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Prepared by: P. Date: 13 September 2010


Crossthwaite, A. Falck, K.
Kenich HUMAN IMPACT
CRITERIA
Issued for RiskNet Ref: T15 Revision No. 03

TECHNICAL NOTE

HUMAN IMPACT CRITERIA

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DNV TECHNICAL NOTE Page 2 of 126

Prepared by: P. Date: 13 September 2010


Crossthwaite, A. Falck, K.
Kenich HUMAN IMPACT
CRITERIA
Issued for RiskNet Ref: T15 Revision No. 03

Table of Content Page

1 SUMMARY OF CONTROLLED ITEMS .................................................................. 5

2 OBJECTIVES .............................................................................................................. 9

3 DEFINITIONS........................................................................................................... 10

4 APPLICABILITY ...................................................................................................... 13
4.1 General 13
4.2 Probabilistic Criteria 13
4.3 Single Value Criteria 14
4.3.1 Individual Risks 15
4.3.2 Group Risks 15

5 TOXIC GASES AND VAPOURS ............................................................................ 16


5.1 Impact criteria 16
5.1.1 Probits for toxic gases and vapours 16
5.1.2 Single value criterion for hydrogen sulphide for use offshore 20
5.2 Effects of some substances 21
5.2.1 Ammonia 21
5.2.2 Chlorine 22
5.2.3 Hydrogen Fluoride 22
5.2.4 Hydrogen Sulphide 23
5.2.5 Hydrogen Cyanide 23
5.2.6 Sulphur Dioxide 24

6 THERMAL RADIATION ......................................................................................... 25


6.1 Introduction 25
6.2 Background 25
6.2.1 The Effects of Thermal Radiation 25
6.2.2 Structural Effects 28
6.2.3 Thermal Radiation Probits 30
6.3 Recommended Criteria for Thermal Radiation 31
6.3.1 Probabilistic Criteria 32
6.3.2 Single Value Impact Criteria 32

7 EXPLOSION OVERPRESSURE.............................................................................. 39
7.1 Introduction 39
7.2 Background 39

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Prepared by: P. Date: 13 September 2010


Crossthwaite, A. Falck, K.
Kenich HUMAN IMPACT
CRITERIA
Issued for RiskNet Ref: T15 Revision No. 03

7.2.1 The Effects of Overpressure 39


7.2.2 Overpressure Probits 49
7.3 Impact Criteria 55
7.3.1 Probabilistic Criteria 55
7.3.2 Single Value Criteria Onshore 56
7.3.3 Single Value Criteria offshore structures. 57

8 SMOKE...................................................................................................................... 59
8.1 Introduction 59
8.2 Composition of Smoke 59
8.3 Effects of Carbon Monoxide 60
8.3.1 Effects of Carbon Dioxide 62
8.3.2 Occupational exposure limits for CO2 65
8.4 Effects of Oxygen Starvation 66
8.5 Effects of High Temperature 66
8.6 Criteria 67

9 ASPHYXIANTS ........................................................................................................ 68
9.1 Literature Review 68

10 CALCULATION OF FATALITIES FOR OFFSHORE FACILITIES..................... 70


10.1 Immediate fatalities local to Event 70
10.2 Ignited Releases – Delayed Ignition and explosions 70
10.3 Immediate fatalities in other areas 71
10.4 Escape fatalities 72
10.5 Evacuation fatalities 73

11 REFERENCES........................................................................................................... 74

Appendix A Probit analyse


Appendix B ERPG values for toxicity
Appendix C Generation of toxicity probits
Appendix D Conversion of probits for different units (mg/m3 and ppm)
Appendix E Probits of mixtures
Appendix F Suggested approach to impairment and incapacitation due to smoke
Appendix G Deriving single value criteria from probits

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DNV TECHNICAL NOTE Page 5 of 126

Prepared by: P. Date: 13 September 2010


Crossthwaite, A. Falck, K.
Kenich HUMAN IMPACT
CRITERIA
Issued for RiskNet Ref: T15 Revision No. 03

1 SUMMARY OF CONTROLLED ITEMS


This document forms part of the technical documentation of DNVs Risk management
services. The technical documentation provides a framework for performance of all
assessments according to established standards for consistency and quality for DNV world
wide. The guideline is a part of a hierarchy of documents which include:
• Guidelines documents which describe the methodologies to be employed
• Technical Notes which describe the detailed models and data to be used;

The following table summarizes the main recommendations in this Technical Note, but the
reader is advised to confirm that any value in the table below is appropriate for the work being
carried out by reading the background for the selection of these values before using it in client
work.

The main updates in revision 3 of this technical note include the following.
o Updates related to effects of Carbone Monoxide (section 8.3)
o New section related to effects of Carbone Dioxide (section 8.4)
o Calculation of fatalities for offshore facilities (section10)
o Updated suggested approach to impairment and incapacitation due to smoke (app.F)

Table 1-1 Summary of Recommended Single Value Criteria


Hazard People Onsite People Offsite
Criterion Fatality probability Criterion Fatality probability
Toxicity Toxic gases and Recommended Probits of the form Y=A + Bln(Cnt)
vapours Probit constants in TABLE
H2S (Offshore) 1550ppm 1 NA
Thermal Radiation1 Inside Outside Inside Outside
Flash fire LFL 0.1 1 LFL 0.1 1
Jet and pool fire 20kW/m2 1 1 12.5kW/m2 0.1 0.7
Fire Ball 250kJ/m2 0.3 1 250kJ/m2 0.3 1
Explosion overpressure2 > 0.5bar 1 0.5 >0.5 1 0.5
Onshore > 0.35bar 0.7 0.3 >0.35 0.7 0.15
Using Phast Risk 3
0.1 0.15 0.01 0.1 0.15 0.01

1
For evaluation of fatalities on Offshore structures, the criterion for onshore “ Onsite” applies.
2
. These fatality rates applies for onshore sites and includes the effect of the explosion pressure only, In a VCE, almost
everyone in the flammable portion of the cloud will be expected to die, due to flame contact, regardless of the
overpressure generated No fatalities related to the VCE cloud it self (heat) or effect of potentially secondary fires due to
rupture of equipment or piping containing flammable materials. These effects must be included additionally.
3
The inside figures are based on the fatality probability of a person in a typical brick dwelling (/100/). Special explosion
rated buildings (e.g. control rooms, special process buildings etc) has to be evaluated separately with respect to indoor
fatality rates.

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DNV TECHNICAL NOTE Page 6 of 126

Prepared by: P. Date: 13 September 2010


Crossthwaite, A. Falck, K.
Kenich HUMAN IMPACT
CRITERIA
Issued for RiskNet Ref: T15 Revision No. 03

Table 1-1 Summary of Recommended Single Value Criteria cont.


Offshore structures Fatalities due to Explosions Fatality fraction
Scenario
Area Criteria Thermal Pressure
Initial Area < 0.1 bar VCE with subsequent fire, no escalation, N.A
0.1 – 0.3 bar VCE with subsequent fire, no escalation, Ref. onshore “Onsite” 0.01
> 0.3 bar VCE escalated to other equipment, 1
Neighbouring < wall cap. No escalated fire Potential thermal and expl. effects
areas4 > wall cap. Escalated fire , 0.5-0.15

Appendix F gives an approach for determining smoke incapacitation, but there is no


recommended single value criterion for smoke as the critical concentration is dependant on
the smoke temperature . Section 10 gives guidance for calculation of fatalities due to smoke
exposure on offshore installations See also section 8 and appendix F
Table 1-2 Recommended Probit Equation Constants for Lethal Toxicity
Chemical Recommended Probit Constants
A B n
Acetonitrile -36.02 3.4 1
Acrolein -3.22 1 1
Acrylamide -17.12 1.7 1
Acrylonitrile -7.52 1 1.3
Allyl Chloride -16.26 1.7 1
Allylalcohol -9.86 1 2
Ammonia -16.21 1.0 2
Aniline -13.01 1.7 1
Arsine -8.78 1.6 1.24
Azinphos-methyl 0.43 1 2
Benzen -109.78 5.3 2
Benzyl Chloride -10.30 1.7 1
Bromine -8.54 1.0 2
Carbon Disulfide -16.61 1.7 1
Carbon Monoxide -7.21 1.0 1
Carbon Tetrachloride -21.80 1.8 1
Chlorine -4.81 0.5 2.75
Crotonaldehyde -13.13 2.0 1
1,2-dichloroethane -16.50 1.7 1

4
The effects related to neighbouring areas are very dependant on the physical layout of the installation and should be
subjected to a separate evaluation for each installation In many cases an area classed as neighbouring might not be
separated from the initial area by a barrier which reduces the overpressure to a point where it is negligible. Separate CFD
analysis could be used for this purpose. In the absence of CFD use can be made of TNO curves or simpler rule sets..
5
These are figure used in a number of DNV studies and should be used as indicative. There exists no specific reference to
this type of fatality fraction but the fraction should be subjected to a platform individual evaluation.

