CPR15 Utmutato

RISK ANALYSIS METHODOLOGY FOR CPR-15 ESTABLISHMENTS
The Hague, October 1997
Ministry for Housing, Spatial Planning and the Environment (VROM)

Directorate-General for Environmental Protection
Directorate for Chemicals, External Safety and Radiation Protection
External Safety Division / IPC 655
P.O. Box 30945
2500 GX The Hague
The Netherlands
Risk Analysis Methodology for CPR-15 Establishments 2
PREFACE
Dangerous materials may each posses widely divergent hazardous properties and can therefore cause
external safety risks during undesirable situations. Depending on the hazardous properties and the type of
packaging material, chemicals are stored at a suitable level of protection. The present report contains a
methodology for calculating the risks of dangerous materials that are stored under various protection levels.
For this purpose, a detailed study has been made to determine which probability factors for failure of fire
fighting systems must be applied. In addition, recent insights into the formation of toxic combustion
products of nitrogenous chemicals have been taken into account. Furthermore, the report contains a
sample risk analysis.
The methodology described with which a quantitative risk analysis can be carried out for stored materials
subject to the CPR 15, number DGM/SVS/97560078 October 1997 circular is applied in the following
cases:
- A company is subject to the Serious Accident Risks Order. A quantitative risk analysis must always be
set up for stored materials, even if storage complies with the distances in the distances table in the
CPR 15 circular. However, this risk analysis for storage does not have to be carried out if the stored
material is not selected within the sub-selection system for carrying out a quantitative risk analysis for
an establishment.
- A company is of the opinion that, on the basis of the hazardous materials stored in combination with
the safety measures installed, a shorter distance to sensitive destinations can be used than stated in
the CPR 15 circular.
- The distances in the CPR 15 circular are insufficient. The circular states that this may be the case if
combustible nitrogen compounds have been stored with a nitrogen content in excess of 1.5% in cases
of materials with 100% active substance percentage, or if the number of persons per hectare indicated
is exceeded as stated in the CPR 15 circular within the distances stated in the table.
- So many processes involving the packaging of very toxic materials occur outside the storage building
that results in greater external safety distances than stated in the tables.
Please refer to the CPR 15 circular for comparing the calculation results to the external safety limits.
The head of the External Safety Department,
Drs. G.C.M. Lommers

Table of Contents
1 INTRODUCTION 5
2. PRECONDITIONS 6
2.1. When is a Risk Analysis necessary? 6
2.2. Materials and Material Categories 7
2.3. CPR 15 Regulations 8

2.3.1. Protection Levels 8
2.3.2. Miscellaneous Preconditions 8
2.4. Risk to the Surroundings 8
3. RISK ANALYSIS OF THE RELEASE OF STORED PRODUCTS 10

3.1. Introduction 10
3.2. Release of Toxic Solids 10

3.2.1. General 10
3.2.2. Source Strength 11
3.2.3. Effect and Damage Calculations 11
3.2.4. Probabilities 12
3.2.5. Sample Calculation for the Release of Toxic Solids (Powders) 13
3.3. Release of Toxic Liquids 14

3.3.1. General 14
3.3.2. Source Strength 15
3.3.3. Effect and Damage Calculations 15
3.3.4. Probabilities 15
3.3.5. Sample Calculation for Release of Toxic Liquids 16
4. FIRE 18
4.1. Introduction 18
4.2.1. Fire Scenarios 20
4.2.2. Stored Materials 21
4.2.3. Burn rate 22
4.2.4. Source Strength of Toxic Combustion Products and Non-combusted very Toxic Materials 24
4.2.4.1. Formation of Toxic Combustion Products 24
4.2.4.2. Emission of Non-combusted Toxic Product 25
4.2.4.3. Source Strength 25
4.2.5. Toxicity 28
4.2.6. Dispersion 28
4.3. Frequency Estimates 29

4.3.1. Introduction 29
4.3.2. Factors that Influence Fire Frequency and Fire Spread 30
4.3.3. Fire Frequency for Chemicals Storage 31
4.3.4. Probability of a Fire Scenario for the Various Protection Levels/systems 31
4.3.4.1. System 1: Automatic Sprinkler Installation 31
4.3.4.2. System 2: Automatic Deluge Installation 32
4.3.4.3. System 3: Automatic Gas Extinguishing Installation 34

4.3.4.4. System 4: Local Fire Department with Dry Deluge System 34
4.3.4.5. System 5: Automatic Hi-ex Installation 35
4.3.4.6. System 6: Company Fire Brigade with Manual Deluge Installation 36
4.3.4.7. System 7: Company Fire Brigade with Dry System 36
4.3.4.9. System 9: Automatic Hi-ex with Inside Air 38
4.3.4.10. Protection Level 2: < 6 Minutes 39
4.3.4.11. Protection Level 2: < 15 Minutes 40
4.3.4.12. Protection Level 3 40
4.4. Calculation of Individual and Group Risk 41
4.5. Sample Calculation for Fire in a Chemicals Storage Facility 41

4.5.1. Description of the Storage Facility 41
4.5.2. Effect and Damage Calculation for Fire 41
4.5.2.1. Fire Scenario 41
4.5.2.2 Stored Materials 42
4.5.2.3. Fire Speed 43
4.5.2.4. Source Strength 43
4.5.2.5. Toxicity 44
4.5.2.6. Dispersion 44
4.5.3. Probability Estimates 45
4.5.4. Risk Calculation and Presentation 46
5. REFERENCES 47
Appendix:
1 Meteorological Conditions at Schiphol Weather Station 49
1 Introduction
Regulations are laid down in the CPR 15-2 and CPR 15-3 guidelines for the storage of hazardous materials
in quantities from 10 metric tons and up and pesticides/herbicides in excess of 400 kg. If the distance of the
storage facility to the residential area is smaller than that indicated in the VROM CPR 15 circular, a
quantitative risk analysis will have to be carried out for such storage facilities. This report will describe the
method for carrying out this risk analysis recommended by VROM. The assumptions and starting points for
the risk calculations will be described in this report. Among other things, this involves:
- the accident scenarios to be considered

- fire development and source strengths of hazardous materials and toxic combustion products
- damage models to be used
- probability of the various accident scenarios.
In many cases no risk analysis need be carried out for CPR 15 storage. Chapter 2.1 indicates under which
circumstances a risk analysis must be carried out and when a risk analysis is not required.
In addition, Chapter 2 discusses which accident types and physical effects are relevant for the external risk
using the content of the CPR 15-2 and CPR 15-3 guidelines for its basis.
Chapters 3 and 4 indicate which calculations must be carried for each of the identified accident types. The
risks of the scene of an accident involving hazardous materials are determined by the amount of material
that is created and/or released, the dispersal of the material in the area and the damage resulting from the
exposure of those present. In addition to this, the chances of an accident occurring and the incidence of
damage are important factors. It is indicated which parameters are important when calculating the source
strength, whether building effects must be taken into account (if so, where) and what the relevant chances
are. A sample calculation is provided for each accident scenario.
This risk analysis method for CPR 15 companies has been drawn up by the Department of Industrial Safety
of TNO Environment, Energy and Processing Innovation by order of the Ministry for Housing, Spatial
Planning and the Environment (VROM). TNO was itself guided in setting up a methodology by a study
group initiated specifically for this purpose.
2. Preconditions
2.1. When is a Risk Analysis necessary?
The CPR 15-2 guideline is applicable to storage facilities with a capacity of at least 10 metric tons in which
hazardous materials, chemical waste materials or pesticides/herbicides which are stored in packaging. The
CPR 15-3 guideline is primarily directed towards the distributors of pesticides/herbicides who are in fact the
link between the user and the synthesizing and formulating company. The guideline consists of a package
of measures for stored materials of between 400 kg and 10 metric tons and a package of measures for
stored materials from 10 metric tons and upward.
If the distance of a CPR 15 storage facility to dwellings or other vulnerable subjects (category II) is smaller
than the indicative distances stated in the VROM CPR 15 [18] circular, a quantitative risk analysis must be
carried out for such storages. If these indicative distances have been complied with but materials have
been stored that pose a greater risk, insight must be provided into the divergent risk to the competent
authorities. This is applicable in cases where flammable nitrogen compounds such as nitrous and amino
compounds and flammable nitrogen compounds with amine, cyanide, cyanohydrine, aniline and isocyanate
are stored. The indicative distances that are stated in the CPR 15 circular are based on an N content of
1.5% for a substance with 100% active substance percentage. If the N content of the total amount of stored
chemicals (involving a substance with 100% active substance percentage) is greater than 1.5%, a
quantitative risk analysis is required. The risk is lower for the storage of formulated active materials. For
these kinds of stored materials the boundary value of the nitrogen content that would require a quantitative
risk analysis lies at 1.5/F%, where F is the fraction for the average active substance stored. For example,
when the active material content stored averages 30% (active material fraction 0.3) the boundary value will
be 1.5/0.3 = 5%. Please see Chapter 4 and the sample calculation for determining the percentage of
nitrogen and the average active material percentage.
A quantitative risk analysis need not be carried out if no toxic materials have been stored and no toxic
combustion products can be formed. This is the case if no materials have been stored with a LD50 (rat) <
25 mg/kg and one of the conditions below has been complied with:
a) only chemicals have been stored that do not contain sulphur, nitrogen, chlorine, fluorine or bromine
b) only the storage of watery inorganic acids and bases has occurred, unless toxic fumes can be released
c) only the storage of inorganic salts occurs
d) only the storage of non-flammable materials occurs
e) combinations of a, b, c, and d.
Companies that are subject to the Major Accident Decree are at all times obligated to draw up a
quantitative risk analysis.
However, it is a requirement for all stored material that a distance of 20 meters is maintained to
dwellings or other vulnerable subjects (category II) [13].
2.2. Materials and Material Categories
The area of operation of CPR-15 extends to the following Environmentally Hazardous Materials Act (WMS)
materials categories:
- oxidizing NOT: peroxides, nitrates

- extremely flammable (K1) NOT: spontaneously combustible materials, flammable gasses,
materials that develop flammable gasses after a reaction with water
- flammable (K2)
- very toxic
- toxic
- harmful
- corrosive
- irritant
- materials hazardous to the environment.
In determining the protection levels (see 2.3.1.) each of these categories is subdivided on the basis of
flammability. The following subdivision results:
- K1/K2 liquids
- K3 liquids
- K4 liquids (flash point > 100°C)
- flammable solid materials
- non-flammable solid materials.
In addition, when determining the protection level, the nature of the packaging has also been taken into
consideration. Non-metal packages are assumed to be more flammable than metal packages
The WMS categories together with the subdivision according to flammability form a matrix that serves as a
basis for determining the scenarios in this study.
The CPR 15-3 guideline is primarily aimed at the pesticide/herbicide agents distribution companies which
are in fact the link between the synthesizing and formulation company and the user. In the CPR 15-3
guideline, a pesticide/herbicide is understood to be a material or mixture of materials as defined in article 1
of the Pesticide/Herbicide Agents Act (Stb. 1962).
Within the parameters of this study, only external “human” risk is considered. Scenarios for flammable
materials and (very) toxic materials are considered. As on the basis of previous studies it has been
determined that the creation of toxic combustion products can be an important cause of mortality in the
area, scenarios for materials that can form toxic combustion products will also be considered.
Gasses are not subject to guidelines CPR 15-2 and CPR 15-3 and, as such, they are not included in this
study.
2.3. CPR 15 Regulations
2.3.1. Protection Levels
The following protection levels have been determined in the CPR 15-2 guideline on the basis of the fire risk
of stored material and the possible damage to the environment of any materials released:
1. (semi-) automatic extinguishing system or firefighting system with company fire brigade, fire detection,
extinguishant collecting provision, preventive measures
2. fire detection, extinguishant collecting provision, preventive measures
3. preventative measures.
No distinction is made between protection levels in the CPR 15-3 guideline. All CPR 15-3 storage facilities
with a storage capacity in access of 10 metric tons are subject to protection level 1.
These protection levels serve as premises for this study.
2.3.2. Miscellaneous Preconditions
In addition to a protection level, CPR 15-2 and CPR 15-3 guidelines require measures with regard to:
- compartmentalization
- product containment
- fire hose water containment.
Compartmentalization can influence development of a fire and therefore the effects on the area. Product
and fire extinguishing water containment not relevant for the external risk to this risk analysis methodology.
2.4. Risk to the Surroundings
As the materials are stored in packaging, the amounts that can be involved simultaneously in case of
accident are limited. Accidents in which consequences for the area may occur are:
1. The release and ignition of a flammable liquid.

