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AMMONIUM NITRATE IN PORTS STORAGE AND TRANSPORTATION

Robert Hutchison and Philip Skinner Lloyds Register; e-mail: robert.hutchison@lr.org and philip.skinner@lr.org
Large quantities of ammonium nitrate are manufactured and transported by ship around Australia supplying the main raw material for explosives used by the mining industry. Thus there is the potential for accidental explosions involving hundreds or thousands of tonnes of ammonium nitrate in stockpiles near ports awaiting loading to ships or on board a ship. The ammonium nitrate used as a raw material for explosives has a lower density and a higher porosity than the ammonium nitrate used in the fertiliser industry, which makes it more sensitive to explosion propagation. There have been numerous accidents involving ammonium nitrate around the world over the past century involving various grades and mixtures of ammonium nitrate. These include the major accidents at Oppau, Texas City and Toulouse. More recently, there have been terrorist attacks that have used ammonium nitrate based explosives such as the Oklahoma City bombing. Risk assessments of the transportation of ammonium nitrate must take account of all these factors, which requires addressing the following questions: . How should the consequences of an explosion of ammonium nitrate be modelled? What is the TNT equivalence of pure and contaminated ammonium nitrate? Will the ammonium nitrate detonate or deagrate? . How should the consequences of a re involving ammonium nitrate be modelled? Can the grade of ammonium nitrate support combustion? What are the products of combustion? . How should the likelihood of an accidental explosion involving ammonium nitrate be estimated? Is history a good predictor of future explosions? . How should the likelihood of terrorist activities be estimated? . What fraction of a load or stockpile of ammonium nitrate could explode? What fraction of a load or stockpile of ammonium nitrate is likely to explode? Risk assessments prepared for Australian ports that handle signicant quantities of ammonium nitrate are used to provide guidance on the above questions. This will assist the preparation of future risk assessments to accurately assess the risk associated with transportation of large quantities of ammonium nitrate by ship.

KEYWORDS: ammonium nitrate, re, explosion, transportation, ports, shipping

INTRODUCTION Within Australia, there is a large market for explosives to support the mining industry. The main explosive used in Australian mining has ammonium nitrate as a precursor. Ammonium nitrate is both manufactured in Australia and imported from overseas. Due to the size of the market in ammonium nitrate, large quantities are transported both internationally and within Australia. Ships are used for the international transportation of ammonium nitrate and potentially for movements between the east and west coasts of Australia. The local manufacturers and the importers of ammonium nitrate want to minimise their costs and so large shipment sizes have occurred and are proposed for the future within Australia. Where the load is sufciently large that a ship can be chartered for exclusive use, the manufacturer or importer has increased control over the condition of the ship and other specic aspects of the transportation. This can improve the delivered quality of the

material through reduced potential for contamination and less damage to the bags. This also reduces the transport cost per tonne. However, larger shipments have potentially larger accident consequences. The larger a shipment of ammonium nitrate, the larger is the maximum possible explosion, the distance travelled by smoke from a re and the pollution potential. This paper examines the changes in risk and costs that occurs with changes in the shipment size of ammonium nitrate. This paper focuses on the accidental explosion risks associated with transportation of ammonium nitrate and does not consider smoke from res and the risks associated with terrorism. Previous Quantitative Risk Assessments (QRAs) that have been undertaken in Australia were used to provide the explosion scenarios and likelihoods. Indicative costing estimates have been provided by people involved in the transportation of ammonium nitrate.

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This paper focuses on the differences in cost and risk associated with an annual trade of 100 000 tonnes (te) of ammonium nitrate through an Australian port. This is a large but credible annual trade volume for an Australian port. The shipment sizes considered are 100 te, 200 te, 500 te, 1000 te, 2000 te, 5000 te, 10 000 te and 20 000 te. SCENARIO IDENTIFICATION Many of the scenarios that are considered in QRAs are not affected by the shipment size. For example the risks associated with explosion of a truck carrying ammonium nitrate to or from the port are only affected by the truck load size and the annual trade, not the quantity that is on the ship transporting the ammonium nitrate. The scenarios that have been considered in this paper are those considered in previous QRAs in Australia: 1. A small explosion of 20 te of ammonium nitrate. This is considered a small explosion only by comparison to the quantities that can be carried on a ship. A re on a ship could conceivably directly affect 20 te of ammonium nitrate, causing it to be heat affected or contaminated by fuel or other organic material. The re could then cause the 20 te of contaminated heat affected AN to explode. 2. A partial explosion of 20% of the ammonium nitrate in the shipment. The scenario that is envisaged here is the explosion of 20 te of ammonium nitrate boosting a fraction of the ammonium nitrate carried on the ship. The historical record suggests that only a fraction of stockpiles of ammonium nitrate involved in explosions have contributed to the overpressure wave. 3. A complete explosion of 100% of the ammonium nitrate in a full shipment. This scenario is considered the worst credible accident and could occur due to an uncontrolled re in a fully laden ship with all the ammonium nitrate stored in one hold or in close proximity. The uncontrolled re could cause a fraction of the ammonium nitrate potentially contaminated and heat affected by the re to detonate and then to propagate through the rest of the shipment. CONSEQUENCES OF SCENARIOS In assessing the consequences of the explosion scenarios, there are a number of important parameters. 1. TNT equivalence. The TNT equivalence of pure ammonium nitrate is considered to be in the range of 30% to 55% based on both theoretical and experimental results. In this study an equivalence of 34.6% is used based on the ratio of the heat of detonation of ammonium nitrate of 378 kcal/kg to the heat of explosion of TNT of 1094 kcal/kg (Lawrence Livermore National Laboratory 2002). If the ammonium nitrate is contaminated during the accident with a fuel, the TNT equivalence is increased to approximately 1.0. For the large shipments of ammonium nitrate being considered in this analysis, it