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DNV TECHNICAL NOTE Page 7 of 126

Prepared by: P. Date: 13 September 2010


Crossthwaite, A. Falck, K.
Kenich HUMAN IMPACT
CRITERIA
Issued for RiskNet Ref: T15 Revision No. 03

Chemical Recommended Probit Constants


A B n
Epichlorohydrin -117.95 10.4 1
Ethylene dibromide -19.43 2.3 1
Ethylene Oxide -6.15 1 1
Ethyleneimine -10.36 1.8 1.13
Fluorine -19.13 1.7 2
Formaldehyde -54.67 6.6 1
Hydrazine -13.48 1.7 1
Hydrogen Chloride -35.62 3.7 1
Hydrogen Cyanide -9.43 1.0. 2.4
Hydrogen Fluoride -8.62 1.0 1.5
Hydrogen Peroxide -16.43 1.7 1
Hydrogen Sulphide -10.76 1 1.9
Methanol -23.67 1.9 1
Methyl Bromide -5.75 1.0 1.1
Methyl Isocyanate -0.57 1 0.7
Methyl Mercaptan -16.33 2.1 0.98
Nitric Oxide -151.1 15.5 1
Nitrobenzene -16.44 1.7 1
Nitrogen dioxide -16.06 1 3.7
O-cresol -9.25 1.7 1
Parathion -1.54 1 2
Perfluoroisobutene -8.51 2.8 1
Phenol -13.49 1.7 1
Phosgene -7.69 2.0 1
Phosphamidon -1.01 1 0.7
Phosphine -6.03 1.0 2
1,2-propylene oxide -15.72 1.7 1
Sulphur dioxide -16.76 1.0 2.4
Sulphuric acid -5.29 0.8 2
Tetraethyl lead -4.53 1.0 2
Toluene -6.79 0.41 2.5
2,4-Toluene diisocyanate -9.34 2.3 1
Vinyl Chloride -22.55 1.7 1

It should be appreciated that several of the impact criteria, probit-based or single-value,


presented and recommended here are not universally accepted (internally or externally). Take
for example the impact criteria for thermal radiation and the recent findings by Raj (/93/ and
/94/) concerning the criteria for incapacitation. The aim of this TN is to provide a common
basis for analysis in DNV based on the latest thinking, However we should continue to

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Prepared by: P. Date: 13 September 2010


Crossthwaite, A. Falck, K.
Kenich HUMAN IMPACT
CRITERIA
Issued for RiskNet Ref: T15 Revision No. 03

follow and participate in the discussions which might develop thinking on human impact from
toxic, flammable and explosive materials.

The probit relationship used in any particular analysis should be discussed and agreed with a
client before carrying out the analysis. If a client requests the use of impact criteria which are
different from those recommended in this technical note, then they should be used (although it
may be appropriate to state in the report that the relationship used is not that recommended for
use by DNV internal guidance. It may also be that offices carrying out work for clients where
the ambient temperature is closer to 25C than 10C would wish to use the probits with a
reference temperature of 25C; this is perfectly acceptable.

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DNV TECHNICAL NOTE Page 9 of 126

Prepared by: P. Date: 13 September 2010


Crossthwaite, A. Falck, K.
Kenich HUMAN IMPACT
CRITERIA
Issued for RiskNet Ref: T15 Revision No. 03

2 OBJECTIVES
The objective of this Technical Note is to provide a consistent set of human impact criteria for
use in Quantified Risk Analysis (QRA) both onshore and offshore in DNV. Some
information on structural impact is also included primarily because it may result in a
secondary hazard to humans in the vicinity (eg. from falling debris, etc). For offshore studies,
TN 8 should be consulted for further information regarding structural impact and impairment
of safety functions.

The impact criteria contained in this Technical Note relate to impact from:
• toxic gases and vapours;
• short and long duration thermal radiation;
• overpressure; and
• smoke.

The background and recommendations for both single value and multiple value criteria are
given for these hazards.

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DNV TECHNICAL NOTE Page 10 of 126

Prepared by: P. Date: 13 September 2010


Crossthwaite, A. Falck, K.
Kenich HUMAN IMPACT
CRITERIA
Issued for RiskNet Ref: T15 Revision No. 03

3 DEFINITIONS
The following are working definitions of terms commonly used in human impact studies.

Probit

The range of susceptibility in a population to a harmful consequence can be expressed


mathematically using a criterion in the form of an equation which expresses the percentage of
a defined population which will suffer a defined level of harm (normally death) when it is
exposed to a specified dangerous load. This is a `Probit' equation which has the form:

Y = A + B Ln (Cn.t)
Y is the probit (or probability measure), A, B and n are constants, C is a concentration and t is
time. The probit, Y, has the properties of the Normal distribution, with a Variance of 1 but a
mean of 5. Its probability values (eg. percentage fatality) can be determined by reference to
any Normal distribution table (single-tailed) by adding 5 to the standard deviation value, or by
reference to published tables (/56/). The most commonly used table is given as Table I.1 in
Appendix I. For further details of probit analysis methodologies see Appendix I.

Lethal Dose (LD)


A combination of concentration and exposure duration which is lethal to a certain fraction of
the exposed population.

LD50
A dose which will cause the deaths of 50% of an exposed population. The dose is a function
of concentration raised to some power and duration of exposure. It is not, in this context, the
amount taken into the body expressed in terms of mg/kg of body weight.

LDLo
The lowest published dose to cause a fatality.

Lethal Concentration (LC)


LC50:A concentration which, for a specified duration of exposure, will cause the deaths of
50% of an exposed population. The associated exposure duration is normally given; if not it
is usual to assume 4 hours though it may be advisable to discard data where the duration is not
given.

LCLo
The lowest published concentration which, for a given duration of exposure, caused a fatality.
Toxic dose (TD)

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Prepared by: P. Date: 13 September 2010


Crossthwaite, A. Falck, K.
Kenich HUMAN IMPACT
CRITERIA
Issued for RiskNet Ref: T15 Revision No. 03

TDLo
The lowest published toxic dose.

Other Concentrations
TLV(/57/)
Threshold limit values published by the American Conference of Governmental Industrial
Hygienists in 1990. The values given are normally 8 hour time weighted averages (TWA) for
a working lifetime. Shorter periods are also specified though less commonly used: Short
Term Exposure Limit (TLV-STEL) and Ceiling (TLV-C).

Emergency Response Planning Guideline (ERPG) (/58/)

Published by the American Industrial Hygiene Association.

ERPG-3 is the maximum airborne concentration below which, it is believed, nearly


all individuals can be exposed for up to 1 hour without experiencing or
developing life threatening health effects.

ERPG-2 is the maximum airborne concentration below which, it is believed, nearly


all individuals can be exposed for up to 1 hour without experiencing or
developing irreversible adverse health effects or symptoms which could
impair an individual's ability to take protective action.

ERPG-1 is the maximum airborne concentration to which nearly all individuals


could be exposed for up to 1 hour without experiencing other than mild
transient health effects or perceiving a clearly defined objectionable odour.
Immediately Dangerous to Life and Health (IDLH) (/62/)
Published by NIOSH. The maximum airborne concentration of a substance to which a
healthy male worker can be exposed for as long as 30 minutes and still be able to escape
without loss of life or irreversible organ system damage.

HSE Dangerous Toxic Load (DTL) (/91/)


Developed by the HSE for land use planning purposes, and describes the exposure conditions,
in terms of concentration and duration of exposure, which lead to a particular level of toxicity.
Two such levels of toxicity are the SLOT and SLOD. The toxic load is expressed in the form
Cnt.

Specified Level of Toxicity (SLOT) (/91/)


Used by the UK Health and Safety Executive (HSE), this level of toxicity (known as a
‘Dangerous Dose’) is defined as that which causes:
o severe distress to almost everyone;

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Kenich HUMAN IMPACT
CRITERIA
Issued for RiskNet Ref: T15 Revision No. 03

o a substantial fraction to require medical attention;


o some people to be seriously injured, requiring prolonged treatment and
o possible fatality for any highly susceptible people.

It is normally assumed that the SLOT/Dangerous Dose is 1% mortality. Thus the SLOT-value
is the toxic load, Cnt, at which 1% mortality is observed.