The release and ignition of flammable liquids can cause injury in the immediate area. Direct ignition of
the pool formed will result in a pool fire. Assuming a maximum pool surface of 1500 m2 and using the
heat radiation model from the Yellow Book [6] the heat intensity in the area has been calculated for
xylene, methanol and benzene. It has been discovered that in cases of a pool fire a thermal intensity of
16.5 kW/m2 (corresponding to 1% lethal injury) can occur at distances of 30 m.
When the released liquid is not directly ignited, evaporation can form a flammable gas cloud. The surface
of the gas could corresponds to the area within which the gas concentration lies above the LEL (Lower
Explosion Limit). For methanol the evaporation rate from a pool of 1500 m2 at an ambient temperature of
20°C equals 0.65 kg/s. At wind speeds of 2 m/s the LEL will be reached for this source strength at a
distance of 30 m [6]. It is assumed that upon ignition, no lethal injury will occur outside the cloud.
On the basis of the limited damage distances for heat radiation and gas cloud combustion, this contribution
to the external risk of the storage of flammable liquids in packaging is considered negligible. The effect of
the storage of flammable liquids in packaging on the creation of toxic combustion products is discussed in
point 3.
2. The release of toxic liquids or powders.
3. A fire in the storage facility with the formation of toxic combustion products.
Table 2.1. The physical effects and the possible contribution to the risk for the area of accidents in a
chemical storage facility.
Accident Type Physical Effects Risk to Area
Failed packaging:
- toxic solid Powder dispersion Yes
- toxic liquid pool formation/evaporation Yes
Fire Heat radiation No
Release and dispersal of Yes

non-combusted toxic products
Release and dispersal of toxic Yes

combustion products
It can be concluded from this table that the following accident types can contribute to area risk:
• release of toxic solids (Chapter 3.2.)

• release of toxic liquids (Chapter 3.3.)
• fire (Chapter 3.4.)
3. Risk Analysis of the Release of Stored Products
3.1. Introduction
The release of pure material refers to the release of (very) toxic materials from their casing. The following
types are distinguished:
- failure of the packaging of toxic solids in which the wind gains purchase on the product and disperse it
in the area
- the release of toxic liquids causing a pool followed by evaporation from this pool and exposure of the
residents to toxic fumes.
The probabilities are distributed as follows:
- data about the presence of the product concerned in the storage facility
- failure data of the packaging
- the development probabilities of the accident, meaning the probability of follow up effects (combustion
for example) the probability of a particular concentration pattern (determined by meteorological
circumstances) etc.
The following constitute meteorological circumstances:

- wind direction
- wind speed
- the stability class (Pasquill Class).
Frequency distributions for the wind direction are known for weather stations in the Netherlands [10]. The
frequency distribution of the weather station closest to the storage facility must be taken as a basis. The IR
has been calculated over a period of 24 hours. The data from the Schiphol weather station is used for the
sample calculations (see Appendix 1).
3.2. Release of Toxic Solids
3.2.1. General
Whenever the packaging of a solid fails, the content may be released, may become airborne and dispersed
in the area. This scenario is only relevant if the particle size of the solid is such that the particulate matter
can be carried off by the wind to the area. This means that this scenario applies only to powders. Solids of
a larger shape, such as granules, pellets, crystalline compounds and the like will not contribute to the
external risk when released.
Solids are transported in various types of packaging (sacks, big bags, IBCs). The amount released will
depend, among other things, on packaging size. In accordance with VLG/ADR, Maximum packaging
volumes have been set for road transport. For transports of toxic solids a maximum packaging size of 400
kg for very toxic solids (these are solids with a LD50(oral, rat) ≤ 5 mg/kg) has been determined. Less toxic
solids may be transported in IBCs. In such cases, packaging size does not exceed the maximum of 3 m3.
3.2.2. Source Strength
The source strength upon the release of powders is equal to the product of:
- the content of the damaged packaging
- the fraction of active substance
- the fraction of the content being released from the packaging
- the fraction of particles that are sufficiently small to be dispersed and inhaled.
The fraction of active substance depends on the product. Pesticides/herbicides are often stored in formulas
in which an active substance percentage of 10-20% is normal. Chemicals are often stored in their pure
state; the active substance percentage will then be 100%. When calculating the risk, the actual value must
be used.
Upon damage, not the entire contents will be released. As for the fraction of particles that are released, this
is assumed to be 10%. This value corresponds to what has been determined in the Bottlenecks
Consultation [9].
Only small particles are dispersed. In addition to this, only those particles with a diameter ≤ 10 μm can be
inhaled and can therefore possible inflict damage upon exposure [4]. Therefore, for this scenario it is
assumed that the source strength of dispersing powder is equal to the amount with a particulate size
smaller or equal to 10 μm. The fraction must be determined through means of an analysis or it must be
indicated by the manufacturer.
3.2.3. Effect and Damage Calculations
Dispersion
Upon dispersal of the powder released, it may be assumed that the powder with particles smaller than 10
μm will be dispersed in a Gaussian fashion [5]. Any recirculation occurring due to the building is taken into
consideration upon dispersion. This is done by modeling the source as a surface source with height. The
root of the surface in m2 is taken as the width and length of this source, the height being equal to the height
of the building. With the aid of the Gaussian dispersion model [6] the concentrations for this
time-dependent source in the area can be calculated.
Damage Calculation
For the risk analysis methodology for CPR 15 companies, a probit function for inhalational exposure is
derived for solids with a LD50(rat, oral) of 5 and 25 mg/kg respectively, in accordance with the methodology
of the Damage Book [7] or the EVR Bottlenecks Consultation [8]. Assuming an n of 2 and an incline b of 1,
the probit function will be:
- for LD50 = 5 mg/kg:

Pr = -5.53 + ln C2t (3.1)
- for LD50 = 25 mg/kg:

Pr = -8.75 + ln C2t (3.2)
In which:
C = concentration [mg/m3];
t = exposure duration [min].
3.2.4. Probabilities
It is in particular calamities of which the effects will be noticeable in the area that are considered when
determining the probability of an accident scenario. In this respect, a calamity is the tearing of the
packaging such that the wind gains purchase on its contents and the powder is dispersed in the area.
However, when a packaging tears within the storage building, an accident scenario with damage outside
the storage facility is not likely. This is why only accidents occurring outside are important. This comes
down to accidents while transferring loads. This has been taken into consideration in determining the failure
frequency of the various packagings.
The failure frequency of the packagings concerned depends on the number of times that a packaging fails
during load transfer. For example: due to a collision or due to careless positioning on the forklift truck and
on the chance of leakage. The [11] publication indicates a failure frequency for packed goods of 10-2 - 10-4
for each packaging handled (a handled packaging includes the full entry, storage and issue cycle). These
values are applicable to standard packaging materials and for normal handling. Due to transport
regulations (VLG/ADR) toxic materials must be transported in approved packagings. In addition, more
attention is paid to the handling of hazardous materials than that of normal packed goods. It is for these
reasons that a low failure rate with release of the contents is assumed for solid chemical materials, namely:
10-5 for each packaging handled (sack, box, big bag, IBC). If sacks or drums have been affixed to a pallet
using shrink wrapping or loops/bands the failure frequency will be applicable to each pallet. This means to
say that the failure rate of a packaging is equal to 10-5 divided by the number of packagings on the pallet.
The over all probability that a toxic solid will be released from a packaging is equal to the product of the
-5
failure rate (10 /per packaging handled) and the average number of packagings handled annually in the
facility. In doing so, the adjustment made for packagings that are affixed to a pallet by means of shrink
wrapping or bands must be taken into consideration.
3.2.5. Sample Calculation for the Release of Toxic Solids (Powders)
Scenario
The accident scenario that is worked out in this example is the failure of a packaging of 400 kg. It is
assumed that the packaging is damaged due to improper handling and that its contents are partially
released as a result. The accident occurs in the proximity of a storage building with a surface of 2500 m2,
a height of 6 m, width of 30 m and a length of 50 m.
Source Strength
The total contents of the packaging amounts to 400 kg.
This sample calculation assumes an active material content of 50%.
10% of the total contents shall be released.
The percentage of inhalable particles (smaller than 10 μm) amounts to 50%.
These assumptions yield the following source strength:

400 kg x 0.5 x 0.1 x 0.5 = 10 kg
Dispersion
The 10 kg of toxic material is released in the proximity of the storage facility at ground level. Therefore,
when determining dispersion, the influence of the recirculation zone must be taken into account. This
means that a source surface area with a length and width equal to the root from the surface area of the
storage (1500 m2) meaning: 38.7 m will be assumed.
The table below provides the maximum dosage that persons will inhale as the cloud passes. The dose
calculations are based on the damage model given under 4.3. for toxic materials: Pr = -8.75 + ln c2.t
Table 3.1. Maximum concentration of the plume axis and inhaled dose for an instantaneous source of
10 kg of azinphosmethyl powder.
Distance F, 2 m/s D, 5 m/s

Maximum Maximum
[m] Conc. Dose Conc. Dose

[mg/m3] [(mg/m3)2.min] [mg/m3] [(mg/m3)2.min]
≤ 19 3700 10.7⋅105 3700 4.3⋅105
25 3200 10.0⋅105 3200 4.0⋅105
50 2300 8.2⋅105 2100 2.6⋅105
100 1400 4.7⋅105 800 0.6⋅105
200 640 2.6⋅105 - -
300 360 0.7⋅105 - -
Probabilities
In calculating the probability of the scenario concerned occurring, the failure frequency of a big bag is used
(10-5 per big bag handled). The number of handled big bags with toxic solids is set at 50 annually.
Therefore, overall probability is 5·10-4 annually.
Individual Risk
Risk calculations have been carried out for an instantaneous source as described above. In doing so, a
neutral gas-dispersion model was used [6]. The meteorological data is derived from the weather station at
Schiphol (Appendix 1).
The individual risk is presented in the form of an F,X curve (figure 3.1.) for the wind direction of 230 - 250°
(sector 2: west, south-west, see Appendix 1 for frequency). This indicates that for this specific example, an
individual risk of 10-6 annually can still occur at a distance of approx. 150 m and that an individual risk of
10-7 annually can still be reached at a distance of 250 m.
(Lethal Injury Frequency)
(Distance to the Accident)

