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.


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.


The time/pressure apparatus consists of a cylindrical steel pressure vessel 89

mm in length and 60 mm in external diameter. (Figure 5)

77

2.1.1.3.4. Example of Results

Source: (United Nations)

78

Figure 5: Time/Pressure Test Apparatus

79

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 self-

sustaining 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.

80

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

81

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 self-

sustaining decomposition.

If propagation does not continue throughout the substance, the

fertilizer is considered to be free from the hazard of self-sustaining

decomposition.

82

Figure 1: Gauze trough with support burners

83

Figure 2: Electrical heating device

84

APPENDIX 3

A-60 CLASS BULKHEAD CERTIFICATE

85

86

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 25°C and 50°C 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 20°C 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.

87

4. Procedure

Test temperature is 15 to 20°C. 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.

88

Figure 1: Test Arrangement

89

Figure 2: Test Arrangement

90

APPENDIX 5

RESISTANCE TO DETONATION CERTIFICATE

91

APPENDIX 6

MATERIAL SAFETY DATA SHEET EXAMPLE

92

93

94

95

96

97

98

99

100

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.

101

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.

102

APPENDIX 8

103

104

105

106

107

108

109

110

111

112

113

114

115

APPENDIX 9

ISM PROCEDURES OF M/V SULTAN ATASOY

116

117

118

APPENDIX 10

LETTER TO PERMISSION

119

APPENDIX 11

Yükleme Öncesi Ambarların Durumunu Kontrol Listesi

(Amonyum nitrat ve amonyum nitrat içerikli gübreler için örnektir)

Gemi Adı Yük Tipi

İnşaa Yılı UN No/IMDG Class

Gross Tonaj Yükleme Limanı

Önceki Yük Tahliye Limanı Ambar Özellikleri □ Tek Güverteli □ Gladoralı □ Kutu Şeklinde

Ambar Kapakları □ Çelik Katlanan □ Çelik Ponton □ Diğer:

Ambar Tabanı □ Çelik □ Diğer

Aşağıdaki maddeler kontrol edilmiştir # # # # #

A Ambar lastiklerinin sağlamlığının kontrolü

B Ambar kapak yan baskı siğillerinin durumu

C Ambar drenaj delik/boru/kanallarının durumu

D Kastanyola ve koç boynuzlarının durumu

E Ambar kapaklarının durumu

F Ambar kapaklarındaki trimming deliklerinin durumu

G Ambar mezarnalarının durumu

H Ambar içinin genel durumu

I Ambar içindeki hareket edebilecek perdelerin kontrolü

J Ambar havalandırmaları kapalı mı?

K Ambara giriş çıkış yapılan merdivenlerin durumu

L Ambar sintineleri boş mu?

M Isı yayabilecek maddeler uzaklaştırıldı mı?

N Liman işçilerinin kullanabileceği platform gibi yerler var mı?

O Ambar içi aydınlatma veya elektrik devresi varsa kapatıldı mı?

P Ultrasound Leak Detector testi (ULD)

İsim ve Soyisim İmza Tarih Saat

Enspektör

Kaptan

Yüklemeye uygun görülen ambarlar

HAZIRLAYAN: RECEP ORUÇOĞLU ONAYLAYAN: ÖĞ. GÖR. BARIŞ KULEYİN

120

APPENDIX 13 Gemi - Sahil Emniyet Kontrol Listesi

(Amonyum nitrat içerikli UN 2071 gübreler için)

Gemi Adı

Liman Rıhtım Varış draftı Kalkış draftı

Varış Tarihi Varış Zamanı Varış air draftı Kalkış air draftı

Yükleme/Tahliye edilecek yük Yük miktarı

Talimatlar Liman operasyonlarının emniyetli bir şekilde yapılabilmesi için aşağıda verilen tüm sorular, gemi ve liman temsilcileri tarafından kesin ve olumlu ise kutulara işaretlenmelidir. Eğer uygun bir cevap verilemiyor ise bir neden belirtilmeli, gemi ve liman arasında uygun önlemler için karar verilmeli ve uygulanmalıdır. Eğer sorularda uygunsuzluk varsa açıklamalar sütununa sebepler yazılmalıdır.

No Kontrol Edilecekler Gemi Terminal Açıklamalar

1 Yanabilecek veya organik bileşikli maddeler ile birlikte gübre yükü beraber taşınıyorsa, söz konusu yükler ayrı bölümlerde -ambarlarda- taşınacak şekilde yüklendi mi?

2 Eğer içinde UN 2071 gübre olan ambara başka bir yük alınacak ise bu iki yük birbiriyle kimyasal değişim geçirmeyecek şekilde uyumlu mu?