Significant Likelihood of Death (/91/)


Used by the UK Health and Safety Executive (HSE) and is the DTL, Cnt, relating to the
mortality of 50% of the exposed population.

HSE Long Term Exposure Limit (HSE LTEL) (/60/)


An 8 hour time weighted average exposure limit which is intended to control exposure to
substances which have long term or cumulative effects as required by the UK COSHH
Regulations (/61/).

HSE Short Term Exposure Limit (HSE STEL) (/60/)


A limit based on a 10 minute exposure duration which is intended to control exposure to
substances with acute effects, also developed under the requirements of the COSHH
Regulations.

Dangerous Thermal Dose (DTD)


Developed by the HSE from work by Hymes (/4/) who considered that the level of injury is
related to the thermal dose received expressed as:
Thermal Dose = I4/3 t
where I is incident flux (kW/m2) and t is time (seconds)

Dangerous Level of Overpressure (DLO)


Also developed by the HSE, for use in explosion impact assessment and based on peak side-
on overpressure.

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Prepared by: P. Date: 13 September 2010


Crossthwaite, A. Falck, K.
Kenich HUMAN IMPACT
CRITERIA
Issued for RiskNet Ref: T15 Revision No. 03

4 APPLICABILITY

4.1 General
The impact criteria in this TN are applicable to all QRAs in which the effect on people from
an accidental release of hydrocarbon or other hazardous material (excluding nuclear radiation)
is to be evaluated.

4.2 Probabilistic Criteria


These use a "sliding scale" of impact (rather than a hazard level/fatality probability envelope)
often based on a probit relationship. Their use is preferred for toxic gas analyses, although
care should be exercised in their application for very low fatality ranges (i.e. less than 5%).

The general expression for (toxic) probits is: /1/

Pr = A + B ln C nt

Where

A,B and n are constants defined for each material (unit specific)

C is concentration (ppm or mg/m3)

t is time (minutes or seconds)

Probits for thermal exposure and harm from explosion overpressure follow the same general
form.

Since the probit values express the relations ship between the dose exposure and expected
human response in terms of a normal distribution, N(5,1), the translation from probit to
percentage of the population affected is not obvious. The following calculation guides may
be helpful:

1% of the population is affected (corresponds to a probit value of 2.67): /2/

1/n
 2.67 - A 
C=
e B 
 t 
 

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Crossthwaite, A. Falck, K.
Kenich HUMAN IMPACT
CRITERIA
Issued for RiskNet Ref: T15 Revision No. 03

for a given time exposure.

2.67 - A
e B
t= /3/
C

for an exposure to a given concentration. 50% of the population is affected (corresponds to a


probit value of 5): /4/

1/n
 5B- A 
C=
e 
 t 
 

for a given time exposure.

5- A
eB
t= /5/
C

for an exposure to a given concentration. Appendix A gives a more detailed introduction to


probit analysis.

4.3 Single Value Criteria


In many assessments single value criteria are used. The criteria given combine a hazard level
and a fatality probability. All people within the envelope of the hazard level are subject to the
fatality probability; people outside the envelope are assumed not to be affected. This step
function is a simplification of actual effects but has historically been used, especially for
thermal radiation and overpressure effects.

Single value criteria described here may have been derived from a probit relationship
according to the method described in Appendix G. If a more detailed approach to fatality
impacts is chosen (e.g. multiple exposure levels or a more detailed approach to societal risk),
the relevant probit should be consulted.

The use of single-value criteria is coarse and the values recommended here are by no means
universally accepted. The aim is to define these criteria in a systematic way so that QRAs are
performed in a uniform manner by DNV.

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Kenich HUMAN IMPACT
CRITERIA
Issued for RiskNet Ref: T15 Revision No. 03

4.3.1 Individual Risks


The use of single value criteria relates to calculation of individual risks, and the criteria used
relate to a person of a particular vulnerability. The lethal doses calculated in this Technical
Note are based upon the LD50 dose. This Technical Note therefore presumes that the use of
the single value criterion in the calculation of individual risk is such that if an individual was
exposed to a LD50 dose the person would be killed (and also that the person is an average
susceptibility to the hazard). If other definitions of risk are applied, the criterion must change
accordingly.

It may be argued that personnel on offshore platforms are relatively young and fit, have better
health and health care etc. compared to an average group of people in society (and therefore
are less susceptible to harm that the average person), and old people are more susceptible.
The derivation of a single value criterion generally ignores this distinction.

4.3.2 Group Risks


In the degree that group risks (e.g. PLL) are calculated in offshore QRAs, these are normally
based upon the individual risk exposures. This strictly speaking is not correct, unless all
people on the platform actually have average susceptibility. This approximation is often
accepted and further detailed calculations are not usually performed. If a more detailed
approach is desirable, the probits and other background material presented should be
consulted. Onshore analyses typically cover a wide area with people being exposed to the
whole range of vulnerabilities. Single value criteria should preferably be replaced by more
accurate vulnerability modelling if the risk from a hazard using a single value approach is
determined to be significant.

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Kenich HUMAN IMPACT
CRITERIA
Issued for RiskNet Ref: T15 Revision No. 03

5 TOXIC GASES AND VAPOURS


For toxic gases and vapours it is generally appropriate to use a probabilistic criterion; these
are normally based on probit relationships. Recommended probits are found in section 5.1.1.
For offshore analyses, a single value criterion has been developed for hydrogen sulphide
(H2S) see section 5.1.2 since modelling tools for offshore generally do not use probits. In
section 5.2 the effects of some of the most common substances are presented.

5.1 Impact criteria


5.1.1 Probits for toxic gases and vapours
A number of different probits are given in Table 5-1. The Probit equation has the form:

Y = A + B ln(Cnt)

Where Y is the probability measure, A, B and n are constants, C is the concentration either in
mg/m2 or in ppm, t is the time in minutes or seconds. DNV generally uses the units of ppm
and minutes.

There are three main publishers of toxicity data and probits referenced in this TN, the Purple
Book (PSG 3 /97/), and the Handleiding Risicoberekeningen /96/(referred to as the ‘New
Purple Book’), the HSE (/91/ dated 2008) and the CCPS (/62/, dated 1980). In Table 5-1, an
overview is given of probits from these three sources, PhastRisk 6.53.1 and the Northern
Belgian required probits (/92/). For each substance the probit recommended for use in DNV is
highlighted (in bold).

Handleiding Risicoberekeningen (/96/() and the CCPS (/62/) give probits for some substances
directly. The HSE publishes toxicity data in the form of SLOT and SLOD values (/91/),
which have been used to derive probit constants.

Different sources use different units for the concentration (mg/m3 or ppm). The concentration
in ppm is dependent on the temperature. The method to convert between units is given in
Appendix D of this TN. It should be noted that in PhastRisk 6.53.1, the probits are given for
concentrations in ppm at 9.85°C.

In the previous revision of this TN, the recommended probit was selected based on different
probits found in the literature and used in previous DNV reports. In this edition, the
recommended probit is chosen based on the following:

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Kenich HUMAN IMPACT
CRITERIA
Issued for RiskNet Ref: T15 Revision No. 03

If the substance is included in the Handleiding Risicoberekeningen (/96/() then the


recommended probit is the one in the Handleiding Risicoberekeningen (/96/).

If the substance is not included in the Handleiding Risicoberekeningen (/96/(), but HSE has
SLOT and SLOD values for a substance (/91/). The recommended probit is calculated based
on the HSE data.

If a material is in neither the Handleiding Risicoberekeningen (/97/) nor the HSE (/91) then
the CCPS probit is used (/62/).

It should be noted that some countries have regulations as to which probits should be used. In
Netherlands, the probits in the Handleiding Risicoberekeningen (/97/) are mandatory. In
Northern Belgium the probits listed below published by the “Departement Leefmiljeu, Natuur
en Energie” (/92/) are mandatory. For a complete overview of the Northern Belgium probits
see /92/.