[insert figure 3.1.]
Figure 3.1. Individual risk/distance curve for failure of a packaging with 400 kgs of toxic solid,
instantaneous source 10 kgs (wind direction 230° - 250° ≈ west, south-west).
3.3. Release of Toxic Liquids
3.3.1. General
Whether and to what degree a material will contribute to the risk for the area depends on the concentration
that shall occur in the area and on the toxicity of the material. The concentration is determined by the
source strength and by the meteorological conditions. The source strength of the evaporating liquid
depends on the evaporation rate from the pool. This is determined by the pool area and also depends on
the ambient temperature and the vapour pressure of the liquid. For risk analyses a standard ambient
temperature of 15°C is often adhered to.
Publication [1] derives information on which combinations of vapour pressure and toxicity will still result in
lethal injury with a probability of 1% at a distance of 100 m (weather class D5, temperature 20°C). This data
is included in table 3.2. When the toxicity of a particular material is greater than or equal to the toxicity that
is given for the vapour pressure concerned (meaning the LD or the LC value of the material is lower than
the given value) the material may contribute to posing an external risk.
Table 3.2. Relevant vapour pressure and toxicity criteria (boundary values) for consideration in risk
analysis.
Vapour Pressure at 20°C LD50(oral, rat) [mg/kg] or

[bar] LC01(person, 30 min) [mg/m3]
< 0.001 < 2.3

0.001 - 0.005 < 13
0.005 - 0.01 < 25
0.01 - 0.03 < 70
0.03 - 0.05 < 1.2⋅102
0.05 - 0.1 < 2.4⋅102
0.1 - 0.2 < 5.2⋅102
0.2 - 0.5 < 1.6⋅103
Liquids are transported and stored in small packaging, drums, IBCs and in tanks of various dimensions.
The maximum packing size for storage inside is an IBC of 3 m3. Materials with a LC50 of no more than 1000
ppm may be transported in packaging sizes of no more than 450 kgs (barrels). This applies to most toxic
liquids.
3.3.2. Source Strength
To calculate the source strength as input in the dispersion model, the evaporation from the pool is
determined on the basis of the pool area and the physical properties of the material (in particular the
vapour pressure). The models from the Yellow Book [6] can be used for this.
3.3.3. Effect and Damage Calculations
Dispersion
When calculating the dispersion, the recirculation caused by the building must be taken into consideration.
This is done by modeling the source as an area source with a height. The root from the area in m2 of the
storage building is used for the width and length of this source. With the aid of the Gaussian dispersion
model [6] the concentrations in the area can be calculated for this semi-continuous source.
Damage Calculation
The probit function for the material released [7] must be used for the toxicity of the material.
3.3.4. Probabilities
The publication in [11] provides a frequency for complete failure for a liquid tank of 5⋅10-5 - 3⋅10-7 annually.
These figures apply to pressureless storage and for stationary tanks. A probability of failure of 10-6 annually
is given for pressure vessels in a note of the Bottleneck Consultation [15]. A failure rate of a factor of 10
higher is maintained for mobile tanks and vessels. Furthermore, as a rule of thumb, a liquid tank will be
stronger than a drum or a vessel. On the other hand, a drum can be placed in an oversized vessel in case
of an accident, which will restrict the outflow. Due to this consideration, the outflow frequency for drums is
determined to be equal to 10-5 annually.
The overall probability is provided by the product of the failure frequency concerned and the annual
average number of packaging units available in the site.
3.3.5. Sample Calculation for Release of Toxic Liquids
General
In the accident scenario it is assumed that 1 vessel and 2 vessels with 200 liters of acrolein fail. Upon the
release of toxic liquids, a liquid pool is formed with a 5 mm thick layer and an area of 40 and 80 m2
respectively.
Source Strength
With the aid of the evaporation model from the Yellow Book [6] is has been calculated that the average
evaporation of acrolein from the pool for A through D weather classes, representative wind speed of 5 m/s,
will amount to 0.17 kg/s (1 vessel) and 0.34 kg/sec (2 vessels) for the duration of approx. 1000 sec. (all
acrolein released has evaporated). For the E through F weather classes, representative wind speed of 2
m/s, average evaporation works out to 0.09 kg/s (failure of 1 vessel) or 0.18 kg/s (failure of 2 vessels).
Dispersion
The acrolein is released in or in the proximity of the storage area at ground level. Therefore, when
determining dispersion, the influence of the recirculation zone will have to be taken into account. This
means that a source surface area with a length and width equal to the root from the surface area of the
storage (1500 m2) meaning: 38.7 m will be assumed. Table 3.3. shows the maximum concentrations of
acrolein on the plume axis.
Table 3.3. Maximum concentration of acrolein (on the plume axis).
Distance to the Concentrations on the Plume Axis [mg/m3]

Source Weather Class
[m] D, 5 m/s F, 2 m/s
≤ 20 65 180
50 50 180
100 30 150
200 20 120
500 - 75
600 - 65
1000 - 35
Damage Calculation
The toxicity of the material is provided by the probit function for acrolein from the Damage Book [7],
namely:
Pr = -4.1 + In Ct (3.3.)
In which:
c = acrolyne in mg/m3
t = exposure time in minutes.
For an exposure of 30 minutes, the LC01 will be 30 mg/m3 on the basis of this damage model.
Probabilities
In calculating the probability of the scenario concerned occurring, the failure frequency of a liquid vessel of
-5
10 per vessel handled is assumed. In addition to this, a scenario is being considered in which two vessels
fail simultaneously (for example, this may be caused because the fork of the forklift truck punctures the
vessels). A probability of failure that is 10 times smaller is used for this: 0.1 x 10-5 = 10-6. This probability of
failure is multiplied with the number of acrolein vessels handled annually which is set to 100. The overall
frequency of the occurrence of these scenarios amounts to:
Failure of 1 vessel: 9 x 10-4 annually.

Failure of 2 vessels: 1 x 10-4 annually.
Individual Risk
Risk calculations have been carried out for a source as described above. The meteorological data is
derived from the weather station at Schiphol.
The results are presented in the F,X curve in figure 3.2. (wind direction of 230 - 250°, see Appendix 1). This
indicates that for the pool evaporation of toxic liquids, an individual risk of 10-6 annually can still occur at a
distance of 200 m and that an individual risk of 10-7 annually can still be reached at a distance of 750 m.
These results can be explained due to the high vapour pressure of acrolein and its great toxicity. Due to
this combination of properties, acrolein can contribute greatly to the external risk.
Figure 3.2. Individual risk/distance curve (F,X curve) for the failure of 200 I vessels of acrolyne (wind
direction 230 - 250° ≈ west, south-west).
4. Fire
4.1. Introduction
In this chapter the risk of a fire in a chemicals storage facility is dealt with. The risk of a fire in a chemicals
storage facility is determined by the release of non-combusted solid material and the creation of gaseous,
toxic combustion products.
Emission of Non-combusted Toxic Materials

During a fire, the stored materials can be emitted in an non-combusted state. If these materials are toxic,
this could pose a risk to people in the area. The release of non-combusted material depends on:
• the amount of material stored that is involved in the fire
• the flash point of the material
• the percentage of active material.
Emission of Toxic Combustion Products

Toxic combustion products like HCl, HF, HBr, SO2 and NO2 etc. are created during the fire if the stored
chemicals are heterogeneous atoms like Cl, F, Br, S and N etc. This is discussed further in point 4.2.4.
4.2. Risk Methodology for a Fire

The risk of a fire in a chemicals storage facility is determined using a risk analysis methodology that is
comparable to the risk analysis methodology for pesticide/herbicide storage [1]. The characteristic of this
methodology is that the risk of a fire is determined on the basis of different fire scenarios that have a certain
chance of occurring. A fire scenario is characterized by the fire duration, the fire area and the burn rate.
The burn rate depends on the composition of the materials stored and the amount of oxygen that is
available during the fire. The composition of the stored material(s) co-determines the nature and the
amount of the toxic combustion products formed. The general rule of thumb here is that the aspects that
play a role during a fire influence each other in various ways. This is reflected in figure 4.1.
┌─────────────────────┐ ┌────────────────────────┐
│ 1. Fire Scenario │ │ 2. Stored Materials │
├─────────────────────┤ ├────────────────────────┤
│ - fire duration │ │ - average structure formula │
│ - fire area │ │ │
│ - ventilation rate │ │ - combustion comparison │
│ │ │
│
└──────┬───────────┬──┘ └┬─────┬────────────┬────┘
│ │ │ │ │
│ ┌──┴───────────────┴┐ │ │
│ │ 3. burn rate │ │ │
│ └───────────┬───────┘ │ │
│ │ │ │
│ ┌────┴────────────┴───┐ ┌────┴────────────────┐
│ │ 4. source term toxic │ │ 5. toxicity
│
│ │ (combustion) │ │
│
│ │ products │ │
│
│ ├─────────────────────┤ ├─────────────────────┤
│ │ - products formed │ │
│
│ │ - emissions per kg │ │ - NO2, SO2, HCl
│
│ │ of combusted material │ │ - non-combusted material │
│ │ - % active material │ └──┬──────────────────┘
│ └────────────────┬────┘ │
│ │ │
│ │ │
│ │ │
┌────────┴───────────────────┐┌─────┴───────────┴──┐
│ 7. probabilities ││ 6. dispersion │
├────────────────────────────┤├────────────────────┤
│ - fire frequency │ │ - weather conditions │
│ - fire fighting system │ │ - damage areas │
│ - weather conditions │└──┬─────────────────┘
└────────────────────────┬───┘ │
│ │
│ │
│ │
┌──┴────────────┴────┐
│ 8. fire risk │
├─────────────────────┤
│ - individual and │
│ - societal risk │
└─────────────────────┘
Figure 4.1. Fire Determining factors and their interrelationships.

4.2.1. Fire Scenarios
Depending on the circumstances at the time of the fire (cause of the fire, materials stored, storage method
etc.) fires in storage facilities can expand with a different speed into a larger fire. This can best be
expressed by defining different fire scenarios for a fire in a particular storage facility that each have a
certain chance of occurring.
A fire scenario is defined by the following three factors:

