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
ii
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:
i
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
ii
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.
iii
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.
iv
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
v
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
2.1.2. Ammonium Nitrate UN 1942 - Class 5.1 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
2.5.1. Ammonium Nitrate UN 1942 - Class 5.1 23
2.5.2. Ammonium Nitrate Based Fertilizer UN 2067 - Class 5.1 23
2.5.3. Ammonium Nitrate Based Fertilizer UN 2071 - Class 9 24
2.5.4. Ammonium Nitrate Based Fertilizer (Non-Hazardous) 24
2.6. Stowage and Segregation Requirements of Ammonium Nitrate 24
2.6.1. Ammonium Nitrate UN 1942 - Class 5.1 24
2.6.2. Ammonium Nitrate Based Fertilizer UN 2067 - Class 5.1 25
2.6.3. Ammonium Nitrate Based Fertilizer UN 2071 - Class 9 25
vi
2.6.4. Ammonium Nitrate Based Fertilizer (Non-Hazardous) 25
2.7. Weather Precautions of Ammonium Nitrate 26
2.8. Loading 26
2.8.1. Ammonium Nitrate UN 1942 - Class 5.1 26
2.8.2. Ammonium Nitrate Based Fertilizer UN 2067 - Class 5.1 27
2.8.3. Ammonium Nitrate Based Fertilizer UN 2071 - Class 9 28
2.8.4. Ammonium Nitrate Based Fertilizer (Non-Hazardous) 29
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
ix
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
x
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
Source: TÜİK, 2010
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
Source: TÜİK, 2010
1.3.2. Import Statistics in Turkey
Turkey generally imports nitrogen based fertilizers rather than phosphate or
sulphur based fertilizers. 85% of fertilizers that Turkey imported in year 2004 are
urea and ammonium nitrate based fertilizers.
Table 1.10.: Import Quantities of Turkey
Fertilizer
(1000 Tons) 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
Source: TÜİK, 2010
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
Source: TÜİK, 2011
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)
2.1.2. Ammonium Nitrate UN 1942 - Class 5.1
White crystals, prills or granules. Wholly or partly soluble in water. Oxidizer,
supports combustion. Odorless.
AN with not more than 0.2% total combustible material, including any organic
substance, calculated as carbon to the exclusion of any other added substance is
described UN number 1942 and Class 5.1. (IMSBC Code, 2010; 67-68)
2.1.3. Ammonium Nitrate Based Fertilizer UN 2067 - Class 5.1
Crystals, granules or prills. Wholly or partly soluble in water. Hygroscopic.
Odorless.
AN based fertilizers classified as UN 2067 are uniform mixtures containing
ammonium nitrate as the main ingredient within the following composition limits:
i) not less than 90% ammonium nitrate with not more than 0.2% total
combustible/organic material calculated as carbon and with added
matter, if any, which is inorganic and inert towards ammonium nitrate; or
ii) less than 90% but more than 80% ammonium nitrate with other inorganic
materals; or
iii) less than 90% but more than 70% ammonium nitrate mixed with calcium
carbonate and/or dolomite (calcium magnesium carbonate) and not more
than 0.4% total combustible/organic material calculated as carbon; or
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:
Fertilizer composition by weight %
Ammonium nitrate 75
Calcium carbonate or dolomite 10
Inert e.g. calcium sulphate or gypsum 15
Answer: The fertilizer is classified as an oxidiser, class 5.1.
Example 3:
Fertilizer composition by weight %
Ammonium nitrate 69
MOP (KCl) 9
Ammonium sulphate 22
Trough test shows it to be not capable of self-sustaining
decomposition.
Answer: The fertilizer is not classified.
Source: (EFMA, 2012; 1-20)
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.
2.5.1. Ammonium Nitrate UN 1942 - Class 5.1
A major fire aboard a ship carrying these materials may involve a risk of
explosion, in the event of contamination with fuel oil. An adjacent detonation may
also involve a risk of explosion.
If heated strongly, this cargo decomposes giving of toxic gases and gases
which support combustion.
Ammonium nitrate dust might be irritating to skin and mucous membranes.
This cargo is hygroscopic (absorbs water, water vapor or moisture) and will
cake if wet. (IMSBC Code, 2010; 67)
2.5.2. Ammonium Nitrate Based Fertilizer UN 2067 - Class 5.1
Supports combustion. A major fire aboard a ship carrying these materials may
involve a risk of explosion, in the event of contamination with fuel oil. An adjacent
detonation may also involve a risk of explosion.