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Table 5-1 Overview of probits from different sources with DNV recommendation in boldface
Substance New Purple Book (/96/) HSE (/91/) CCPS (/62/) PhastRisk 6.53.1 Northern Belgium (/92/)
A B n ppmn*min C in ppm C in ppm @ 25°C C in ppm @ 9.85°C C in mg/m3
ppm
MW Recom- ppm @
Name g/mol mendation mg/m3 @ 25°C 9.85°C SLOT SLOD A B n A B n A B n A B n
Acetonitrile 41.7 HSE 8.10E+04 1.60E+05 -36.02 3.42 1
Acrolein 56.1 PB -4.1 -3.27 -3.22 1 1 4.20E+02 1.68E+03 -7.48 1.68 1 -9.931 2.049 1 -3.21 1 1 -11.7 2 1
Acrylamide 71.08 HSE 1.30E+05 5.20E+05 -17.12 1.68 1 -10.26 1.678 1
Acrylonitrile 53.1 PB -8.6 -7.59 -7.52 1 1.3 9.60E+03 2.52E+04 -19.47 2.41 1 -29.42 3.008 1.43 -7.52 1 1.3 -7.27 0.86 1.3
Allyl Chloride 76.5 HSE 7.80E+04 3.12E+05 -16.26 1.68 1 -20.20 1.82 1.1
Allylalcohol 58 PB -11.7 -9.97 -9.86 1 2 6.30E+03 2.52E+04 -12.03 1.68 1 -15.1 2 1
Ammonia 17 PB -15.6 -16.33 -16.21 1 2 3.78E+08 1.03E+09 -43.24 2.32 2 -35.9 1.85 2 -16.21 1 2 -34.70 1.85 2
Aniline 93.1 HSE 1.16E+04 4.66E+04 -13.01 1.68 1 -16.9 2 1
Arsine 78 PB -11.2 -8.88 -8.78 1.61 1.24 3.71E+03 5.90E+04 -4.25 0.84 2 -11.20 1.61 1.24
Azinphos-methyl 317.3 PB -4.8 0.33 0.43 1 2
Benzen 78.1 CCPS low acute toxicity not relevant to assessment work -109.78 5.3 2 -109.8 5.3 2 -116.00 5.3 2
Benzyl Chloride 126.6 HSE 2.25E+03 9.00E+03 -10.30 1.68 1 -10.28 1.678 1
Bromine 159.8 PB -12.4 -8.65 -8.54 1 2 1.60E+01 2.60E+01 -10.64 4.80 1 -9.04 0.92 2 -12.36 1 2
1,2-dichloroethane 99 HSE 9.00E+04 3.60E+05 -16.50 1.68 1
Carbon Disulfide 76.14 HSE 9.60E+04 3.84E+05 -16.61 1.68 1 -16.52 1.674 1 -23.44 2.33 0.86
Carbon Monoxide 28 PB -7.4 -7.26 -7.21 1 1 4.01E+04 5.70E+04 -67.68 6.64 1 -37.98 3.7 1 -7.21 1 1 -17.9 1.43 1.4
Carbon Tetrachloride 153.8 HSE 7.20E+05 2.60E+06 -21.80 1.81 1 -6.29 0.408 2.5 -17.9 0.71 2.84
Chlorine 70.9 PB -6.35 -4.89 -4.81 0.5 2.75 1.08E+05 4.84E+05 -15.33 1.55 2 -8.29 0.92 2 -4.81 0.5 2.75 -10.31 0.92 2
Crotonaldehyde 70.1 HSE 3.19E+03 1.05E+04 -13.13 1.96 1 -12.83 1.72 1.16
Epichlorohydrin 92.5 HSE 1.04E+05 1.30E+05 -117.95 10.44 1 -20.28 2.38 1
Ethylene dibromide 187.9 HSE 1.60E+04 4.44E+04 -19.43 2.28 1 -16.30 1.73 1.16
Ethyleneimine/Aziridine 43.1 PB -11.6 -10.47 -10.36 1.77 1.13 1.16E+03 8.25E+03 -5.69 1.19 1 -11.60 1.77 1.13
Ethylene Oxide 44.1 PB -6.8 -6.21 -6.15 1 1 4.68E+04 1.87E+05 -15.40 1.68 1 -6.15 1 1 -18.6 2 1
Fluorine 38 HSE 3.80E+05 1.50E+06 -19.13 1.70 2 -9.15 1 2
Formaldehyde 30 HSE 5.70E+03 8.10E+03 -54.67 6.63 1 -12.24 1.3 2 -12.53 1.3 2
Hydrazine 32.05 HSE 1.51E+04 6.05E+04 -13.48 1.68 1 -13.45 1.676 1 -19.02 2.48 0.81
Hydrogen Chloride 36.5 PB -37.3 -35.82 -35.62 3.69 1 2.37E+04 7.65E+04 -17.36 1.99 1 -16.85 2 1 -15.69 1.69 1.18 -18.20 2 1
Hydrogen Cyanide 27 PB -9.8 -9.56 -9.43 1 2.4 1.92E+05 4.32E+05 -32.28 2.87 2 -29.42 3.008 1.43 -5.8 1.08 1.85 -81.5 6.7 2
Hydrogen Fluoride 20 PB -8.4 -8.7 -8.62 1 1.5 1.20E+04 2.10E+04 -36.44 4.16 1 -25.87 3.345 1 -8.62 1 1.5 -8.40 1 1.5
Hydrogen Peroxide 34.01 HSE 8.60E+04 3.44E+05 -16.43 1.68 1 -16.39 1.678 1
Hydrogen Sulphide 34.1 PB -11.5 -10.87 -10.76 1 1.9 2.00E+12 1.50E+13 -30.08 1.16 4 -31.42 3.008 1.43 -8.53 0.44 4.55 -32.92 3.01 1.43
Methanol 32.04 HSE 8.02E+05 2.67E+06 -23.67 1.94 1 -6.347 0.664 1
Methyl Bromide 95 PB -7.3 -5.81 5.75 1 1.1 3.00E+04 4.80E+04 -48.44 4.96 1 -56.81 5.27 1 -5.74 1 1.1 -64.42 5.27 1
Methyl Isocyanate 57.5 PB -1.2 -0.6 -0.57 1 0.7 7.50E+02 1.68E+03 -16.46 2.89 1 -5.642 1.637 0.653 -0.57 1 0.7
Methyl Mercaptan 48.1 PB -17.8 -16.44 -16.33 2.05 0.98
Nitric Oxide 30.01 HSE 2.09E+04 2.43E+04 -151.10 15.46 1 -150.8 15.43 1
Nitrobenzene 123.1 HSE 8.54E+04 3.41E+05 -16.44 1.68 1 -19.13 2 1
Nitrogen dioxide 46 PB -18.6 -16.26 -16.06 1 3.7 9.60E+04 6.24E+05 -11.61 1.24 2 -13.79 1.4 2 -16.05 1 3.7 -15.65 1.4 2

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Substance New Purple Book (/96/) HSE (/91/) CCPS (/62/) PhastRisk 6.53.1 Northern Belgium (/92/)
n
A B n ppm *min C in ppm C in ppm @ 25°C C in ppm @ 9.85°C C in mg/m3
ppm
MW Recom- ppm @
Name g/mol mendation mg/m3 @ 25°C 9.85°C SLOT SLOD A B n A B n A B n A B n
O-cresol 108.1 HSE 1.20E+03 4.80E+03 -9.25 1.68 1 -15.50 1 2
Parathion 291.3 PB -6.6 -1.64 -1.54 1 2
Perfluoroisobutene 200 HSE 5.40E+01 1.24E+02 -8.51 2.80 1
Phenol 94.1 HSE 1.50E+04 6.00E+04 -13.49 1.68 1 -13.46 1.678 1 -15.2 1 2
Phosgene 98.9 PB -10.6 -7.81 -7.69 2 1 1.08E+02 3.48E+02 -6.65 1.99 1 -19.27 3.686 1 -7.69 2 1 -29.60 4.55 1
Phosphamidon 299.7 PB -2.8 -1.05 -1.01 1 0.7
Phosphine 34 PB -6.8 -6.14 -6.03 1 2 6.90E+03 1.08E+04 -43.30 5.20 1 -9.06 1.63 1.23
1,2-propylene oxide 58.1 HSE 5.16E+04 2.04E+05 -15.72 1.70 1 -7.415 0.509 2 -15.69 1.692 1
Sulphur dioxide 64 PB -19.2 -16.89 -16.76 1 2.4 4.66E+06 7.45E+07 -10.23 0.84 2 -15.67 2.1 1 -16.75 1 2.4 -27.90 1.14 3.7
sulphuric acid 98.1 HSE 1.30E+04 2.08E+05 -5.29 0.84 2
Tetraethyl lead 323.4 PB -9.8 -4.64 -4.53 1 2 1.52E+03 3.79E+03 -16.01 2.55 1 -9.81 1 2
Toluene 92.14 CCPS -6.79 0.41 2.5 -6.794 0.408 2.5
2,4-Toluene diisocyanate 174 HSE 1.76E+02 4.80E+02 -9.34 2.32 1 -27.14 2.43 2
Vinyl Chloride 62.5 HSE 3.39E+06 1.36E+07 -22.55 1.68 1 -22.5 1.674 1

The minor differences between cols 11,12 and cols 17,18 are due to rounding. Most of the values in /96/ are also in /97/ and /16/

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5.1.2 Single value criterion for hydrogen sulphide for use offshore
Appendix G gives a methodology for defining single value criteria based on a probit. Using
the following assumptions possible criteria are presented in Table 5-2:
• Time to escape is set (personnel have to secure their work or may not be able to
escape immediately) as either 2, 5 or 30 minutes.
• Incapacitation dose is set to 75% of lethal dose

Table 5-2 Possible single-value criteria from H2S probits.