• fire duration
• fire area (size of the fire)
• ventilation rate (oxygen supply to the fire).
Fire Duration
On the one hand, fire duration is determined by the conditions during the fire and, on the other, by the fire
fighting tactic applied. Paragraph 4.3. deals with the influence of fire fighting in greater detail.
In this study, it is assumed that the duration of the fire is equal to the time needed to extinguish the fire.
Among other things, this depends on the method used to fight the fire. However, a limit is set for the
duration of the fire (in compliance with [12]) that is equal to the assumed maximum exposure duration of
people in the area, namely: 30 minutes. For non-fire -resistant buildings and fire fighting in which smoke
hatches or other ventilation systems are applied, the maximum duration of exposure is 20 minutes as it is
assumed that after that plume rise will occur. Once this effect has occurred, the smoke gasses from the fire
will rise to great heights. Before they reach the surface of the earth again, they have been greatly diluted,
making hazardous effects negligible.
Analogous to [1], it is assumed here that the initial phase of a fire takes about approx. 20 minutes. No
plume shall rise within this period because the combustion products are cooled by the building which has
not yet been warmed up. During the course of the first half hour of the fire, the building will more or less
gradually become damaged. It may be assumed that there will be a gradual transition from a situation
without plume rise to one with plume rise. The effects of such a general change are however difficult to
quantify. Therefore, it is assumed here that plume rise will not occur at all in the initial phase.
Fire Area
The size of the fire area is largely determined by the supply of oxygen and it is also dependent on the fire
fighting system. On the basis of this data, a distribution of probability can be arrived at for a number of fire
areas. Chapter 4.3. discusses this in greater detail. In determining the distribution of probability, it has been
assumed that the fire surface’s maximum will equal the area for the storage space. However, calculations
have shown that during an oxygen restricted fire (low ventilation rate) the maximum area of the fire will be
300 m2.
Ventilation rate
The course of a fire is co-determined by the amount of oxygen available. This is derived from the air that is
present in the storage space and from the air that is supplied through the ventilation openings. The volume
of air supply is expressed in the ventilation rate (number of times per hour that the air in the building is
refreshed). The amount of kilograms per second that burn is particularly dependent on this.
If sufficient oxygen is supplied, the evaporation of the fuel present during the fire (i.e. the burning product)
2
will be the limiting factor. This evaporation is expressed in kg/m .s and is thereby directly related to the fire
area. This evaporation speed will for most chemicals not exceed 0.025 kg/m2.s (K1 en K2 solvents: 0.1
kg/m2.s maximum) and therefore corresponds to the maximum burn rate. If the evaporation speed
determines the burn rate, the fire is referred to as ‘area-restricted’. If too little oxygen is supplied to the fire
to achieve this maximum burn rate, the fire is ‘oxygen-restricted’.
The CPR 15-2 and CPR 15-3 guidelines discuss the ventilation rate for stored materials. It is recommended
to realize a ventilation rate of between 1 to 4 in a storage building. It is assumed that during a fire, the
suction effect of the fire will cause the ventilation rate to reach 4 per hour. This is applicable to a standard
building. Exceptions to this are:
• The use of smoke hatches (for automatic hi-ex installations and for corporate fire departments with
inside access) such that ventilation is unrestricted (ventilation rate ∞).
• Upon use of an automatic gas extinguishing installation a gas-tight space is used and the ventilation
rate is therefore zero.
• If it can be shown that special provisions have been made for the building to restrict ventilation in case
of fire, a lower ventilation rate may be used.
4.2.2. Stored Materials
The stored materials constitute the fuel for the fire. If very toxic materials are present in the storage
(LD50rat,oral ≤ 25 mg/kg) they may pose a threat to the area when released. In addition, materials can form
toxic combustion products when burnt. It is assumed that only materials containing the elements N, S, F, Cl
or Br can contribute to the production of toxic combustion products. Compounds containing chlorine can in
principle also for dioxins (PCDD/PCDFs) although earlier studies have shown that the amounts formed are
so small as to pose no acute threat to the population in the area [2]. All materials are subdivided into a
category (category0) for the emission of toxic combustion products (HCl, SO2, NO2). The stored very toxic
materials from category0 are also sub-divided into (sub)categories1 to determine the emission of very toxic
materials.
Category Description
0 All stored materials.
1 Highly toxic materials (Ld50rat,oral ≤ 25 mg/kg).
To determine the burn rate and the emission of toxic combustion products and very toxic materials, the
average structure formula of the stored materials will have to be determined.
Determining the Average Structure Formula per Category

The starting point for the formation of toxic combustion products selected in the Pesticide/herbicide study
[1] was the “average structure formula” of the stored materials. For example, the average structure formula
contains the elements C, H, O, N, S, Cl, F and Br. It is assumed that the packaging materials, the solvents
and other additives will burn as quickly as the chemicals. It is for this reason that we assume that the
structure formula of the additives is the same as that of the chemicals. The numbers present of the various
elements in the average structure formula for a category are determined as shown below from the amount
(kmol) and the structure formulas of all the active materials stored.
ñ = Σ ni Ni / Σ Ni (4.1)
in which:
ñ = average number of atoms of an element in the average structure formula

Ni = kmoles of particular material i
It is determined by multiplying the inventory of the stored amount (kg) of material i by the
percentage of active material i and to divide it by the molar mass of material i.
ni = number of atoms of an element in the structure formula of material i.
In addition, the average mol mass M of the stored materials in a category is determined from the total
amount of kgs stored in a category divided by the total amount of stored material moles ( = Σ Ni ).
With the aid of formula 4.1., the following structure formula is determined for a category:
Ca Hb Oc Xd Ne Sf
Here X = Cl, Br, F and a, b, c,... are the average number of atoms A for the elements C, H, O,... as
calculated with equation 4.1.
Combustion Formula
A combustion comparison is set up based on the average structure formula. In doing so, a quantitative
conversion is assumed. Nitrogen is not quantitatively converted into NO2. A maximum 35% conversion of N
into NO2 is assumed (see 4.2.4.1). The combustion formula appears as follows:
Ca Hb Oc Xd Ne Sf + {a + (b-d)/4 + 0.35.e + f - c/2} O2 --->
a CO2 + (b-d)/2 H2O + d HX + 0.35.e NO2 + 0.325.e N2 + f SO2 (4.2)
The amount of chemical material that can be burnt at a particular oxygen supply to the fire (burn rate, see:
4.2.3.) and which emissions will occur (source strength, see: 4.2.4.) is derived from these combustion
formulas.
4.2.3. Burn rate
The burn rate is a measure of the amount of material that burns per unit of time. It is assumed here that the
combustion is complete; smoldering fires are not taken into account. The burn rate depends on the amount
of fuel present, in other words: the amount of oxygen required, and on the amount of oxygen available.
Area Restricted Fire

If the amount of oxygen available exceeds the amount of oxygen required, oxygen is not a restricting factor
and the fire is an area restricted fire (see: 4.2.1). In that case, the maximum burn rate per area unit will be
-1 -2
equal to the evaporation speed of the material. For chemicals it is approx. 0.025 kg.s .m [7]. The
maximum burn rate is equal to the product of the evaporation speed and fire area A:
Bmax = 0.025 x A [kg/s] (4.3)
Oxygen Restricted Fire

If the amount of oxygen available is smaller than the required amount of oxygen, the fire is oxygen
restricted. Burn rate will then be determined on the basis of the amount of oxygen available. It is calculated
as follows:
mO2 = 0.2 (1 + 0.5.F) V / (24 x 1800) [kmol/s] (4.4)
with:
mO2 = available (or supplied) amount of oxygen [kmol/s]
F = ventilation rate of the space (number of refreshs of the air per hour)
V = volume of the space [m3]
0.2 = oxygen content of the air
24 = molar air volume [m3/kmol];
1800 = oxygen supply period [s].
The required amount of oxygen (Z0) is equal to the term {a + (b-d)/4 + 0.35.e + f - c/2} from the combustion
equation of the stored material(s) (4.2). The burn rate B in kg/s will then be equal to:
B0 = mO2 x M / Z0 (4.5)
with:
B0 = burn rate of category 0 materials [kg/s]
mO2 = available (or supplied) amount of oxygen [kmol/s]
M = average molecule mass of the stored material(s) [kg/kmol]
Z0 = required amount of oxygen for the combustion of 1 mole of the material(s) stored
[mol/mol].
Differentiation between Area Restricted vs. Oxygen Restricted

Initially, the ventilation rate is considered in order to determine whether the fire is area restricted or oxygen
restricted. If ventilation is unrestricted (F = ∞), the fire is always area restricted. When the ventilation rate is
finite, the fire area will be restricted to a particular fire area. The fire will be oxygen restricted if the areas
are larger. The transition point is determined by comparing Bmax with B0:
- if Bmax ≤ B0 : area restricted

- if Bmax > B0 : oxygen restricted
4.2.4. Source Strength of Toxic Combustion Products and Non-combusted very Toxic
Materials
4.2.4.1. Formation of Toxic Combustion Products
Toxic combustion products are formed during the fire if the stored chemicals contain heterogeneous atoms
like N, S, Cl, F, Br, Mn, Zn and so on. Upon the formation of toxic combustion products, only the formation
of NO2, SO2, HCl, HF and Hbr will be considered. Analogous to the Damage Book [7], it is assumed in
doing so that the calculated formation of NO2 is indicative of the amount of nitrogen oxides formed in
general (NOx) and also for the formation of any HCN. The toxicity of NO2 and that of HCN are comparable.
The amount of toxic combustion products that is released is not only determined by the amount of material
involved in the fire, but also on the degree to which NO2, SO2 and HCl (and/or HF and/or HBr) are formed.
This in turn depends on the composition of the burning materials and on the conditions during the fire. For
the conversion of S into SO2, Cl into HCl, F into HF and Br into HBr, it is assumed that conversion in a fire
is 100% complete. In a separate study group for the conversion of N into NO2 during a fire, NOx formation,
consisting of members from the risk evaluation subcommittee of the Commission for the Prevention of
Disasters it has been agreed that the conversion of N into NO2 during a fire will be determined as indicated
below.
On the basis of literature research [17] it has been determined that the actual conversion percentage from
N to NOx is on average set to 10%. In order to take into account uncertainties upon the conversion of N to
NOx (non-combusted initial products and other toxic components that can result from the combustion) an
additional 25% is added to this. This means that in a fire in a storage shed containing chemicals and/or
pesticides/herbicides a conversion percentage amounting to 35%, including the supplement, must be taken
into account. If the actual conversion percentage from N to NOx is available in the literature, the actual
conversion percentage, increased by the 25% supplement, can be taken into account in a quantitative risk
analysis.
No distinction is made between the conversion of N to NOx in a fire in heterogeneous and monotype
storage.
Table 4.1. Conversion Factors for Combustion Products
Element Combustion Product Conversion Factor
C CO2 1
H H2O 1
Cl HCl 1
Br HBr 1
F HF 1
N NO2 0.35
S SO2 1
4.2.4.2. Emission of Non-combusted Toxic Product
The amount of non-combusted material that is released during a fire depends greatly on the properties of
the burning materials and on the conditions during the fire. Considering the current level of technology, a
quantitative evaluation in this respect would go too far. This is why providing the following rules of thumb [1]
will suffice:
• for materials with a flash point ≤ 100°C, 10% shall be released

• for materials with a flash point > 100°C, 2% will be released.
This rule of thumb is based on the fact that materials with a low flash point evaporate quickly and therefore
burn less completely than materials with a low evaporation speed (high flash point).
4.2.4.3. Source Strength
Introduction
In addition to the above-mentioned conversions, the source strength of the various materials being
released is determined by the burn rate (see 4.3.) and by the amount of the chemicals from the material
category concerned in the fire. It is difficult to quantify exactly what part the various materials categories in
a fire will play. Among other things, this depends on the flammability of the materials and the oxygen
requirement for the combustion of the materials. This is why it is assumed that the part that a category
plays in the fire is equal to the oxygen requirement for complete combustion of the materials in that
category (formula 4.8).
During a fire in a storage space, the packaging materials and the flammable formula components will also
burn. For those chemicals that are formulated with non-flammable materials, the burn rate will be lower as
not all chemicals will reach sufficiently high temperatures that will permit them to evaporate and thus
contribute to the fire.
Both the influence of the burning of packaging materials and formulated components and the influence of
inert filler materials on the resulting burn rate of the active materials cannot be quantified by current level of
technology. In this study it has been assumed that the burn rate of the packaging materials and additives is
the same as the burn rate of the chemicals.
Based on the average structure formula, the emission for a particular toxic combustion product per kg of
burnt product can be calculated as shown below.
Emission Combustion Products HCl, NO2, SO2