3 Gemi personeli, amonyum nitrat içerikli gübre gemideyken; her türlü ateş ve kıvılcım çıkarabilecek kesim, kaynak veya diğer işlerle uğraşılmayacağının farkında mı?

4 Ambarlar tam olarak kapatılmadan veya yük operasyonu devam ederken herhangi bir yakıt ikmali veya transferi işi yapılmadığından emin oldunuz mu?

5 Yangın pompalarınız dakikada tercihen en az 1 m³ veya daha fazla su basabilecek kapasitede mi?

6 Yangın hortumlarınız acil bir durumda kullanılmak üzere serilip hazırlandı mı?

7 Gemi personeli, amonyum nitrat içerikli gübre gemideyken güverte üzerinde ve ambar içinde sigara içilmeyeceğinin bilincinde mi?

8 "Sigara İçilmez" tabelaları, amonyum nitrat içerikli gübre gemideyken sürekli asılı ve görünür durumda mı?

9 Yükleme / Tahliye operasyonunda yangın vardiyası tutuluyor mu?

10 Ambarlarda duman dedektörü yok ise, en az her 4 saatte bir ambarların içinde bulunan yükün kontrolü yapılıyor mu? (örnek alma kanalından koklama ile)

11 Yük bulunan ambar ile makine dairesi ayrımı yangın önleyici çuvallar ile veya yeterli otorite tarafından eşdeğer görülen aynı işi yapacak madde ile korunuyor mu?

12 Gemide amonyum nitrat içerikli gübreleri taşıyabileceğini gösteren klas onaylı sertifikası bulunuyor mu?

13 Yüklenecek ambarlar, tutuşabilecek herhangi bir maddeden arındırıldı mı?

14 Ambarlara teğet bulunan yakıt tanklarındaki fuel oil 50°C yi geçmeyecek şekilde tutuluyor mu?

15 Yüklemede/Tahliyede/Sefer boyunca, ambarlardaki elektrikli lambalar, kablolar ve elektrik sigortaları açılmayacak şekilde yerlerinden alındı mı?

16 Ambar içinde veya yüzeylerinde ısı yayan devreler bulunuyorsa bunlar kapalı tutuluyor mu?

17 Ambarlarda saatte 6 kez içerideki havayı değiştirebilme kapasitesi olan havalandırma fanları var mı?

Gemi Liman

İsim ve Ünvan

İsim ve Ünvan

İmza İmza

Tarih - Saat Tarih - Saat


121

APPENDIX 14 Gemi - Sahil Emniyet Kontrol Listesi

(Tüm gübre çeşitleri için)

Gemi Adı Liman Rıhtım Varış draftı Kalkış draftı Varış Tarihi Varış Zamanı Varış air draftı Kalkış air draftı Yükleme/Tahliye edilecek yük Yük miktarı Talimatlar Liman operasyonlarının emniyetli bir şekilde yapılabilmesi için aşağıda verilen tüm sorular, gemi ve liman temsilcileri tarafından kesin ve olumlu ise kutulara işaretlenmelidir. Eğer uygun bir cevap verilemiyor ise bir neden belirtilmeli, gemi ve liman arasında uygun önlemler için karar verilmeli ve uygulanmalıdır. Eğer sorularda uygunsuzluk varsa açıklamalar sütununa sebepler yazılmalıdır.

No Kontrol Edilecekler Gemi Terminal Açıklamalar

1 Yükleme veya tahliye operasyonu öncesi rıhtımdaki su derinliği ile air draft emniyetli seviyelerde mi? (air draft köprü geçişi, kreyn çalışma yüksekliği vs var ise)

2 Yerel akıntı, gelgit, hava etkilerine geminin palamarlama ekipmanları yeterli mi?

3 Acil bir durumda gemi hemen liman dışına çıkabilecek durumda mı?

4 Rıhtım ile gemi arasındaki giriş çıkış emniyetli mi?

5 Liman-gemi haberleşmesi için uygun görülen; Metod: Dil: Kanal/Tel No:

6 Acil durumlar için gemideki ve limandaki personel yeterli mi?

7 Amonyum nitrat gemiden tahliye edilirken veya gemiye yüklenirken, yakıt/yağ alımı operasyonu yapılacak mı?

8 Amonyum nitrat gemiden tahliye edilirken veya gemiye yüklenirken, gemi güvertesine veya rıhtıma yapılması planlanan bir tamir işi/sıcak iş var mı?

9 Yük operasyonları sırasında gelebilecek hasarların kaydı ve raporlanması prosedürü konusunda anlaşıldı mı?

10 Liman ve rıhtımın emniyet, çevre koruma ve diğer yönetmelikleri kopyaları ile acil durum servisleri bilgileri gemiye liman tarafından verildi mi?