LC50 LC50
LC50 after 2 after 5 after 30
Probit minutes Criterion minutes Criterion minutes Criterion
Purple Book 2950 2530 1820 1550 710 610
HSE 1655 1540 1320 1225 840 780

For offshore studies using a single-value criterion for H2S, 1550 ppm is recommended based
on the use of the probit recommended for use (the Purple Book) with a an exposure duration
of 5 minutes. Note however that this value may well be somewhat higher than values derived
by other methods, and higher than a value derived from the effects given in Table 5-6.

Background

The immediate effect of inhalation of very high concentrations of hydrogen sulphide is


respiratory paralysis after a breath or two and inhibition of the respiratory centre of the brain.
At slightly lower concentrations, respiratory paralysis is preceded by a period of rapid
breathing or hyperpnea and death will result unless the victim is removed from exposure and
artificially ventilated.

Even at moderate concentrations, hydrogen sulphide is extremely irritating to the mucous


membranes of the respiratory tract and the eyes. Pulmonary edema, which can be life-
threatening, almost always occurs. Extended exposure to gas at relatively low concentrations
of 50 ppm can lead to inflammation of the epithelia of the entire respiratory tract. The
epithelia of the eye, especially the conjunctivae and the cornea, are similarly affected,
resulting in "sore eye" or "gas eye". Only at relatively low concentrations, not associated with
significant damage, except to the eyes, is the obnoxious, rotten egg-like odour of the gas a
warning of its presence. At levels above 150 ppm, the olfactory sense is lost, and there are
increasing levels of irritation of the eyes, nose, and throat as well as increased difficulty in
breathing.

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CRITERIA
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5.2 Effects of some substances


As background material, the effects that might be experienced by humans to various
concentrations of the following materials are included below. It is recognised that the
concentrations for fatalities may not agree with those predicted using the probits given above.
They are useful, however, as a general guide. The chemicals included here are:
• Ammonia
• Chlorine
• Hydrogen Fluoride
• Hydrogen Sulphide
• Hydrogen Cyanide
• Sulphur Dioxide

5.2.1 Ammonia
The following table illustrates the effects likely to be experienced by humans exposed to
various concentrations of ammonia (/52/). It is recognised that the concentrations for
fatalities may not agree with those predicted using the probits given above. They are useful,
however, as a general guide.
Table 5-3 Human Impact from Ammonia Exposure
Ammonia Effects Exposure Duration
Concentration (ppm)
50-53 Odour detectable by most Prolonged repeated exposure produces
persons. no injury.
100 No adverse effects for average Maximum allowable concentration for 8
workers hour working day.
300 Maximum tolerated without 1 hour.
serious disturbance.
400-700 Nose and throat irritation. Eye Infrequent, short (1 hr) exposures
irritation with tearing. ordinarily produces no serious affects.
2000-3000 Convulsive coughing, severe No permissible exposure.
eye irritation.
5000-7000 Respiratory spasm, rapid No permissible exposure. Rapidly fatal.
asphyxia.

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CRITERIA
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5.2.2 Chlorine
The following table illustrates the effects likely to be experienced by humans exposed to
various concentrations of chlorine (/52/). It is recognised that the concentrations for fatalities
may not agree with those predicted using the probits given above. They are useful, however,
as a general guide.
Table 5-4 Human response to Chlorine exposure
Chlorine Effect
Concentration
(ppm)
1 Minimum concentration causing slight symptoms after several hours.
3.5 Minimum concentration detectable by odour.
4 Minimum concentration that can be breathed for 1 hour without damage.
15 Minimum concentration causing throat irritation.
30 Minimum concentration causing coughing.
40-60 Concentration dangerous in 30 minutes.
1000 Concentration likely to be fatal after a few deep breaths.

5.2.3 Hydrogen Fluoride


The following table illustrates the effects likely to be experienced by humans exposed to
various concentrations of hydrogen fluoride (/53/). It is recognised that the concentrations for
fatalities may not agree with those predicted using the probits given above. They are useful,
however, as a general guide.
Table 5-5 Human response to hydrogen fluoride exposure
Hydrogen Effect
Fluoride
Concentration
(ppm)
2-3 Detectable by smell.
5 Least amount causing throat irritation.
50 - 250 Dangerous amount for short term exposure.

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5.2.4 Hydrogen Sulphide


The following table illustrates the effects likely to be experienced by humans exposed to
various concentrations of hydrogen sulphide (/54/). It is recognised that the concentrations
for fatalities may not agree with those predicted using the probits given above. They are
useful, however, as a general guide.
Table 5-6 Human response to hydrogen sulphide exposure
Hydrogen Effect
Sulphide
Concentration
(ppm)
20-30 Conjunctivitis.
50 Objection to light after 4 hours exposure. Lacrimation.
150-200 Objection to light, irritation of mucous membranes, headache.
200-400 Slight symptoms of poisoning after several hours.
250-600 Pulmonary edema and bronchial pneumonia after prolonged
exposure.
500-1000 Painful eye irritation, vomiting.
1000 Immediate acute poisoning.
1000-2000 Lethal after 30 to 60 minutes.

5.2.5 Hydrogen Cyanide


The following table illustrates the effects likely to be experienced by humans exposed to
various concentrations of hydrogen cyanide (/54/). It is recognised that the concentrations for
fatalities may not agree with those predicted using the probits given above. They are useful,
however, as a general guide.

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Table 5-7 Human expose to hydrogen cynanide exposure


HCN Effect
Concentration
(ppm)
0.2 - 5.1 Threshold of odour.
18 - 54 Reported symptoms vary from none after 6 hours exposure to
complaints of headache, nausea, vomiting and cardiac distress
after an unspecified time.
50 Numbness, weakness, vertigo, nausea, rapid pulse, flushing of
face, headache, gastric distress.
110 - 135 Fatal after ½ - 1 hr or dangerous to life.
135 Fatal after 30 minutes.
181 Fatal after 10 minutes.
280 Immediately fatal.

5.2.6 Sulphur Dioxide


The following table illustrates the effects likely to be experienced by humans exposed to
various concentrations of sulphur dioxide (/54/). It is recognised that the concentrations for
fatalities may not agree with those predicted using the probits given above. They are useful,
however, as a general guide.
Table 5-8 Human response of sulphur dioxide exposure
Concentration Effect
(ppm)
3-5 Threshold of odour.
8-12 Slight irritation of eyes and throat, resistance of air tracts.
20 Coughing and eye irritation.
30 Immediate strong irritation, remains very unpleasant.
100-250 Dangerous to life.
600-800 Death in a few minutes.

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6 THERMAL RADIATION

6.1 Introduction
When flammable materials are burned a number of different forms of combustion can take
place. These, for QRAs, are commonly categorised as flash fires, pool fires, jet fires and
fireballs. This Technical Note concentrates on the effects of thermal radiation from these fire
types on humans but gives some information on the effects on structures and/or materials.
Probits are then reviewed and single impact criteria are given.

6.2 Background
6.2.1 The Effects of Thermal Radiation
The degree of harm to people exposed to thermal radiation is a function of both the intensity
of thermal radiation and the time for which the individual is exposed. As the radiation
intensity is increased, the time to feel pain reduces (see Table 6-1). Data suggests that the
degree of harm is best correlated by a thermal dose of the form:

Thermal dose = I4/3 t

Where

I = incident thermal radiation (kW/m2)

t = exposure time (sec)

Injuries from burns result from prolonged exposure to radiation, and are usually characterised
as:

First degree burns - superficial burn giving red dry (painful) skin

Second degree burns - blister formation with the epidermis being affected

Third degree burns - full thickness burn when the dermis and nerve
extremities are affected resulting in a dry skin which
has no feeling.

Second and third degree burns can lead to disability and there is a possibility of mortality.