Material category 0 contains all stored materials. The amount of combustion products being released is
derived from the combustion comparison (4.2). The following conversions in kg per kg of burnt material
have been derived from the combustion comparison (4.2). Due to the comparable toxic effects, the
emissions of HF and HBr are considered to be HCl emissions and added to the HCl emission.
HCl: (cl x 36.5 + f x 20 + br x 81) / M
NO2: (n x 46) / M
SO2: (s x 64) / M
η = ( cl x 36.5 + f x 20 + br x 81 + 0.35.n x 46 + s x 64 ) / M (4.6)
in which:
η = total conversion in kilograms HCl, NO2 and SO2 per kg of burnt chemicals
M = average molar mass of the stored materials (kg/kmol)
cl = number of HCl moles formed per mole burnt (mol/mol)
f = number of HF moles formed per mole burnt (mol/mol)
br = number of HBr moles formed per mole burnt (mol/mol)
0.35.n = number of NO2 moles formed per mole burnt (mol/mol)
s = number of SO2 moles formed per mole burnt (mol/mol)
36,5 = molar mass of HCl (kg/kmol)
20 = molar mass of HF (kg/kmol)
81 = molar mass of HBr (kg/kmol)
46 = molar mass of NO2 (kg/kmol)
64 = molar mass of SO2 (kg/kmol)
The source strength at NO2, HCl and SO2 is calculated from the conversion above and the burn rate:
m = η x B0 (4.7)
in which:
m = source strength of toxic combustion products NO2, HCl and SO2 (kg/s)
B0 = burn rate of category 0 materials determined using formula 4.5
Emission from Non-combusted Material

This scenario is important for the chemicals that also fall into subcategory 1: highly toxic materials (LD50
rat,oral ≤ 25 mg/kg).
The burn rate for subcategory 1 materials are determined as follows:

• With the aid of formula 4.1. an average structure formula is determined for the subcategory 1 materials.
• The oxygen requirement for the burning of 1 mole of average subcategory 1 material is determined
using equation 4.2.
• The burn rate of subcategory 1 materials is equal to the burn rate of category 0 multiplied by the relative
oxygen requirement of subcategory 1 with regard to the oxygen requirement of category 0:
B1 = [O2]1 / [O2]0 x B0 (4.8)
in which:
B1 = burn rate of subcategory 1 materials (kg/s)
B0 = burn rate of category 0 materials (kg/s)
[O2]0 = oxygen requirement for complete burning of the category 0 materials; this is equal to the
total number of category 0 material moles multiplied with the oxygen requirement per mole
of category 0 material (equation 4.2.)
[O2]1 = oxygen needed for complete burning of the subcategory 1 materials; this is equal to the
total number of subcategory 1 material moles multiplied with the oxygen requirement per
mole of subcategory 1 material (equation 4.2.)
The source strength of the non-combusted material is determined as follows:
m = 0.02 or 0.1 x %active1 x B1 (4.9)
in which:
m = source strength of non-combusted very toxic material (kg/s)
%active1 = weighted average weight percentage of active category 1 material
B1 = burn rate for subcategory 1 materials (kg/s)
4.2.5. Toxicity
This paragraph deals with the toxicity of the various materials that may be released in a fire, namely: the
toxic combustion products NO2, HCl, SO2 and non-combusted, very toxic material.
Toxic Combustion Products NO2, HCl, SO2

The source strength for toxic combustion products is determined in 4.2.4. The source strength consists of a
mixture of NO2, HCl and SO2. The calculation of the damage resulting from exposure to a particular
concentration of a toxic material for a certain length of time occurs through the use of the probit function
concerned. The Damage Book [7] provides a methodology for calculating the probit functions of people. For
some 30 materials probit functions have been derived from this. Whenever there is a case of exposure to a
mixture of materials, as is often the case for toxic combustion products, a special probit must be used. It
has been derived from publication [4] that for mixtures of materials with a comparable toxic effect, the
common probit is provided by:
Pr = a1 + ln { [(f1C)n1+Σi δi(fiC)ni] x t} (4.10)
in which:
Pr probit value
a1, n1 probit constants for material 1
ai, ni probit constants for material i (i = 2, 3, ...)
f1 , f i weight fraction of the material concerned in the mixture
C sum of the concentrations of the materials [mg/m3]
δi exp(ai - a1).
For a mixture of NO2, SO2 and HCl and assuming the probit functions from the Damage Book [7] it means:
Pr = -18.6 + ln { [ (fNO2C)3.7 + 0.549 (fSO2C)2.4 + 1.47 x 105 (fHClC) ] x t } (4.11)
The 4.11 probit function can only be derived if b=1 in Pr = a + b ln Cnt.

In the risk evaluation subcommittee of the Commission for the Prevention of Disasters, it has been agreed
that for HCl the probit function will be Pr = -37.3 + 3.69 ln Ct. This probit function will not allow the probit for
the mixture to be derived as b 3.69. If the user wishes to take Pr = -37.3 + 3.69 ln Ct for HCl into account
then the risks for NO2, SO2 en HCl can be calculated separately and the results of the individual
calculations can then be added up. The probit relations for SO2 and NO2 are:
SO2: Pr = -19.2 + ln C1.9t

NO2: Pr = -18.6 + ln C3.7t
(The results of the two calculation methods differ marginally).
Very Toxic Material

The damage models in the Damage Book [7] can be used to calculate the damage resulting from exposure
to non-combusted very toxic products.
4.2.6. Dispersion
An important aspect of the dispersion of materials as a result of a fire is the possibility of plume rise. It has
already been indicated in 4.2.1. that the emissions into the area of the fire scenarios are related to the
duration of the fire in which plume rise occurs. Therefore, plume rise does not play a part in dispersion
calculations in this study.
The source height for the dispersion of materials being released from the storage space is equated to the
height of the ventilation outlets. If the ventilation outlets have been created at the top of the storage area,
the source height is equal to the height of the storage space.
Considering that it is assumed that the products being released will disperse like a neutral gas in the area,
a neutral, gas-dispersion model can be used for the dispersion calculations. As the release occurs from
within a (burning) building, mixing of the material being released in the recirculation zone of the building
must be taken into consideration. The resulting concentration and the measurements of the source are
calculated in an analogue fashion as in 3.3.3.
With the aid of the dispersion model the concentrations of the toxic materials that could occur in the area
are calculated. The resulting concentrations will be averaged within the dispersion model for a time period
that is equal to the exposure duration for people in the area. The concentrations calculated are related to
the damage models in 4.2.5. This indicates the damage areas to be expected as a result of a fire in a
chemicals storage.
4.3. Frequency Estimates
4.3.1. Introduction
The risk analysis method differentiates between the frequency (number of times annually) that a fire will
occur in a storage facility and the (development) probability, given a fire, that the fire will grow to a
particular fire surface. This development of a fire into a certain volume is expressed in fire scenarios. How
quickly a fire develops depends on the effectiveness and reliability of the extinguishing system. If there is a
fast-response, effective fire extinguishing system, such as a gas extinguishing system for example, the
chance that the fire will spread is small. This means that there is a good chance that the fire area will be
small and little chance that it will be large. If the extinguishing system responds slowly, or if there is a delay
such as a fire department having to break in for example, the probability of a small fire area will be small as
the fire will have plenty of time to develop. This means that there will be little chance that the fire area will
be small and a good chance that it will be large. In order to express these potentially different fire
developments, different fire scenarios have been defined for each extinguishing system that each have a
probability of occurring. If the fire frequency for a storage area is multiplied by the probability of a particular
scenario, the frequency of the fire scenario will be derived. If the frequencies for all fire scenarios for a
particular storage are added up, this will result in the fire frequency for the storage.
In CPR-15/2 it is indicated which fire fighting systems are allowed or required for each protection level. For
each of these systems requirements with regard to storage have been formulated that, among other things,
concern the permitted storage surface area and the fire resistance of the storage facility. Paragraph 4.3.2.
deals with the factors that play a role in determining the fire surface area for the various fire fighting
systems.
Paragraph 4.3.3. provides the fire frequency of a chemicals storage facility and 4.3.4. indicates the various
frequencies of a particular fire scenario for the various fire fighting systems.
4.3.2. Factors that Influence Fire Frequency and Fire Spread
The following factors influence the fire frequency and the fire spread.
Flammable Materials (K1 and K2)

When they are released, flammable materials will greatly contribute to fire spread due to the formation of a
burning liquid pool that is expanding. If this may be the case, this must be taken into account when
determining the probability of a fire area. Flammable liquids will be released during a fire when as a result
of heat radiation from a fire, the packaging fails. A difference must be pointed out here between metal
packaging and synthetic packaging. Calculations indicate that with respect to metal packaging, if a metal
drum filled with a flammable material is located above a liquid fire of 800 l (4 drums leaking) the drum will
not fail. Above the liquid surface the drum will be damaged (flange, filling opening) although this will not
cause the drum to empty its contents. It is assumed that synthetic packaging will melt and due to the
release of the flammable content will contribute to fire development. On the basis of the considerations
above, it is assumed in the risk analysis methodology that:
• K1 and K2 materials stored in metal will not influence the spread of fire
• K1 and K2 materials in synthetic packaging, if stored in a rack with a floor with a partition, will have no
effect on the spread of fire
• If the extinguishing system does not provide cooling, the storage of K1 and K2 materials in synthetic
packaging in a rack without a floor partition will have an effect on the spread of fire. This means a
greater probability for a larger fire area.
The presence or absence of flammable materials also affects the probability of fire. This is dealt with in
greater detail in the section on probability of fire.
Storage Size
Maximum storage size for the various extinguishing systems is indicated in the CPR 15-2 and CPR 15-3
guidelines. At its maximum, the fire area will not exceed the maximum storage volume (see also: 4.2.1).
The probability of the occurrence of a fire area smaller than 300 m2 is derived from data of the Sprinkler
Security Bureau (see: 4.3.4.1). When determining distribution of probability over the larger fire areas for the
various systems, it is assumed that the probability of the largest fire areas is the smallest for the most
quickly responding systems. This is why for the faster systems a distribution across areas of 300, 900,
1500 and 2500 m2 of 50:40:9:1 was opted for. For those systems with outside intervention, the division is
about inversely proportional to the surface areas (P(300):P(900):P(1500) = 5:3:1). The difference between
the company fire brigade and the local fire department is to be found in the probability of the creation of a
fire area of 300 m2 or more.
Ventilation rate
During the duration of the fire considered, the building structure is not affected by the fire. If during the
duration of the fire the doors are closed, the ventilation rate will be 4 (see also: 4.2.1). If during a fire the
doors do not close, the ventilation rate is unlimited. The probability of doors not closing depends of the type
of door:
• automatic, self closing doors, in case of fire: 0.02