11 Yükün özellikleri, SOLAS Bölüm 6 gereklilikleri altında taşıtan tarafından gemi kaptanına sağlandı mı?

12

Ambar içinin ve girilmesi gerekebilecek kapalı mahallerin atmosferi emniyetli mi? Fümigasyon yapılan kargolarda girilecek mahalin atmosferinin ölçülmesi gerekliliği gemi - liman arasında kararlaştırıldı mı?

13 Yükleme/tahliye yapacak olan kreynlerin yük elleçleme kapasiteleri istenenleri karşılıyor mu? Kreyn No: Hız: ton/saat Kreyn No: Hız: ton/saat

14 Yükleme/tahliye planının ve balast operasyonlarının tüm adımları hesaplanmış mı?

15 Yükleme/tahliye planında çalışılacak ambarların sırası ve miktarı hesaplanıp verilmiş mi? Liman verilen planı uyguluyor mu?

16 Trimming operasyonu olup olmayacağı, olacaksa yöntemi tartışıldı mı?

17 Balast alma/basma planında bir aksaklık olursa yükleme/tahliye operasyonunun kesintiye uğrayacağı gemi ve liman tarafından kabul ediliyor mu?

18 Tahliye operasyonunda yükün kalıntılarının nasıl alınacağı konusundaki prosedür gemiye anlatılıp, kabul gördü mü?

19 Yüklenen geminin kalkış trimini ayarlamada nasıl bir prosedür izleneceğine karar verildi mi?

20 Gemi, limanı yükleme/tahliye operasyonundan ne kadar sonra denize çıkmaya hazır olacağı konusunda bilgilendirdi mi?

21 Gemi seferi boyunca taşıyacağı gübre yükünü korumak için alacağı önlemler hakkında bilgilendirildi mi?

22 Gemi yüklemeden önce aşağıdaki evrakları aldı mı? - MSDS - Amonyum nitrat yükleme/taşıma/tahliyesi sırasında herhangi bir ısı kaynağını uzak tutma hakkında gemi personelinin uyacağı talimat - Amonyum nitratın kimyevi bozunuma uğraması durumunda yapılcaklar hakkında gemi personelinin uyacağı talimat


122

AMONYUM NİTRAT YÜKLEMESİNDE/TAHLİYESİNDE VE

SEFERDE İKEN PERSONELİN ISI YAYACAK KAYNAKLARI

KULLANMAKTAN KAÇINMALARI UYARISI

Klasına bakılmaksızın, tüm amonyum nitrat gübrelerinde tüm ısı yayan kaynaklar

yükten uzak tutulmalıdır. Potansiyel ısı kaynakları şunlardır: ampuller, ısıtıcı

sistemler, buhar (stim) boruları, elektrikli kaynak ve kesim makineleri, elektrik

kabloları, tüm çıplak ateş kaynakları.

Dolayısıyla:

Sefer boyunca ambarların içindeki tüm ışıkları ve ısı yayacak kaynakları

kapatın.

Ambar içindeki tüm elektrik sigortalarını sökün ve yükün tahliyesine kadar

takmayın.

Sıcak iş kategorisine giren herhangi kesim, kaynak vb. veya kıvılcım

çıkartabilecek kesim, raspa vb. işlerin güvertede yapılmasına izin vermeyin.

"Sigara İçilmez" levhalarını asılı tutun.

123

AMONYUM NİTRATIN KİMYASAL BOZUNMAYA

UĞRAMASI DURUMUNDA ACİL OLARAK GEMİ

PERSONELİNİN YAPMASI GEREKENLER

Gemi limanda ise, yerel acil yardım servisleriyle irtibata geçin.

Gemi seyirde ise, gemi acentesine, şirketinize veya yük sahibiyle irtibata

geçin.

MSDS te bulunan talimatları uygulayın.

Yangın durumunda, eğer mümkünse ısı kaynağını ortadan kaldırmaya

çalışın. Yangın ve kimyasal bozunmada su ile söndürme çalışması yapın.

Sadece kimyasal bozunma var ise, yükün kimyasal değişime uğramış

bölümünü sağlam olan bölümünden mümkünse ayırın ve su ile ıslanmasını

sağlayın. (tatlı veya tuzlu su)

Yükü zarar görmemiş kısımdan ayırmanız mümkün değilse, ambar içindeki

yükün tamamını su ile ıslatın. Suyun, yükün içine kadar işlemesi için tazyikli

su kullanın.

Yangına veya kimyasal bozunmaya karşı köpük, CO2, kum veya yükün kalan

kısmını kesinlikle kullanmayın.

Date post:	29-Jul-2015
Category:	Documents
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