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Kenich

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As the dose is increased above that required to give third degree burns, ignition of clothing
could be anticipated. Certain effects of different doses of thermal radiation are given in
Table 6-2 and effects of different heat fluxes and exposure times are shown in Table 6-1.
Based on the data given in Table 6-1, API produced recommendations for flare radiation
(excluding solar radiation) as given in Table 6-3.
Table 6-1 Exposure Time Necessary to Reach the Pain Threshold (API, /63/)
Radiation Intensity Time to Pain Threshold
kW/m2 BTU/hr/ft2 (s)
1.74 550 60
2.33 740 40
2.90 920 30
4.73 1500 16
6.94 2200 9
9.46 3000 6
11.67 3700 4
19.87 6300 2

Table 6-2 Summary of Effects of Certain Levels of Thermal Radiation


Effect Required Thermal Dose Comments
(W/m2)4/3t/104
Threshold second degree or From about 210 to about 700. There is considerable evidence for
blistering of exposed skin. a region of constant injury
between these dose levels.
Second degree-plus burns (>0.1 About 1200 (means of several Figure of 1200 is approximately
mm deep) to exposed skin. sources) with burn depth increasing same dose as 1% lethality to
linearly with heat input to about averagely dressed exposees.
2600.
Third degree burns to exposed About 2600 (mean as above). Approximately same dose as 50%
skin (2.0mm) i.e. full Dermis. lethality to averagely dressed
exposees.
Melting of nylon, polyester From about 1500 to 3000. Potentially severe burns from
fabrics. molten fabric.
Piloted ignition of clothing. From about 2500 to 8000 Serious secondary effects from
burning garments.
Auto ignition of every day From about 3500 to 12000
clothing.

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Table 6-3 Recommended design thermal radiation personnel (API 521, /63/)
Btu/h/ft2 kW/m2 Conditions
3000 9.5 Maximum radiant heat intensity at any location where urgent emergency action
by personnel is required. When personnel enter or work in an area with the
potential for radiant heat intensity greater than 6,31 kW/m2 (2 000 Btu/h·ft2),
then radiation shielding and/or special protective apparel (e.g. a fire approach
suit) should be considered.
SAFETY PRECAUTION — It is important to recognize that personnel with
appropriate clothing a cannot tolerate thermal radiation at 6,31 kW/m2 (2 000
Btu/h·ft2) for more than a few seconds.
2000 6.3 Maximum radiant heat intensity in areas where emergency actions lasting up to
30 s can be required by personnel without shielding but with appropriate clothinga
1500 4.7 Maximum radiant heat intensity in areas where emergency actions lasting 2 min
to 3 min can be required by personnel without shielding but with appropriate
clothinga
500 1.6 Maximum radiant heat intensity at any location where personnel with appropriate
clothinga can be continuously exposed
a
Appropriate clothing consists of hard hat, long-sleeved shirts with cuffs buttoned, work gloves, long-legged pants and work shoes.
Appropriate clothing minimizes direct skin exposure to thermal radiation.

In addition to the incident thermal flux and the duration of exposure, a number of other factors
also affect the degree of harm. These include:
• Source of thermal radiation e.g. hydrocarbon fire or thermonuclear device
• Area of skin exposed
• Age of person
• Type of clothing
• Speed and type of medical attention after exposure

Further, a significant factor in the consideration of the impact of thermal radiation when
carrying out a QRA is whether a person is considered to be outdoors or indoors, and further if
a person originally outdoors can find shelter and if person originally indoors tries to escape
from the building.

It should be noted that there is an ongoing discussion relating to human tolerance to fire
radiant heat exposure. In recent studies (/93/ and /94/), Raj questions the US regulatory
criterion of 5kW/m2 for 30 seconds to define the safety distance for LNG plants. The author
himself was exposed to heat levels from 3.5kW/m2 to 5kW/m2 for several tens of seconds
without any injury or pain. He also shows that using dummies to measure the effect of

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Kenich

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radiation on skin temperature is not plausible due to the protective systems of the human
body. The experiments also suggest that normal clothing can reduce the heat flux to the skin
by a factor of 2-3. This is valid for the general public; most installations will have protective
clothing for personnel, which one must suppose will reduce this even further. Raj also
questions the use of exposure times as high as 30 seconds stating that it should be possible for
a grown person to move up to 40-80 meters in this time span, taking into account reaction
time of untrained personnel.

6.2.2 Structural Effects


The effect of thermal radiation on plant and structures is, offshore, generally of more
significance than the effect on people, particularly the jet and pool fires. Information is given
below on the effects on various materials but the original reference should be consulted before
specific criteria are used in QRAs.

Lees (/71/) reports work by Lawson and Simms (/72/) who give relationships between
incident radiation and ignition of wood. The relationship for spontaneous ignition is:

(I - Is) t4/5 = k1

where I is the incident radiation (kW/m2), Is is the critical intensity for spontaneous ignition
(equal to 25.4 kW/m2), t is time in seconds and k1 is a constant (equal to 6.73 kJ/m2 s1/5).

For piloted ignition the relationship is: (I – Ip) t2/3 = k2

where Ip = 13.4 kW/m2 and k2 = 8.05 kJ/ m2s1/3.

Other sources (/73/) suggest that the values for k1 and k2 are in error and should have values,
based on American Whitewood, of 167.6 kJ/m2s1/5 and 118.4 kJ/ m2s1/3 respectively. The
source also gives values of Is and Ip of 25.6 kW/m2 and 14.7 kW/m2 respectively.

Table 6-4 and Table 6-5 give critical radiation intensities for ignition and are taken from the
TNO report (/59/) and the PhastRisk User Manual (/74/).

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Kenich

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Table 6-4 Critical radiation intensities for ignition (TNO)


Material Critical radiation intensity [kW/m2]
With ignition flame; in With ignition flame; Without ignition flame
contact with the surface without contact with the
surface
Wood 5 15 35
Hemp, jute, flax 40
Roofing material soaked in 3
asphalt-bitumen
Roofing material protected 75
by aluminium plates
Textile 35
Soft board 6 25
Hard board 5 10 30
Cork 30 23

Table 6-5 Critical radiation intensities (PhastRisk)


Radiation Intensity Observed Effect
(kW/m2)
37.5 Sufficient to cause damage to process equipment.
25 Minimum energy required to ignite wood at indefinitely
long exposures (non-piloted).
12.5 Minimum energy required for piloted ignition of wood,
melting of plastic tubing.

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6.2.3 Thermal Radiation Probits


The most commonly used probit to determine the percentage lethality from thermal radiation
is the well known Eisenberg probit (/65/) developed for the U.S. Coast Guard:

Y = -14.9 + 2.56 ln (I4/3 t)

where I is thermal radiation flux in kW/m2 and t is exposure time in seconds.

The probit is based on thermal radiation from nuclear explosions. TNO (/16/) present the
probit as

Y = -38.48 + 2.56 ln (I4/3 t)

where I is in W/m2. These two forms are equivalent.

From a later version of the vulnerability model (/66/), a thermal radiation probit for
hydrocarbon fires is derived and presented in the TNO report as:-

Y = -36.38 + 2.56 ln (I4/3 t) where I is in W/m2

Or

Y = -12.80 + 2.56 ln (I4/3 t) where I is in kW/m2

It will be noted that the thermal dose required for a given lethality level is lower for
hydrocarbon fires than for nuclear explosions. Both these probits are for naked human flesh;
a probit for lethality of clothed personnel exposed to hydrocarbon pool fires has been derived
as (/67/):

Y = -37.23 + 2.56 ln (I4/3 t) where I is in W/m2

or

Y = -13.65 + 2.56 ln (I4/3 t) where I is in kW/m2

Probits have also been developed for impact other than lethality. The Eisenberg Vulnerability
Model (/65/) presents the limit value for first degree burns as:

t I1.15 = 5.5 x 105 (W/m2)1.15 sec.

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and for second degree burns

t I 4/3 = 8.7 x 106 (W/m2) 4/3 sec.

For hydrocarbon fires, probits for first and second degree burns are presented as16:

Y = -39.83 + 3.0186 ln (I4/3 t) (first degree)


and
Y = -43.14 + 3.0186 ln (I4/3 t) (second degree) where I is in W/m2
or
Y = -12.03 + 3.0186 ln (I4/3 t) (first degree)
and
Y = -19.56 + 3.0186 ln (I4/3 t) (second degree) where I is in kW/m2

As an illustration the LD50 has been calculated using the Eisenberg probits for naked and
clothed person in Table 6-6.
Table 6-6 LD50 using the Eisenberg probits
Exposure time 30s 20s 10s
Naked person 14 19 33
Clothed person 27 36 61

6.3 Recommended Criteria for Thermal Radiation

In some countries, the use of probabilistic criteria using a probit is mandatory, see Section
6.3.1. Where probits are not mandatory DNV may use either a probit or single value criteria
(see section 6.3.2).