• manually operated doors: 0.10
Automatic self-closing doors are a requirement if the storage area must have been built to resist fire.
4.3.3. Fire Frequency for Chemicals Storage
The probability of fire in a chemical storage facility is equal to the probability of fire in a pesticide/herbicide
storage area. This has been set to 8.8⋅10-4 annually [1] in the Pesticide/Herbicide study on the basis of
casuistry.
Materials can be stored in a chemicals storage facility at 3 different levels of protection. For protection
levels 1 and 2, the same probability of fire is assumed as for pesticide/herbicide storage, namely: 8.8⋅10-4
annually [1]. The reason for this is that chemicals stored under protection levels 1 and 2 are comparable in
the risk they pose with pesticides/herbicides.
A lower probability of fire has been determined for chemicals stored at protection level 3. The reason for
this is that under protection level 3 no K1, K2 and even virtually no K3 products, except for irritants, may be
stored. In other words, materials with a high initial probability of fire are not present. In chemical storage
facilities equipped with facilities as required by protection level 3, flammable materials with a flash point
higher than 100 oC may be stored in metal packaging. The non-flammable materials may be stored in
non-metallic packaging. The probability of a ignition source starting a fire in such a storage without K1, K2
and almost no K3 is lower. Due to this, it is assumed that in materials stored at protection level 3, the
probability of the occurrence of a fire is lower by a factor of 5 than the probability of starting fires in stored
materials at protection level 1 or 2.
4.3.4. Probability of a Fire Scenario for the Various Protection Levels/systems
The CPR 15-2 guideline distinguishes between three protection levels. At protection level 1 nine different
fire fighting systems are differentiated. The options for the various probabilities of a particular fire area are
given consecutively for the nine fire fighting systems and the protection levels 2 and 3.
The CPR 15-3 guideline does not distinguish protection levels. All stored materials are subject to the
protection level 1.
4.3.4.1. System 1: Automatic Sprinkler Installation
On the basis of field data from the Sprinkler Security Bureau, an imperical distribution of probability has
been derived for pesticide/herbicide storage from a number of possible fire areas that can occur in the case
of sprinkler installations. Areas of 20, 50, 100 and 300 m2 are assigned a probability of 0.45, 0.44, 0.10 and
0.01 respectively. In doing so, larger areas are equated to 300 m2. If for stacking the sprinklers have been
mounted in the racks, a slightly higher probability of smaller fire areas will be assumed, equivalent to the
automatic deluge (system 2).
In cases of an infinite ventilation rate fire areas larger than 300 m2 can contribute to the risk and this is why
in this study the above-mentioned distribution of probability has been extended with fire areas as 900, 1500
and 2500 m2. In determining the distribution of probability for the larger fire areas it is assumed that the
probability of the largest fire areas is the smallest. A subdivision for areas of 300, 900, 1500 and 2500 m2 of
50:40:9:1 has been assumed (see: 4.3.2). The probability of the various fire areas must be multiplied by the
probability of closed doors: 1-Pdo (ventilation rate 4) or the probability of open doors: Pdo (ventilation rate ∞).
Considering the extinguishing system, the storage of flammable products has no influence on the
probability of a particular fire area, but does influence the probability of a fire.
Table 4.2. Fire Scenarios System 1: Automatic Sprinkler

-1
Fire Area Ventilation rate [hour ]
4 ∞
2
[m ] Fire Duration Probability Fire Duration Probability
[min.] [-] [min.] [-]
20 30 0.45 (1-Pdo) 30 0.45 Pdo

3) 3)
0.63 (1-Pdo) 0.63 Pdo
50 30 0.44 (1-Pdo) 30 0.44 Pdo

0.263) (1-Pdo) 0.263) Pdo
100 30 0.1 (1-Pdo) 30 0.1 Pdo
300 202) 0.01 (1-Pdo) 202) 0.005 Pdo
9001) - - 202) 0.004 Pdo
1500 - - 202) 0.0009 Pdo
2500 - - 202) 0.0001 Pdo
Notes:
1) If K1 and K2 is stored in synthetics without a floor partition, the maximum area will be
800 m2. The probability of this fire area is 0.005
2) If the fire resistance of the storage space is greater than 20 minutes, the fire duration
will be 30 minutes.
3) These probabilities apply to a sprinkler installation that has been mounted in storage
racks.
4.3.4.2. System 2: Automatic Deluge Installation
With regard to the automatic sprinkler, the automatic deluge has the advantage that immediately after fire
detection an entire section will be kept wet. A sprinkler is one step behind the fire (heat) development. This
advantage is expressed particularly clearly in cases of more compact stacking and pool fires. This is
indicated in the table by a slightly higher probability of a small fire area than that for a sprinkler.
Table 4.3. Fire Scenarios System 2: Automatic Deluge

Fire Area Ventilation rate [hour-1]
4 ∞
Fire Duration Probability Fire Duration Probability

[m2] [min.] [-] [min.] [-]
20 30 0.63 (1-Pdo) 30 0.63 Pdo
50 30 0.26 (1-Pdo) 30 0.26 Pdo
100 30 0.1 (1-Pdo) 30 0.1 Pdo
300 201) 0.01 (1-Pdo) 201) 0.005 Pdo
900 201) 0.004 Pdo
1500 201) 0.0009 Pdo
2500 201) 0.0001 Pdo
Note:
1) If the fire resistance of the storage area is greater than 20 minutes, the fire duration
will last 30 minutes.
4.3.4.3. System 3: Automatic Gas Extinguishing Installation
An automatic gas extinguishing installation may only be installed in a storage area of no more than 600 m2
and that has a fire resistance of 30 minutes and in which no smoke hatches may be applied. The space is
therefore considered to be gas-tight. In deviation from the distribution of probability for sprinkler
installations, it is assumed in the case of a gas extinguishing installation that due to the small storage
space and the limited supply of oxygen only a small oxygen-restricted fire is possible during normal
operation. In that case, the fire duration is set to 5 minutes.
The probability of failure of the gas extinguishing installation is equal to that for a sprinkler, namely: 0.01.
The cause of failure could be no extinguishing (probability: 0.005) or non-closure of the doors (probability
0.005). If the cause of failure is the non-automatic closure of the doors, a maximum area-restricted fire will
occur.
Table 4.4. Fire Scenarios System 3: Automatic Gas Extinguishing

4 ∞

[m2] [min.] [-] [min.] [-]
20 5 0.99 - -
600 30 0.005 30 0.005
4.3.4.4. System 4: Local Fire Department with Dry Deluge System
When the local fire department is to fight fires, the storage area may not be larger than 500 m2 with a fire
resistance of 60 minutes (30 minutes if the deployment time of the local fire department < 6 minutes). It is
assumed that the fire has achieved its maximum volume in the period up to the possibility of deployment of
the fire department. This could be an oxygen-restricted fire, probability: 1-Pdo, or an area-restricted fire,
probability: Pdo. If ventilation is unlimited (probability: Pdo) the fire can expand to 500 m2. It is assumed that
the probability of a fire of 300 m2 or 500 m2 is inversely proportional to the area for systems in which the fire
department must take action. For this system this means the probability of 300 m2 is 0.6; probability for 500
m2 is 0.4.
Table 4.5. Fire Scenarios System 4: Local Fire Department with Dry Deluge
-1
Fire Area Ventilation rate [hour ]
4 ∞

[m2] [min.] [-] [min.] [-]
300 30 1 . (1-Pdo) 202) 0.6.Pdo
5001) - - 202) 0.4.Pdo
Notes:
1 If the storage of K1 and K2 materials is in synthetic packaging the maximum storage
size may not exceed 100 m2.
2 If the fire resistance of the storage space is greater than 20 minutes the fire duration
will be 30 minutes.
4.3.4.5. System 5: Automatic Hi-ex Installation
When an automatic hi-ex installation is used, the storage area must have been built to resist fire for 30
minutes and the storage space may not exceed 1500 m2. The storage is equipped with a smoke and heat
conveyance installation (smoke hatches). A hi-ex installation extinguishes the fire using high-expansion
foam. This means that if the fire is to be extinguished properly, the smoke hatches must be open and there
must be an unlimited supply of oxygen to the fire. The fire extinguishing activity is about the same as a gas
extinguishing installation. Considering that the system is somewhat more complex than a gas extinguishing
system, probabilities are slightly higher up to 100 m2.
Table 4.6. Fire Scenarios System 6: Automatic hi-ex Installation

Fire Area Ventilation rate ∞
Fire Duration Probability

[m2] [min.] [-]
20 10 0.89
50 10 0.09
100 10 0.01
300 30 0.005
900 30 0.004
1500 30 0.001
4.3.4.6. System 6: Company Fire Brigade with Manual Deluge Installation
When utilizing this fire fighting system the storage must be designed to be resistant to fire for 30 minutes.
The maximum area is 2500 m2. When determining the distribution of probability for the fire areas, it is
assumed that it will take more time to switch on a manually operated deluge installation than to get an
automatic one operational. In this case, the probability of failure lies in the installation not being operational.
As this involves human failure, this probability is derived from data about human failure under stress [3] and
is set at 0.1. If the doors are not closed (probability: Pdo), a larger area-restricted fire could also occur. This
probability is distributed across the fire areas of 300 m2 and more in the same manner as for the sprinkler
system.
Table 4.7. Fire Scenarios System 6: Company Fire Brigade with Manual Deluge
4 ∞

[m2] [min.] [-] [min.] [-]
20 30 0.35 (1-Pdo) 30 0.35 Pdo
50 30 0.45 (1-Pdo) 30 0.45 Pdo
100 30 0.1 (1-Pdo) 30 0.1 Pdo
300 30 0.1 (1-Pdo) 30 0.05 Pdo
9001) - - 30 0.04 Pdo
1500 - - 30 0.009 Pdo
2500 - - 30 0.001 Pdo
Note:
1) Maximum storage space 600 m2 when storing K1 and K2 materials in synthetic
packaging (probability: 0.05).
4.3.4.7. System 7: Company Fire Brigade with Dry System
Also when applying this fire fighting system will the storage area have to be fire resistant for 30 minutes
and the maximum storage area will not exceed 2500 m2. When determining the distribution of probability is
was assumed that extinguishing with a dry system is slower than using a deluge system. Therefore, there
is a greater probability of larger fire areas. If the doors are not closed (probability: Pdo), a larger
area-restricted fire could also occur. This probability is distributed across the fire areas of 300 m2 and more
in the same manner as for the sprinkler system.
Table 4.8. Fire Scenarios System 7: Company Fire Brigade with Dry System
4 ∞

[m2] [min.] [-] [min.] [-]
50 30 0.2 (1-Pdo) 30 0.2 Pdo
100 30 0.3 (1-Pdo) 30 0.3 Pdo
3001) 30 0.5 (1-Pdo) 30 0.25 Pdo
900 - - 30 0.2 Pdo
1500 - - 30 0.045 Pdo
2500 - - 30 0.005 Pdo
Note:
1 Maximum storage space 300 m2 when storing K1 and K2 materials in synthetic
packaging (probability: 0.5).
4.3.4.8. System 8: Company Fire Brigade with on-site Extinguishing (interior fire attack)
When this fire fighting system (company fire brigade interior fire control capability) is applied the storage
must be designed to resist fire for 60 minutes. The area may not exceed 1500 m2. The storage area is
equipped with smoke hatches. When the fire brigade is deployed the smoke hatches must be open.
Ventilation will then be unlimited. The distribution of probability across the various fire areas for opened
smoke hatches (ventilation rate ∞) is determined analogically as it is for system 7, taking into account that it
is now even more difficult to extinguish the fire. The probability of fires ≥300 m2 is distributed across 300,
900 and 1500 m2 as 5:3:1, approximately inversely proportional to the areas. If in the case of the system
flammable liquids have been stored, a minimum fire volume of 300 m2 will be assumed.
Table 4.9. Fire Scenarios System 8: Company Fire Brigade with Interior Fire Control Capability

2
[m ] [min.] [-]
50 30 0.2
100 30 0.3
1)
300 30 0.28
900 30 0.16
1500 30 0.06
Note:
1 Maximum storage space 300 m2 when storing K1 and K2 materials in
synthetic packaging (probability: 0.5).
4.3.4.9. System 9: Automatic Hi-ex with Inside Air
In this system there is no smoke and heat conveyance installation present. The extinguishing effectiveness
is approximately equivalent to a gas extinguishing installation. Considering that the system is somewhat
more complex than a gas extinguishing installation, the probabilities are a somewhat higher up to 100 m2.
A hi-ex installation will not work if ventilation is ∞ and this is why a fire duration of 30 minutes is assumed
each time.
Table 4.10. Fire Scenarios System 9: Automatic hi-ex with Inside Air
4 ∞