If heated strongly decomposes, risk of toxic fumes and gases which support
combustion, in the cargo space and on deck.
Fertilizer dust might be irritating to skin and mucous membranes.
This cargo is hygroscopic (absorbs water, water vapor or moisture) and will
cake if wet. (IMSBC Code, 2010; 69)
24
2.5.3. Ammonium Nitrate Based Fertilizer UN 2071 - Class 9
These mixtures may be subject to self-sustaining decomposition if heated. The
temperature in such a reaction can reach 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 hygroscopic (absorbs water, water vapor or moisture) and will
cake if wet. (IMSBC Code, 2010; 71)
2.5.4. Ammonium Nitrate Based Fertilizer (Non-Hazardous)
This cargo is non-combustible or with low fire risk.
Even though this cargo is classified as non-hazardous, it will behave in the
same way as the ammonium nitrate based fertilizers classified in class 9 under UN
2071 when heated strongly, by decomposing and giving off toxic gases. (IMSBC
Code, 2010; 74)
2.6. Stowage and Segregation Requirements of Ammonium Nitrate
Stowage and segregation requirements of ammonium nitrate cargoes shown
below.
2.6.1. Ammonium Nitrate UN 1942 - Class 5.1
There should be no sources of heat or ignition in the cargo space.
"Seperated by a complete compartment or hold from" combustible materials,
chlorates, chlorides, chlorites, hypochlorites, nitrites, permanganates and fibrous
materials (e.g. cotton, jute, sisal).
"Seperated from" all other goods.
If the bulkhead between the cargo space and the engine room is not insulated
to class A-60 standart (see Appendix 3; A-60 Class Bulkhead Certificate), this
cargo shall be stowed "away from" the bulkhead. (IMSBC Code, 2010; 67)
25
2.6.2. Ammonium Nitrate Based Fertilizer UN 2067 - Class 5.1
"Seperated by a complete compartment or hold from" combustible materials,
bromates, chlorates, chlorites, hypochlorites, nitrites, perchlorates, permanganates,
powdered metals and vegetable fibres.
"Seperated from" all other goods.
"Seperated from" sources of heat or ignition.
Not to be stowed immediately adjacent to any tank or double bottom tank
containing fuel oil heated to more than 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)
2.6.3. Ammonium Nitrate Based Fertilizer UN 2071 - Class 9
Stowage and segregation requirements are the same as 2.4.2. (IMSBC Code,
2010; 71)
2.6.4. Ammonium Nitrate Based Fertilizer (Non-Hazardous)
The compatibility of non-hazardous ammonium nitrate based fertilizers with
other materials which may be stowed in the same cargo space should be
considered before loading.
"Seperated from" sources of heat or ignition.
Not to be stowed immediately adjacent to any tank or double bottom tank
containing fuel oil heated to more than 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.
2.8.1. Ammonium Nitrate UN 1942 - Class 5.1
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)
2.8.2. Ammonium Nitrate Based Fertilizer UN 2067 - Class 5.1
Angle of Repose Bulk Density (kg/m³) Stowage Factor (m³/t)
27° to 42° 900 to 1200 0.83 to 1.11
Size Class Group
1 to 5 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.
28
Due consideration shall be paid to the possible need to open hatches in case
of fire to provide maximum ventilation and to apply water in an emergency, and the
consequent risk to the stability of the ship through fluidization of the cargo.
During loading, the following provisions shall be complied with:
Bunkering of fuel oil shall not be allowed. Pumping of fuel oil in spaces
adjacent to the cargo spaces, other than the engine room, shall not be allowed.
As far as reasonably practicable, combustible securing and protecting
materials shall not be used. When wooden dunnage is necessary, only a minimum
shall be used. (IMSBC Code, 2010; 69-73)
2.8.3. Ammonium Nitrate Based Fertilizer UN 2071 - Class 9
Angle of Repose Bulk Density (kg/m³) Stowage Factor (m³/t)
27° to 42° 900 to 1200 0.83 to 1.11
Size Class Group
1 to 5 mm 9 B
Prior to loading, the following provisions shall be complied with:
All electrical equipment, other than those of approved intrinsically safe type, in
the cargo spaces to be used for this cargo shall be electrically disconnected from
the power source, by appropriate means other than a fuse, at a point external to the
space. This situation shall be maintained while the cargo is on board.
Due consideration shall be paid to the possible need to open hatches in case
of fire to provide maximum ventilation and to apply water in an emergency, and the
consequent risk to the stability of the ship through fluidization of the cargo.