In PhastRisk 6.53, human impact criteria for thermal radiation from pool and jet fires can be
defined in two ways:

By use of a Probit (the TNO probit is the default)

By use of one or several single-value criteria. For example, 100% mortality inside the
25kW/m2 radiation limit, 50% mortality between the 12.5kW/m2 and 25kW/m2, no fatalities
outside the 12.5kW/m2 radius (these numbers are examples only).

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6.3.1 Probabilistic Criteria


As indicated previously, probit relationships offer the opportunity for a simple but direct
relationship between thermal load and fatality. Some predictions from the probits are given in
Figure 6-2-Figure 6-4:

Figure 6-2 Percentage Fatality for 10 Seconds Exposure

Figure 6-3 Percentage Fatality for 20 Seconds Exposure

Figure 6-4 Percentage Fatality for Exposure to Various Thermal Doses

In the Netherlands (/16/) and Northern Belgium (/92/), it is required to use the criteria in
Table 6-7 for pool and jet fires, where Plethal is found using the probit below and an exposure
time of 20s.

Y = -36.38 + 2.56 ln (I4/3 t) where I is in W/m2


Table 6-7 Green Book Impact Criteria (/16/)
Area Individual Risk Societal Risk Indoors Societal Risk Outdoors
Inside flame area (LFL) 1 1 1
Radiation > 37.5 kW/m2 1 1 1
Radiation < 37.5 kW/m2 Plethal 0 0.14 * Plethal

6.3.2 Single Value Impact Criteria

The different fire types have historically been associated with different forms of criteria:
• for vapour cloud fires a specific concentration of vapour in air (usually LFL, but
sometimes 0.5 LFL) is used;
• for stable fires of `long' duration (i.e. more than about one minute) a criterion thermal
radiation flux (kW/m2) is used;
• for short duration fires (principally fireballs) a combination of thermal radiation flux
and time is used - this would be either in the form of kJ/m2 or (kW/m2)4/3s (generally
termed a thermal dose).

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Different criteria have been used for various studies for various reasons. From a review of
these criteria it is recommended that certain fixed criteria are used for the various fire types
together with a value for fatality for people within the criterion level. A short comment gives
the background to the selection of the value.
6.3.2.1 Flash Fire

When a flammable cloud is ignited a flame travels through the cloud and combustion occurs
in such a way that the hot gases produced rise; there is little expansion horizontally.
Consequently people within the cloud are subject to flame engulfment for a short period of
time; people outside the cloud are not engulfed in flame and are only subject to thermal
radiation for a short time. For the cloud to burn as a whole (sustained combustion) and burn
back to the source of release, the concentration needs to be above 0.9 LFL (/68/). At lower
concentrations (down to 0.6 LFL) combustion gives only pockets of flames. The LFL
envelope is recommended as a criterion. For people located outdoors, the mortality within this
limit is expected to be high, however buildings give good protection against flash fire. Thus a
mortality probability of 1 for people outside and 0.1 for people inside is often applied when
using this criterion. The use of fire retardant overalls, training and ease of movement in a
horizontal direction enable lower fatality probabilities to be used for workers who are
outdoors. For buildings such as workshops where there are large open doors, it may be more
appropriate to treat them as outdoors rather than indoors. Some buildings (eg with positive
pressure ventilation and automatic shutdown on flammable gas detection) will give virtually
complete protection against flash fire (fatality probability of zero).
Table 6-8 Human impact from flash fire
Fire Type Type of Criterion Recommended Fatality Comments
QRA Probability
(Range of Values)
Outdoors Indoors
Flash Fire Onshore and LFL 1.0 0.1 A high probability of fatality
Offshore (0.5-1.0) (0.01-0.3) for people outdoors but within
the burning cloud. Buildings
provide good protection from
flash fire.

6.3.2.2 Pool Fire, Jet Fire

The effects of pool and jet fires vary extremely widely depending on the circumstances. The
first consideration is whether the person of interest is trained and clothed for work on the
installation (onsite) or a member of the public (offsite). One can assume a higher vulnerability
for the latter both because of protective equipment and better reaction level due to training
and awareness.

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In PhastRisk, it is possible to model fatalities from thermal radiation using a probit (the TNO
probit is the default) or by using one or more criterion level combined with a fatality
probability for each.

Single criterion level

For QRAs applying a single criterion level the thermal radiation levels and fatality
probabilities for people onsite and offsite used historically are summarised in Table 6-9.

To define these criteria the method in appendix G for defining single-value criteria based on a
probit was used together with the following:
• Use of the Eisenberg probit for clothed personnel (onsite) and naked skin (offsite)
• Time taken to escape is greater than 30 seconds. Onsite personnel may have to secure
their work prior to exit from the module.
• Incapacitation occurs at 75% of LD50
• North Sea standard clothing for onsite personnel

It should be noted that for installations in warmer climates and with different safety
regulations, the type of clothing could be very different. In these cases a lower criteria for
radiation intensity should be considered especially for people onshore.
Table 6-9 Human impact from heat loads from pool and jet fires
Criterion Level Fatality probability Likely Effects at Used for people
Criterion Level
Outdoors Indoors
20 kW/m2 1 1 Incapacitation, leading to Onsite
fatality unless rescue is
effected quickly
12.5kW/m2 0.7 0.1 Extreme pain within 20 Offsite
seconds and movement to
shelter is instinctive.
Limiting flux for
secondary fires.

Historically several other single-value criteria have been used in DNV, Table 6-10 gives an
overview of these criterion levels. In defining the single value criterion it is important to
remember that people subject to thermal radiation levels just below the criterion level will be
assumed to be unaffected. This may be of significance for large populations just outside the
criterion envelope.

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Table 6-10 Human impact from heat loads from pool and jet fires
Criterion Level Comment
40kW/m2 Immediate fatality
37.5 kW/m2 Used in the United States
25 kW/m2 Used for personnel onsite on onshore installations.
This is the intensity which is often used to indicate that
normal buildings can be ignited spontaneously

6.3.2.3 Fireballs

DNV has for many years used a dose value in kJ/m2 rather than (kW/m2)4/3s. Although data
support the use of the latter form, use of kJ/m2 instead may not be significant in the context of
the overall modelling. Two criterion values have historically been used (Table 6-11)..
Table 6-11 Human impact from short duration radiation doses (fire balls)
Criterion Level Effect at Criterion Fatality probability Recommended for
(kJ/m2) Level (Range of values)
Outdoors Indoors
375 3rd degree burns (0.7-1.0) (0.1-0.3)
250 2nd degree burns 0.7 0.2 Onsite and offsite
(0.7-1.0) (0.1-0.3) personnel

Note there are many of combinations of flux intensity and impact level which are basically
equivalent. Choosing a low flux / low impact combination is good where societal risk is a
major factor and populations are farther away. Where individual risk to site workers is
important, a high flux / high impact combination may be more appropriate.

Note also that the impact is based on the average intensity over the whole impact area, and
users must not confuse impact levels corresponding to those at the outer envelope boundary,
with those for an average impact over the entire envelope. As thermal intensity falls off at
faster than the square of distance, there might actually be less difference in average impact
from 250 to 375 kJ/m2 than might initially be envisaged.

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Figure 6-1 Tolerance Times to Burn Injury Levels

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100

90

80

70
Percentage Fatality

60 TNO probit for hydrocarbons

TNO probit for clothed personnel exposed to


50
hydrocarbones
Eisenberg Probit
40

30

20

10

0
0 10 20 30 40 50 60 70 80 90 100 110 120
2
Thermal Radiation (kW/m )

Figure 6-2 Percentage Fatality for 10 Seconds Exposure

100

90

80

70
Percentage Fatality

60 TNO probit for hydrocarbons

TNO probit for clothed personnel exposed to


50
hydrocarbones
Eisenberg Probit
40

30

20

10

0
0 10 20 30 40 50 60 70 80
Thermal Radiation (kW/m2)

Figure 6-3 Percentage Fatality for 20 Seconds Exposure

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100

90

80

70
Percentage Fatality

60 TNO probit for hydrocarbons

TNO probit for clothed personnel exposed to


50
hydrocarbones
Eisenberg Probit
40

30

20

10

0
100 1000 10000
Thermal Dose (kW/m2)(4/3)s

Figure 6-4 Percentage Fatality for Exposure to Various Thermal Doses

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7 EXPLOSION OVERPRESSURE

7.1 Introduction
Overpressures which can be hazardous to people may be caused by a number of mechanisms.
These include condensed phase explosions, vapour cloud explosions (VCE), thermal
explosions etc. The characteristics of the overpressures generated by these means are slightly
different. The hazardous effects described in this section are biased towards VCE effects,
although the principles are appropriate for all types of explosion effects and most data have
been derived from condensed phase or nuclear explosions.