[m2] [min.] [-] [min.] [-]
20 10 0.89 (1-Pdo) 30 0.89 Pdo
50 10 0.09 (1-Pdo) 30 0.09 Pdo
100 10 0.01 (1-Pdo) 30 0.01 Pdo
300 30 0.01 (1-Pdo) 30 0.005 Pdo
900 - - 30 0.004 Pdo
1500 - - 30 0.0009 Pdo
2500 - - 30 0.0001 Pdo
4.3.4.10. Protection Level 2: < 6 Minutes
The distribution of probability for the fire areas for protection level 2 with a mobilization time for the
community fire department of less than 6 minutes is equated to the company fire brigade with interior fire
control capability (system 8).
Table 4.11. Fire Scenarios Protection Level 2: Mobilization Time < 6 Minutes
Fire Duration Probability [-] Probability [-]

[m2] [min.] no K1 and K2 in K1 and K2 in
Synthetics Synthetics
50 30 0.2
100 30 0.3
300 30 0.28 0.72
800 30 0.28
900 30 0.16
15001) 30 0.04
2500 30 0.02
Note:
1 Maximum storage space 1500 m2 when storing K1 and K2 materials in metal packaging
(probability: 0.06).
4.3.4.11. Protection Level 2: < 15 Minutes
The distribution of probabilities for the fire areas for protection level 2 with a mobilization time for the
community fire department less than 15 minutes is slightly more conservatively assumed than for protection
level 2 with a mobilization time of 6 minutes.
Table 4.12. Fire Scenarios Protection Level 2: Mobilization Time < 15 Minutes
Fire Duration Probability [-] Probability [-]

2
[m ] [min.] no K1 and K2 in K1 and K2 in
synthetics Synthetics
300 202) 0.78 0.55
800 202) 0.45
900 202) 0.16
15001) 202) 0.04

2)
2500 20 0.02
Notes:
1) Maximum storage space 1500 m2 when storing K1 and K2 materials in metal packaging
(probability: 0.06).
2) Fire duration is 30 minutes if the fire resistance is ≥ 30 minutes.
4.3.4.12. Protection Level 3
At protection level 3 it is not assumed that the fire department will restrict the fire to smaller than 300 m2.
The probabilities of a particular fire area are inversely proportional to the assumed area. As indicated in
-4
4.3.3., the fire frequency for protection level 3 is: 1.8 10 annually.
Table 4.13. Fire Scenarios Protection Level 3

[m2] [min.] [-]
300 201) 0.78
900 201) 0.16
1500 201) 0.04
2500 201) 0.02
Notes:
1) Fire duration is 30 minutes if fire resistance is ≥ 30 minutes.
2) Fire frequency 1.8 10-4 annually.
4.4. Calculation of Individual and Societal Risk
In addition to the data above, a number of subsequent probabilities are important for risk calculation. These
subsequent probabilities refer to the prevention of meteorological conditions. The meteorological
conditions: stability of the atmosphere, wind speed and wind direction are important to the dispersion
calculations. This data has been included in Appendix 1 for the weather station at Schiphol. The risk
calculation consists of jointly considering the damage areas of the distinguished fire scenarios and the
corresponding probabilities of occurrence, development and lethality.
4.5. Sample Calculation for Fire in a Chemicals Storage Facility
4.5.1. Description of the Storage Facility
In order to determine the risk of a fire in a chemicals storage facility, the following storage is assumed in
this sample calculation. The storage area has a total surface area of 1500 m2; length times width of 50 x 30
and a height of 6 m. The ventilation rate of the storage amounts to 4. The storage area is equipped with an
automatic hi-ex installation with inside air (system 9, see: Paragraph 4.3.4). The area is equipped with
manually operated doors.
The following materials are present in the storage facility:
Material Amount
[Metric Tons]
aniline 200
chloroform 320
ethylene glycol 250
phenol 200
furfural 100
hexandiol 185
formic acid 140
salicydic acid 320
sulfurylchloride 200
ethene tetrachloride 305
urea 100
Very toxic materials with a LD50 (rat, oral ≤ 25 mg/kg) are not present in the sample storage.
4.5.2. Effect and Damage Calculation for Fire
The effect and damage calculations occur in accordance with the schedule in figure 4.1. from Paragraph
4.2.
4.5.2.1. Fire Scenario
Fire Duration
The fire duration for a fire in which an automatic hi-ex installation goes into operation, is set at 10 minutes
(= time to extinguish fire). If the extinguishing installation fails, the fire duration is set to a maximum of 30
minutes (see table 4.10).
Fire Area
The size of the fire area is largely determined by the oxygen supply and also depends on the fire fighting
system. The distribution of probability drawn up for a hi-ex installation with inside air is given in table 4.10.
for a number of fire areas. The maximum fire area will be equal to the area of the storage area, namely:
1500 m2.
Ventilation rate
The ventilation rate (the number of air cycles per hour) of the storage area is 4. This ventilation rate is
applicable if the doors of the storage space are closed. If the doors (manually operated) are open during
the fire, the ventilation is unlimited.
Table 4.14. contains a summary of the effect of the premises above for the fire scenario with regard to fire
duration, fire area and ventilation rate.
Table 4.14. Ventilation rate, Fire Area and Fire Duration for the Sample Storage Facility
Fire Scenario Ventilation rate Fire Area Fire Duration

2
[m ] [min]
Fire in the storage space Doors closed: 4 20 10
4 50 10
4 100 10
4 300 30
Doors open: ∞ 20 30
∞ 50 30
∞ 100 30
∞ 300 30
∞ 900 30
∞ 1500 30
4.5.2.2 Stored Materials
From the list of stored products provided in Paragraph 4.5.1. it follows that:
• no flammable K1 or K2 materials are stored

• no highly toxic materials (LD50rat, oral ≤ 25 mg/kg) are stored.
All stored materials belong to category 0: materials that produce (toxic) combustion products. The storage
involves technically pure materials, meaning 100% active material.
Fire in the Storage Space
Materials : 'mix': see 4.5.1.

Storage amount : 2320 metric tons
Average Structure Formula
(according to formula 4.1) : C3.28H4.35O1.38Cl1.10N0.23S0.06
Average molecule weight : 110.1 kg/kmol
Combustion formula : quantitative conversion, see formula 4.2.a
C3.28H4.35O1.38Cl1.10N0.23S0.06 + 3.543 O2 →
3.28 CO2 + 1.625 H2O + 1.10 HCl + 0.0805 NO2 + 0.07475 N2 + 0.06 SO2
Oxygen requirement Z0 : 3.543 kmol O2/kmol 'mix'
4.5.2.3. Burn Rate
Burn rate refers to the amount of the material (or mix of materials) that burns per time unit (kg/s).
Paragraph 4.2.3. describes how the burn rate is calculated.
Area-restricted Fire
An area-restricted fire is said to exist if the amount of oxygen available does not constitute a restriction to
the fire (in case of unrestricted ventilation through open doors or in case of closed doors and a small fire
area). In that case, the burn rate per surface area unit will at its maximum be equivalent to the evaporation
speed of the material which in general is 0.025 kg/s.m2. Maximum burn rate is then calculated by
multiplying by fire area A (formula 4.3.):
Bmax = 0.025 x A kg/s
Oxygen-restricted Fire
When the available amount of oxygen is smaller than the amount of oxygen required for an area-restricted
fire (the maximum burn rate) the fire is oxygen-restricted (this will occur quite rapidly if doors are closed).
The available amount of oxygen comes from the air that is present in the storage area (1500 m2 x 6 m) and
from the ventilation air conveyed (ventilation speed = 4). The amount of oxygen available when the doors
are closed is determined on the basis of equation 4.4.:
mO2 = 0.2 (1 + 0.5 x F) V / (24 x 1800)

= 0.2 (1 + 0.5 x 4) x (1500 x 6) / (24 x 1800) = 0.125 kmol/s
Subsequently, the burn rate is calculated based on the oxygen requirement of burning Z0 (see Paragraph
4.5.2.2). The following burn rate has been calculated for an oxygen-restricted fire (in accordance with
formula 4.5.):
B0 = mO2 x M/Z0 = 0.125 x 110.1 / 3.543 = 3.88 kg/s
Burn rates for the Scenario

The burn rates for the scenario are arrived at by multiplying the fire area of the scenario with the maximum
burn rate (0.025 kg/m2) on the understanding that if the ventilation rate is 4, the burn rate can never
become greater than the burn rate calculated above for an oxygen-restricted fire. The burn rates are
provided in table 4.15.
4.5.2.4. Source Strength
It can be deduced from Paragraph 4.5.2.2. that no highly toxic materials are stored. Due to this, the release
of toxic non-combusted product does not contribute significantly to the risk for the environment of a fire in
the storage space. The release of the following toxic combustion products determine the risk: NO2, SO2
and HCl. The creation of these products result from the combustion formula as set up in Paragraph 4.5.2.2.
In general, it is assumed that there will be a quantitative conversion.
The emission of toxic combustion products (in kg per kg of burnt product) for a fire in the storage space is
calculated according to formula 4.6.:
η = ( Cl x 36.5 + n x 46 x 0.35 + s x 64 ) / M (4.6)
η = ( 1.10 x 36.5 + 0.23 x 46 x 0.35 + 0.06 x 64 ) / 110.1

= 0.4332 kg combustion product / kg of burnt material
HCl fraction in the combustion product:

1.10 x 36.5 / (1.10 x 36.5 + 0.23 x 46 x 0.35 + 0.06 x 64 ) = 0.842
SO2 fraction in the combustion product:
0.06 x 64 / (1.10 x 36.5 + 0.23 x 46 x 0.35 + 0.06 x 64 ) = 0.080
NO2 fraction in the combustion product:
0.23 x 46 x 0.35 / (1.10 x 36.5 + 0.23 x 46 x 0.35 + 0.06 x 64 ) = 0.078
The source strength in kg/s (formula 4.7) is then determined by multiplying by the burn rate that is
determined in paragraph 4.5.2.3. The resulting values are provided in table 4.17.
4.5.2.5. Toxicity
Damage models have been derived in accordance with the methodology described in 4.2.5. for the toxic
combustion products determined in Paragraph 4.5.2.4.
Fire in the Storage Space
Toxic combustion product : 7.8% NO2, 84.2% HCl, 8.0% SO2

filled in in equation 4.11. this results in:
3.7 2.4 5
Pr = -18.6 + ln { [ (fNO2C) + 0.549 (fSO2C) + 1.47⋅10 (fHClC) ] x t }
Pr = -18.6 + ln { [ 7.96⋅10-5 C3.7 + 1.28⋅10-3 C2.4 + 1.238⋅105 C ] x t }
From this probit function, the following lethal concentrations for an exposure duration of 10 and 30 minutes
were calculated:
t = 10 min LC50 = 3735 mg/m3 t = 30 min LC50 = 2473 mg/m3

LC01 = 1224 mg/m3 LC01 = 461 mg/m3
4.5.2.6. Dispersion
The emissions to the environment for the fire scenario are related to the duration of the fire in which no
plume rise occurs. Therefore, plume rise plays no role in dispersion calculations in this study. For the
purpose of calculating the dispersion in the area it is assumed that the smoke gasses will first be mixed in
the recirculation zone of the storage building. In order to attribute this, an area source with a length and
2
width that is equal to the root of the surface area (in m ) of the storage is assumed. In this example this
2
would be the root of 1500 m which is approx. 39 m. The distribution is calculated with the neutral gas
dispersion model from [6]. The concentrations of the toxic combustion products that may occur in the
environment have been calculated. The concentrations that occur are averaged out within the dispersion
model over a duration that is equal to the exposure duration of people in the area. The concentrations
calculated are related to the probit functions for lethality in 4.5.2.5. from which the damage areas to be
expected follow for a fire in the chemicals storage. The results of the dispersion calculations are
summarized in table 4.16.
4.5.3. Probability Estimates
In Paragraph 4.3. the probability estimate for various fire fighting systems has been worked out. As the
storage facility in question is equipped with an automatic hi-ex installation with inside air, the probabilities
provided for system 9 are applicable. This involves the following probability aspects:
• Fire frequency = 8.8.10-4 annually

