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# 2007 IChemE

IChemE SYMPOSIUM SERIES NO. 153

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 deflagrate?
. How should the consequences of a fire 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 significant 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, fire, explosion, transportation, ports, shipping

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 fire 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 fires 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.

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 sufficiently
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 specific aspects of the transportation. This can improve the delivered quality of the

# 2007 IChemE

IChemE SYMPOSIUM SERIES NO. 153

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:

2.

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 fire 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 fire 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 fire in a fully laden ship with all the
ammonium nitrate stored in one hold or in close proximity. The uncontrolled fire could cause a fraction of the
ammonium nitrate potentially contaminated and heat
affected by the fire to detonate and then to propagate
through the rest of the shipment.

3.

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

is unlikely for an accident to cause contamination of a


significant 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 confinement 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 filled its bunker tanks. The fuel flowed 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.

# 2007 IChemE

IChemE SYMPOSIUM SERIES NO. 153

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
fictitious 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 flow 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 fire precedes the
explosion. This period can be used to evacuate people
from the vicinity of the ammonium nitrate, which can
significantly reduce the numbers of people who may
be killed or injured by an explosion. This factor has
not been considered in this study.

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), significant changes were
made to the composition of ammonium nitrate and the emergency response actions that would occur in the event of
a fire.
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:
.
.
.

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
specific individual fatality risk contours and the risk of
defined 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 official 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 fire or the potential for property
to be damaged.

30.0

1200

25.0

1000

20.0

800
15.0

600

10.0

400
200

5.0

0.0
2500

500

1000

1500

2000

People per Hectare

People in Rings
Surrounding Ship

Local Population
1400

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.

Population

Population
Density

COST OF SHIPPING
The cost of shipping ammonium nitrate comprises two components:

Distance (m)

1.
Figure 1. Populations surrounding shipment of ammonium
nitrate

A fixed administration cost per shipment which is independent of the size of the shipment. This is assumed to
be $5000.

# 2007 IChemE

IChemE SYMPOSIUM SERIES NO. 153


Average cost per tonne

Fatality Risk

Cost per Tonne

$200

1.E-06

$150

Small ship
explosion

1.E-07

Partial ship
explosion

$100

1.E-08

$50
$0

Complete ship
explosion

1.E-09
0

5000

10000

15000

Total

20000

1.E-10

Shipment Size (te)

Figure 2. Average cost per tonne of ammonium nitrate


shipments

500

1000

1500

Figure 4. Location specific 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 fixed 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.

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.

The costing is shown in Figure 2. It is significantly 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

70

100

60

200

Societal Risk
F (frequency of events
causing N or more fatalities)

Peak Overpressure (kPa)

80

500

50

1000

40

2000

30

5000

20

10000

10

20000

0
0

1000

2000

3000

4000

5000

6000

Distance (m)

100 te
200 te

1.E-04

500 te
1.E-05

1000 te
2000 te

1.E-06

5000 te
10,000 te

1.E-07

20,000 te
1.E-08

Lower Limit
Upper Limit

1.E-09
1

10

100

1000

10000

N (Fatalities)

Figure 3. Overpressure from explosions of various sized


shipments

Figure 5. Societal risk as a function of shipment size

# 2007 IChemE

IChemE SYMPOSIUM SERIES NO. 153

Cost vs Benefit
$200

0.0003

$150

0.0002

$100

0.0001

$50

Shipment Cost ($/te)

PLL

0.0004

Potential
Loss of Life
Average
Cost of
Shipment
Ratio

$0
0

5000

10000 15000 20000

Shipment Size (te)

Figure 6. Costs and benefits 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 benefits 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 significant 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 significant
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 significantly 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