2.

3.

is unlikely for an accident to cause contamination of a signicant fraction and a TNT equivalence of 34.6 has been used. Despite the variation in the values of TNT equivalence for ammonium nitrate, this is a parameter with less uncertainty than the others in the analysis and the differences in equivalence do not greatly affect the consequence distances. Fraction of inventory that contributes to the explosion. The fraction of inventory that contributes to the overpressure shockwave produced by the explosion is a critical parameter but is very uncertain. In historical accidents, the fraction of the inventory that has contributed to the overpressure has ranged over two orders of magnitude from less than 1% at Cherokee Nitrogen in 1973 (Freeman 1975), to 10% at Oppau in 1921(Medard 1990), to 10% 60% for Toulouse in 2001 (Creemers, et al. 2002) and close to 100% at Texas City in 1947 (Klintz, et al. 1947). The reasons for the differences in the inventory fractions that contributed to the explosions include differences in the material or grade of ammonium nitrate, the degree of connement and the proximity of the initial explosion to the bulk pile. In QRAs within Australia, the uncertainty surrounding the fraction of inventory that will contribute to the shock wave has been accommodated by postulating different likelihoods for various explosion scenarios. In this study, the three different accident scenarios primarily differ in the quantity of ammonium nitrate that explodes and thus are considered with different likelihood estimates. This method implicitly utilises a risk based framework where both the consequence and likelihood are considered. The regulators in Australia have established risk-based criteria for assessing new developments. Explosion modelling. Most recent QRAs in Australia on ammonium nitrate have modelled explosion of an equivalent quantity of TNT to represent the explosion of the ammonium nitrate. The relationship between quantity of TNT and overpressure is well known and documented (Mannan 2005). The explosion modelling estimates the overpressure as a function of distance. There are also rudimentary models that estimate the shrapnel distribution from an explosion but they are not considered further in this study. The relationship between overpressure and likelihood of fatality varies whether the affected person is inside or in the open air. In this study, an overpressure of 14 kPa was considered to have negligible fatality risk, 21 kPa to have a 20% fatality risk, 35 kPa to have a

One accident that has occurred was where a bunker hatch at the bottom of a hold was not sealed correctly. After loading with ammonium nitrate bags, the ship lled its bunker tanks. The fuel owed into the base of the hold and over the duration of the voyage soaked into the bags. If this material was exploded a TNT equivalence of 1 would be appropriate.

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50% fatality risk and 70 kPa to have a 100% fatality risk (DIPNR, 1990). 4. People in the vicinity of the explosion. The modelling must consider the people who may be in the danger zone when an explosion occurs. In addition, the property that may be damaged also should be considered, particularly to assess the potential for domino or knock-on accidents. In this study, consequences have been restricted to fatalities to people. The port considered in this study is ctitious but is based on the numbers of people at distances from a number of the ports that handle ammonium nitrate in Australia. In the immediate vicinity of the ship (, 50 m from the centre of the accidental explosion), there are likely to be 20 people including ship personnel, stevedores and inspectors. In the area between 50 m and 100 m from the centre of the accidental explosion, there is likely to be 4 people, primarily associated with security, port administration and truck ow management. Between 100 m and 500 m there are likely to be other ships and local storages and buildings on the port. 50 people are assumed to be present in this region. The area between 500 m and 1000 m is likely to include administration buildings, as well as general port facilities, including warehouses, storages, container loading onto trucks or rail cars. In this large area 1000 people are assumed to be present. Beyond 1000 m is likely to be commercial areas and residential areas. The population density in this area is assumed to be 20/ha (which is the average residential density in Sydney). Figure 1 illustrates this data and shows the concentration of people at the ship during the loading/unloading operation. However the density of population generally increases with distance from the ship, as does the numbers of people. In most of the explosion scenarios, a re precedes the explosion. This period can be used to evacuate people from the vicinity of the ammonium nitrate, which can signicantly reduce the numbers of people who may be killed or injured by an explosion. This factor has not been considered in this study.
Local Population 1400 1200 30.0