• Probability distribution for the two ventilation rates considered:
Ventilation rate = 4, manually operated doors are closed: probability = 1-Pdo = 0.90
Ventilation rate = ∞ (= unlimited), doors open: probability = Pdo = 0.10.
• Probability of fire expansion in case of an automatic hi-ex installation with inside air. The probability of
the differentiated fire areas from table 4.15. are derived from table 4.10:
Table 4.15. Probability of Occurrence of Various Fire Surface Areas
Fire Scenario V.M. Fire Area Burn rate Probability [-]

2
[m ] [kg/s] (x Pdo of 1-Pdo)
Fire in Storage Space 4 20 0.5 0.89 x 0.9
4 50 1.25 0.09 x 0.9
4 100 2.5 0.01 x 0.9
4 300 3.88 0.01 x 0.9
∞ 20 0.5 0.89 x 0.1
∞ 50 1.25 0.09 x 0.1
∞ 100 2.5 0.01 x 0.1
∞ 300 7.5 0.005 x 0.1
∞ 900 22.5 0.004 x 0.1
∞ 1500 37.5 0.001 x 0.1
The resulting frequencies are presented in table 4.16. In addition to the frequencies and probabilities
above, the frequency distributions of the weather classes and the wind directions are relevant to the risk
calculations. The data for the weather station at Schiphol are provided in Appendix 1.
Table 4.16. Results for Fire in Storage Space
Ventilation Fire Area Fire Source

2
Frequency Maximum Damage Distances for
rate [m ] Duration Strength
[annually] Toxic Combustion Products
[min] [kg/s]
[m]
D5 Neutral F2 Very Stable
LC01 LC01
4
-4
Doors 20 10 7.05⋅10 0.217 50 425
Closed
-5
50 10 7.13⋅10 0.541 140 870
-6
100 10 7.92⋅10 1.083 260 1365
-6
300 30 7.92⋅10 1.681 410 2220
∞
-5
Doors Open 20 30 7.83⋅10 0.217 70 515
-6
50 30 7.92⋅10 0.541 170 1045
-7
100 30 8.80⋅10 1.083 295 1675
-7
300 30 4.40⋅10 3.249 645 3295
-7
900 30 3.52⋅10 9.747 1295 5960
-8
1500 30 8.80⋅10 16.244 1770 7780
4.5.4. Risk Calculation and Presentation
On the basis of the results of the effect and damage calculations and the probability estimate for the fire
scenario, as summarized in table 4.16., the risk calculations have been carried out with the aid of the risk
analysis software package RISKCURVES developed by TNO (Dutch organization for applied scientific
research). The results for the individual risks are provided in the diagram below.
Figure 4.2. Individual risk/distance curve (F, X curve) for a fire in the sample storage space of
1500 m , with Hi-Ex inside air (wind direction 230 - 250° ≈ west, south-west).
2
5. References
[1] M. Molag en J.M. Blom-Bruggeman (1991).

Onderzoek naar de gevaren van de opslag van bestrijdingsmiddelen - risico-analysemethodiek. [study of
the dangers of the storage of pesticides/herbicides - risk analysis methodology]
TNO-rapport 90-424, TNO-MT, Apeldoorn, 1991.
[2] M. Molag en J.M. Blom-Bruggeman (1990).

Individueel en groepsrisico opslag bestrijdingsmiddelen voor verschillende brandbestrijdingssystemen.
Ministerie VROM (Publikatiereeks Milieubeheer, nr. 1990/9), [individual and group risk of storage of
pesticides/herbicides for various fire fighting systems] 's-Gravenhage, 1990.
[3] TNO (1983).

LPG-Integraal. Vergelijkende risico-analyse van de opslag, de overslag, het vervoer en het gebruik van
LPG en benzene (i.o.v. Ministerie VROM). [LPG integral. Comparative risk analysis of the storage,
transshipment and the use of LPG and benzene]
TNO-MT, Apeldoorn, 1983.
[4] D. de Weger (1990).

Onderzoek naar de gevaren van de opslag van bestrijdingsmiddelen - Deelrapport 1: Toxiciteitsgegevens
[study of the dangers of the storage of pesticides/herbicides - report part 1: toxicity data]
TNO-rapport 88-174, TNO-MT, Apeldoorn, 1990.
[5] A.H. Heemskerk et al.

Onderzoek naar de gevaren van de opslag van bestrijdingsmiddelen - Deelrapport 2: Dispersie, brand en
explosie eigenschappen [study of the dangers of the storage of pesticides/herbicides - report part 2:
dispersion, fire and explosion properties]
Prins Maurits laboratorium TNO.
Ref.nr. 1991-C61, Rijswijk, februari 1991.
[6] TNO (1988).

Methoden voor het berekenen van fysische effecten (Gele Boek) [methods for calculating physical effects
(yellow book)]
Commissie Preventie van Rampen door Gevaarlijke Stoffen, CPR-14. [Commission for the Prevention of
Disasters caused by Hazardous Materials]
Directoraat-Generaal van de Arbeid (Ministerie van Sociale Zaken en Werkgelegenheid), Voorburg, 1988
(2e druk).
[7] TNO (1989).

Methoden voor het bepalen van mogelijke schade (Schadeboek) [methods for determining possible
damage (damage book)]
Commissie Preventie van Rampen door Gevaarlijke Stoffen, CPR-16. [Commission for the Prevention of
Disasters caused by Hazardous Materials]
Directoraat-Generaal van de Arbeid (Ministerie van Sociale Zaken en Werkgelegenheid), Voorburg, 1989.
[8] Notitie Knelpuntenoverleg EVR (KO 18-2) - Gebruik toxiciteitsgegevens [notes on EVR bottleneck
consultation (KO 18-2) - use of toxicity data]
Ministerie VROM, Leidschendam, 1990.
[9] Notitie Knelpuntenoverleg EVR - KO 20 [notes on EVR bottleneck consultation KO 20]

[10] Klimatologische gegevens van Nederlandse Stations, No. 8 - Frequentietabellen van de stabiliteit van de
atmosfeer [climatological data from Dutch stations, No. 8 - frequency tables of the stability of the
atmosphere]
KNMI, De Bilt, 1972.
[11] C.L. van Deelen (1990).

Een methodiek voor de bepaling van het risico van bodemverontreiniging door bedrijven. (2 deelrapporten)
[a methodology for determining the risk of soil pollution by companies--2 part report]
TNO-rapport 87-044/85-013205, TNO-MT, Apeldoorn, 1990.
[12] Ministerie VROM.

Omgaan met risico's. [dealing with risks]
Tweede Kamer 1988-1989, 21137, nr.5.
[13] Circulaire betreffende werkprogramma aanpassing opslagplaatsen gevaarlijke stoffen en chemisch afval.
[circular regarding the work program for modifying storage sites for hazardous materials and chemical
waste]
Ministerie VROM, Hoofddirectie Ketenbeheer en Milieuzorg, directie Industrie, Bouw, Produkten,
Consumenten, kenmerk IBP 0389009, 31 augustus 1992.
[14] Short Distance Emissions

Publicatie S37-1,
Directoraat-Generaal van de Arbeid,
Voorburg, 1989.
[15] Notitie Knelpuntenoverleg EVR - KO 37-2 [notes on EVR bottleneck consultation KO 37-2]
[16] Notitie Knelpuntenopverleg t.a.v. de Rookgassenproblematiek [notes on bottleneck consultation for the
smoke gasses question]
Ministerie VROM, Leidschendam, 29 april 1992.
[17] G.M.H. Laheij

Studie naar de gevormde hoeveelheid stikstofoxiden bij brand in opslagen van chemicaliën of
bestrijdingsmiddelen [study of the amount of nitrous oxides created during a fire in storages for chemicals
or pesticides/herbicides]
RIVM rapport nr. 60066003, Bilthoven december 1995
[18] Circulaire CPR-15 [CPR-15 circular]

Ministerie van VROM (DGM/SVS/97560078, oktober 1997).
Appendix 1: Meteorological Conditions at the Schiphol Weather Station
Wind Direction Frequency Distribution
Wind Direction W N O Z
Sector 1 2 3 4 5 6 7 8 9 10 11 12
Stability Class Day Night
A through D 40.0 40.0 13.0 11.0 9.0 9.0 8.0 7.0 7.0 8.0 7.0 7.0 8.0 9.0
E and F 0.0 20.0 5.0 6.0 5.0 6.0 9.0 13.0 9.0 7.0 10. 12. 10. 9.0
0 0 0

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RISK ANALYSIS METHODOLOGY FOR CPR-15 ESTABLISHMENTS

The Hague, October 1997

Ministry for Housing, Spatial Planning and the Environment (VROM)

The head of the External Safety Department,

Drs. G.C.M. Lommers

2.2. Materials and Material Categories 7

2.3. CPR 15 Regulations 8

2.4. Risk to the Surroundings 8

3. RISK ANALYSIS OF THE RELEASE OF STORED PRODUCTS 10

3.2. Release of Toxic Solids 10

3.3. Release of Toxic Liquids 14

4.3. Frequency Estimates 29

4.3.4.3. System 3: Automatic Gas Extinguishing Installation 34

4.4. Calculation of Individual and Group Risk 41

4.5. Sample Calculation for Fire in a Chemicals Storage Facility 41

- the accident scenarios to be considered

2.1. When is a Risk Analysis necessary?

2.2. Materials and Material Categories

- oxidizing NOT: peroxides, nitrates

2.3. CPR 15 Regulations

2.3.1. Protection Levels

These protection levels serve as premises for this study.

2.3.2. Miscellaneous Preconditions

2.4. Risk to the Surroundings

1. The release and ignition of a flammable liquid.

2. The release of toxic liquids or powders.

Accident Type Physical Effects Risk to Area

Fire Heat radiation No

Release and dispersal of Yes

Release and dispersal of toxic Yes

• release of toxic solids (Chapter 3.2.)

3. Risk Analysis of the Release of Stored Products

The probabilities are distributed as follows:

The following constitute meteorological circumstances:

3.2. Release of Toxic Solids

3.2.2. Source Strength

3.2.3. Effect and Damage Calculations

- for LD50 = 5 mg/kg:

- for LD50 = 25 mg/kg:

3.2.5. Sample Calculation for the Release of Toxic Solids (Powders)

These assumptions yield the following source strength:

Distance F, 2 m/s D, 5 m/s

[m] Conc. Dose Conc. Dose

≤ 19 3700 10.7⋅105 3700 4.3⋅105

25 3200 10.0⋅105 3200 4.0⋅105

50 2300 8.2⋅105 2100 2.6⋅105

100 1400 4.7⋅105 800 0.6⋅105

200 640 2.6⋅105 - -

300 360 0.7⋅105 - -

(Lethal Injury Frequency)

(Distance to the Accident)

3.3. Release of Toxic Liquids

Vapour Pressure at 20°C LD50(oral, rat) [mg/kg] or

< 0.001 < 2.3

3.3.2. Source Strength

3.3.3. Effect and Damage Calculations

3.3.5. Sample Calculation for Release of Toxic Liquids