In addition, if decomposition occurs, the residue left after decomposition may
have only half the mass of the original cargo. Due considetation shall be paid to the
effect of the loss of mass on the stability of the ship.
During loading, the following provisions shall be complied with:
29
Bunkering of fuel oil shall not be allowed. Pumping of fuel oil in spaces
adjacent to the cargo spaces, other than the engine room, shall not be allowed.
(IMSBC Code, 2010; 72-74)
2.8.4. Ammonium Nitrate Based Fertilizer (Non-Hazardous)
Angle of Repose Bulk Density (kg/m³) Stowage Factor (m³/t)
27° to 42° 1000 to 1200 0.83 to 1.0
Size Class Group
1 to 4 mm Not applicable C
Prior to loading, the following provisions shall be complied with:
All electrical equipment, other than those of approved intrinsically safe type, in
the cargo spaces to be used for this cargo shall be electrically disconnected from
the power source, by appropriate means other than a fuse, at a point external to the
space. This situation shall be maintained while the cargo is on board.
Due consideration shall be paid to the possible need to open hatches in case
of fire to provide maximum ventilation and to apply water in an emergency, and the
consequent risk to the stability of the ship through fluidization of the cargo.
In addition, if decomposition occurs, the residue left after decomposition may
have only half the mass of the original cargo. Due considetation shall be paid to the
effect of the loss of mass on the stability of the ship.
During loading, the following provisions shall be complied with:
Bunkering of fuel oil shall not be allowed. Pumping of fuel oil in spaces
adjacent to the cargo spaces, other than the engine room, shall not be allowed.
(IMSBC Code, 2010; 73-77)
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
Source: Author, 04.01.2012
58
Figure 4.4.: UN 2067 Ammonium Nitrate Based Fertilizer Sample Sack
Source: Author, 04.01.2012
4.4.3. Checklist Proposal
Checklists and instructions were prepared by EFMA, very useful, simple but
effective questionnaire. The approach is to focus on specific hazards that obligate
these measures.
Conditions of Hatches Prior to Loading (see Appendix 11)
Ship/Shore Safety Checklist (UN 2067) (see Appendix 12)
Ship/Shore Safety Checklist (UN 2071) (see Appendix 13)
Ship/Shore Safety Checklist (All Fertilizers) (see Appendix 14)
Instruction to the 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
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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
2.1.1.2.2. Test criteria and method of assessing results
The result is considered "+" and the substance to show some effect on heating
under confinement if the limiting diameter is 1.0 mm or more. The result is
considered "—" and the substance to show no effect on heating under confinement
if the limiting diameter is less than 1.0 mm.
The following effects are differentiated:
"O": Tube unchanged;
"A": Bottom of tube bulged out;
"B": Bottom and wall of the tube bulged out;
"C": Bottom of tube split;
"D": Wall of tube split;
"E": Tube split into two fragments;
"F": Tube fragmented into three or more mainly large pieces which in
some cases may be connected with each other by a narrow strip;
"G": Tube fragmented into many mainly small pieces, closing device
undamaged; and
"H": Tube fragmented into many very small pieces, closing device
bulged out or fragmented.
Examples for the effect types "D", "E" and "F" are shown in Figure 4. If a trial
results in any of the effects "O" to "E", the result is regarded as "no explosion". If a
trial gives the effect "F", "G" or "H", the result is evaluated as "explosion".
2.1.1.2.3. Test Apparatus
The apparatus consists of a non-reusable steel tube, with its re-usable closing
device, installed in a heating and protective device. The tube is deep drawn from
sheet steel of suitable quality. The mass of the tube is 25.5 ± 1.0 g. The open end of
the tube is flanged. The closing plate with an orifice, through which the gases from
the decomposition of the test substance escape, is made from heat-resisting chrome
steel. (Figure 2)
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.
2.1.1.3.2. Test criteria and method of assessing results
The test results are interpreted in terms of whether a gauge pressure of 2070
kPa is reached and, if so, the time taken for the pressure to rise from 690 kPa to
2070 kPa gauge.
The result is considered "+" and the substance to show the ability to deflagrate
if the maximum pressure reached is greater than or equal to 2070 kPa. The result is
considered "—" and the substance to show no likelihood of deflagration if the
maximum pressure reached in any one test is less than 2070 kPa gauge. Failure to
ignite does not necessarily indicate that the substance has no explosive properties.
2.1.1.3.3. Test Apparatus
The time/pressure apparatus consists of a cylindrical steel pressure vessel 89
mm in length and 60 mm in external diameter. (Figure 5)
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
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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
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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.
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