LIKELIHOOD The likelihood of the explosion scenarios is the area of greatest uncertainty. Since the three ship explosions in 1947 and the one in 1953, I am unaware of any ship explosions involving ammonium nitrate. Following those explosions (over 50 years ago), signicant changes were made to the composition of ammonium nitrate and the emergency response actions that would occur in the event of a re. However, the historical record cannot show that a ship explosion is impossible. Thus, fault trees have been developed for numerous QRAs, which identify the causal sequences that are required for an explosion to occur and suggest likelihood or frequency values for the scenarios. The likelihood estimates of the explosion scenarios considered in this study are based on recent QRAs prepared in Australia. These likelihood estimates are: . . . 20 te AN explosion on a ship in a port for loading or unloading of ammonium nitrate: 1.1 1028 per cargo. Partial explosion of shipment (20% of full load): 2.5 1029 p.a. Complete explosion of shipment (100% of full load): 1.1 1029 p.a.

People per Hectare

People in Rings Surrounding Ship

25.0 20.0 15.0 10.0 5.0 0.0 2500

1000 800 600 400 200 0 0 500 1000 1500 2000 Distance (m)

Population

RISK OF ACCIDENT SCENARIOS The risk of the explosions is estimated taking into account the physical consequences and the likelihood. In Australia, the New South Wales Department of Planning criteria are used by many state governments to assess the risk of proposed developments. The criteria are based on location specic individual fatality risk contours and the risk of dened overpressure and heat radiation levels. The criteria apply to various land uses e.g. a new development should not expose any residential land to fatality risks above 1 1026 p.a. Another criterion that is often considered is societal risk expressed as an FN curve. There are no ofcial FN criteria in Australia but there are various criteria that have been applied elsewhere in the world. However, in a comparative risk assessment, such as the subject of this study, a single measure of risk was desired. The Potential Loss of Life (PLL) is the summation of the individual fatality risk levels at all the locations where a person is assumed to be located. This estimate of risk does not take account of the potential for people to be injured but not killed, neither does it include the potential for shrapnel to strike people, for people to be injured by smoke from a re or the potential for property to be damaged.

Population Density

COST OF SHIPPING The cost of shipping ammonium nitrate comprises two components: 1. A xed administration cost per shipment which is independent of the size of the shipment. This is assumed to be $5000.

Figure 1. Populations surrounding shipment of ammonium nitrate

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Average cost per tonne $200

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Fatality Risk 1.E-06 1.E-07 1.E-08 1.E-09 Small ship explosion Partial ship explosion Complete ship explosion Total 0 500 1000 1500

Cost per Tonne

$150 $100 $50 $0 0 5000 10000 Shipment Size (te) 15000 20000

1.E-10

Figure 2. Average cost per tonne of ammonium nitrate shipments

Figure 4. Location specic individual fatality risk surrounding 10 000 te shipments

2. The cost of the shipping. For loads smaller than a full ship, the cost is a xed price per tonne (assumed to be $120 per tonne). For loads of 5000 te and above, a full ship can be chartered. The cost for loads of 5000 te to 20 000 te is assumed to be $120 5000 $600 000. The costing is shown in Figure 2. It is signicantly less costly to transport larger shipments, particularly if a ship can be chartered for a full load. RESULTS The overpressure produced by explosions of shipments of ammonium nitrate is shown in Figure 3. The distances to fatal overpressures of 35 kPa range from less than 200 m for 100 te of AN to approximately 1000 m for 20 000 te of AN. The distances to overpressure that will not cause fatality and only has a low likelihood of injury (3.5 kPa) range from 1 km for 100 te AN to 5.6 km for 20 000 te AN. The fatality risk to people located in the vicinity of a port undertaking 10 000 te shipments of ammonium nitrate is shown in Figure 4. The fatality risk to people located close to the ship (, 150 m) is dominated by the small ship explosion because the likelihood is higher. The risk to people located between 150 m and 500 m is dominated by the partial ship explosion and for distances between 500 m and 1400 m the risk is dominated by the complete ship explosion. The magnitude of the risks at all locations is
80
Peak Overpressure (kPa)

very low, less than 1.5 1027 p.a. This value should be juxtaposed with the NSW Department of Planning individual fatality risk criterion for sensitive locations in the vicinity of a proposed development, which is 5 1027 p.a. The societal risk as a function of shipment size is shown in Figure 5. The larger shipments have generally lower likelihoods of explosions but the consequences are substantially larger. With the smallest shipment size (100 te), the likelihood of a complete ship explosion is 1.1 1026 p.a. and this could kill 28 people. All these people are working on the port and have some degree of voluntary acceptance of risk. With the largest shipment size, the likelihood of a complete ship explosion is much lower at 5.5 1029 p.a. but the number of people who could be killed is much higher at 3600. Also, the majority of these people would be members of the public with no voluntary acceptance of the risk. The criteria lines shown are the indicative societal risk criteria suggested in NSW but are not mandatory. The societal risk associated with 1000 te and 2000 te shipments is closer to the lower criteria line. The smaller shipments lie closer to the upper criteria line and the 10 000 te and 20 000 te shipments extend beyond the upper criteria line because they could cause in excess of 1000 fatalities, which is the limit tolerable using these criteria lines. However, other criteria lines are used in other jurisdictions and the conclusions of the analysis would be different.

70 60 50 40 30 20 10 0 0 1000 2000 3000 4000 5000 6000 Distance (m)

100 200 500 1000 2000 5000 10000 20000

F (frequency of events causing N or more fatalities)
1.E-04 1.E-05 1.E-06 1.E-07 1.E-08 1.E-09 1 10

Societal Risk

100 te 200 te 500 te 1000 te 2000 te 5000 te 10,000 te 20,000 te Lower Limit Upper Limit

100 N (Fatalities)

1000

10000

Figure 3. Overpressure from explosions of various sized shipments

Figure 5. Societal risk as a function of shipment size

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Cost vs Benefit
0.0004 0.0003
PLL

$200 $150 $100 $50 $0

0 5000 10000 15000 20000 Shipment Size (te)

Shipment Cost ($/te)

Potential Loss of Life Average Cost of Shipment Ratio

0.0002 0.0001 0

Figure 6. Costs and benets as a function of shipment size

Figure 6 shows the comparison between the cost of larger shipments to society due to the potential explosion risk and the benets to the owner of the shipment through lower costs. The overall fatality risk, measured by PLL, decreases as a function of shipment size until the 2000 te shipment size is reached. The PLL is larger for 5000 te shipments, lower for 10 000 te shipments and higher for 20 000 te shipments. These changes in fatality risk are due to the combination of the further extent of larger explosions, the population distributions and the lower likelihood of larger explosions. The lowest PLL is at the 10 000 te shipment size. The ratio between the shipment cost and the PLL is lowest at the 2000 te shipment size. Either side of the 2000 te shipment size, the changes in PLL are greater than the changes in the shipment cost. However the risks are still very low for all the shipment sizes.

that is closest to the lower societal risk criterion suggested for use in NSW. When considering the tolerability of the risk from larger shipment sizes, it is important to consider societal risk and not just the individual fatality risks as the magnitude of the consequences can be signicant if a large shipment of ammonium nitrate explodes. REFERENCES
Creemers, A.F.L., Kersten, R.J.A., van der Steen, A.C., Opschoor, G. 2002, The ammonium nitrate explosion in Toulouse, France The incident and its consequences for industrial activities, TNO web site. DIPNR 1990, Risk Criteria for Land Use Planning, NSW Department of Infrastructure, Planning and Natural Resources: Hazardous Industry Planning Advisory Paper No. 4 Freeman, R. 1975, The Cherokee Ammonia Plant Explosion, Chemical Engineering Progress 71(11), November 1975 Klintz, G.M., Jones, G.W. and Carpenter, C.B. 1947, Report of Investigations Explosions of Ammonium Nitrate Fertilizer on Board the S.S. Grandcamp and S.S. High Flyer at Texas City, Tex., April 16, 17, 1947. Lawrence Livermore National Laboratory 2002, Cheetah Model Description, web page current in September 2002, http://www.llnl.gov/str/Fried.html. Mannan, S. 2005, Lees Loss Prevention in the Process Industries, 3rd Edn. Medard, L.A. 1990, Accidental Explosions Volume 2: Types of Explosive Substances, Translator P. Fawcett, Ellis Horwood Limited, chapter 23 (Ammonium nitrate and its thermal decomposition) and chapter 24 (The explosive properties of ammonium nitrate).

CONCLUSIONS The risks of transporting large shipments of ammonium nitrate through Australian ports is low due to the very low likelihood of large explosions coupled with the signicant distances (. 1 km) to large populations. The risk is likely to meet current individual fatality risk based criteria. The societal risk associated with shipments of ammonium nitrate varies signicantly with larger shipments. The distance from the ship to residential or commercial populations is an important factor in determining the fatality risk. For the population distribution and shipment costs considered in this study, the lowest ratio between PLL and shipment cost is for a shipment size of 2000 te. This shipment size also corresponds to the societal risk