This section gives an indication as to the possible impact of different levels of overpressure on
both people and structures, gives probit equations which have been derived for different levels
of impact and single value impact criteria.

7.2 Background
7.2.1 The Effects of Overpressure
The effects of overpressure on humans are normally categorised as follows:

Direct or Primary injury to the body as a result of the pressure change

Secondary injury as a result of fragments or debris produced by the overpressure


impacting on the body

Tertiary injury as a result of the body being thrown bodily by the explosion wind
and impacting on stationary objects or structures

If the explosion is accompanied by combustion of a vapour cloud (as in a VCE), people in the
vicinity of the explosion may also be affected by this combustion directly or by fires which
occur as a result of loss of containment from equipment containing flammable material and
subsequent ignition.

The actual form of overpressure generated by any explosion is characterised by:


o the shape of the waveform
o the peak overpressure (Ps)
o the positive phase duration (tp)
o the impulse (½ Ps tp, assuming a triangular waveform)

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When examining the effects of overpressure it is common for the effect to be related to peak
side on overpressure (pressure at a surface) as this is relatively easy to both calculate and
measure and is the most important single parameter to determine the effects on structures.
This simplification is therefore reasonable for many effects, but in some circumstances e.g.
whole body translation, control room design, it may be necessary for other wave
characteristics to be determined. It should be emphasised that due to reflection a structure or a
person will be exposed to a higher explosion load (factor 1.5- 3) than what you ideally could
measure if you looked at the pressure wave passing.

Primary Effects

The human body is capable of adapting to pressure changes. However, organs can be
damaged if the change is sudden. The lung is generally regarded as the most susceptible
organ which is affected by overpressure and damage to it can lead to death. The ear is more
sensitive but damage to it does not lead to fatality. Peak overpressures which cause damage
to these organs are given in Table 7-1. The values given for VCEs are derived assuming a
similar impact for a peak overpressure which is three times that of the condensed phase
explosion (/81/). It should be emphasised that in an explosion scenario, people in the vicinity
of the accident may also be affected by the burning VCE cloud as covered in section 6.3.

Table 7-1 Human Injury Levels Resulting from Blast Waves, /81/
Injury Type Injury Level Peak Overpressure (bar)
Condensed Phase Vapour Cloud
Explosion
Eardrum Threshold 0.35 1
Failure 50% 1 – 1.4 3 – 4.2
Lung Damage Threshold 0.7 – 0.8 2.1 – 2.4
Lethality Threshold 2.1 - 2.9 6.3 - 8.7
50% 2.9 - 3.9 8.7 - 11.8
Virtually 3.9 - 5.5 11.8 - 16.6
100%

Secondary Effects
Secondary effects cause an impact on people either because of structural e.g. building
collapse, because of missiles e.g. glass fragments or secondary fires from ruptures of
equipment containing flammable material. The former effects are generally of most
significance for people offsite and for people located inside buildings on a process plant,
while the latter one is more relevant for people in the vicinity of an accident and for people on
offshore installations.

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Buildings or process equipment can collapse or be damaged when subject to blast loadings far
lower than those required to produce primary effects on humans.

Empirical data relating the degree of damage of a building and equipment subject to an
overpressure wave are generally given in terms of peak overpressure and are usually from
observations following condensed phase explosions. Typical examples of these data are given
in Table 7-2 and Table 7-3. These lists are oversimplifications as different explosive masses
give different overpressure values for similar effects and wave reflection which can cause
significant damage may not be taken into account.
Table 7-2 Damage Produced by Blast (After Clancey, /75/)
Bar (pressure) Psig (pressure) Damage
0.0014 (0.02) Annoying noise (137 dB), if of low frequency (10 - 15 cps).
0.0021 (0.03) Occasional breaking of large glass windows already under strain.
0.0028 (0.04) Loud noise (143 dB). Sonic boom glass failure.
0.0069 (0.1) Breakage of windows, small, under strain.
0.01 (0.15) Typical pressure for glass failure.
0.02 (0.3) "Safe Distance" (probability 0.05 no serious damage beyond this value).
Missile imit. Some damage to house ceilings; 10% window glass broken.
0.028 (0.4) Limited minor structural damage.
0.034-0.069 (0.5-1) Large and small windows usually shattered occasional damage to
window frames.
0.048 (0.7) Minor damage to house structures.
0.069-0.138 (1-2) Corrugated asbestos shattered. Corrugated steel or aluminium panels,
fastenings fail, followed by buckling. Wood panel (standard housing)
fastenings fail, panels blown in.
0.090 (1.3) Steel frame of clad building slightly distorted.
0.138 (2) Partial collapse of walls and roofs of houses.
0.138-0.207 (2-3) Concrete or cinder block walls, not reinforced, shattered.
0.159 (2.3) Lower limit of serious structural damage.
0.207 (3) Heavy machines (wt 3000lbs) in industrial building suffered little damage.
Steel frame building distorted and pulled away from foundations.
0.207-0.276 (3-4) Frameless, self-framing steel panel building demolished.
Rupture of oil storage tanks.
0.276 (4) Cladding of light industrial buildings ruptured.
0.345 (5) Wooden utility poles (telegraph etc) snapped. Tall hydraulic press
(40000lbs wt) in building slightly damaged.
0.345-0.483 (5-7) Nearly complete destruction of houses.
0.483 (7) Loaded train wagons overturned.
0.483-0.552 (7-8) Brick panels, 8 - 12" thick, not reinforced, fail by shearing and flexure.
0.621 (9) Loaded train box-cars completely demolished.
0.689 (10) Probable total destruction buildings. Heavy (7000lb) machine tools
moved and badly damaged.
Very heavy (12000lb) machine tools survived.
20.68 (300) Limit of crater lip.

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Table 7-3 Blast Damage (After Scilly and High, /76/)


Structural Element Failure Approximate Peak Side on
Mode Overpressure in bar (psi)
1 Te 10 Te 100 Te
Window panes 5% broken 0.01 (.15) 0.001 (.1) 0.007 (.1)
50% broken 0.025 (.36) 0.017 (.24) 0.014 (.21)
90% broken 0.062 (.9) 0.041 (.6) 0.037 (.54)
Houses Tiles 0.044 (.64) 0.029 (.42) 0.026 (.38)
displaced

Doors and
window frames 0.09 (1.3) 0.059 (.86) 0.053 (77)
may be blown in

Category D damage 0.045 (.71) 0.03 (.44) 0.029 (.42)

Category Ca
damage 0.124 (1.8) 0.079 (1.15) 0.076 (1.10)

Category Cb
damage 0.276 (4.0) 0.165 (2.4) 0.154 (2.3)

Category B 0.793 (11.5) 0.359 (5.2) 0.345 (5.0)


damage

Category A damage 1.827 (26.5) 0.793 (11.5) 0.758 (11.0)

Telegraph poles Snapped 3.585 (52) 1.793 (26) 1.655 (24)

Large trees Destroyed 3.930 (57) 1793 (26) 1.655 (24)

Primary missiles Limit of travel 0.014 (.20) 0.01 (.14) 0.008 (.12)

Where damage categorisation as given below is according to Jarrett (/77/)


o Category A: Housing completely demolished
o Category B: House so badly damaged that it is beyond repair
o Category Cb: House rendered uninhabitable by damage
o Category Ca: House rendered uninhabitable but can be repaired quickly
o Category D: House requires repairs but remains habitable

When buildings collapse people inside can be expected to suffer injuries ranging from minor
to fatal. Experience with earthquakes (/16/) has indicated that between 20 and 50% of people
would be expected to be killed. In VCE incidents higher probabilities of fatalities have been
recorded e.g. Flixborough where everyone in the control room at the time of the incident was
killed, although not all fatalities were necessarily due to blast. Factors which are likely to
affect the probability of fatality/survival of a person within a collapsed building are building

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size (larger buildings give higher fatalities), age of the person (young and old are more
susceptible), the age of the building (old housing causing higher fatalities than new houses)
and the basic construction of the building.

Guidance on the vulnerability of people in buildings of different types when subject to


overpressure is available from a number of sources:

API RP 752 (/98/) contains information for a number of building types

Table 4 Building Types in API 752

Building Type Description

B1 Wood frame trailer/shack

B2 Steel framed/metal sided or pre engineered building

Unreinforced masonry bearing wall building. Similar to domestic/small


B3 commercial buildings

B4 Steel or concrete frame with unreinforced masonry infill or cladding

B5 Reinforced concrete or reinforced masonry shear wall building

with % serious injury or fatality vs. overpressure relationships, commencing at 10%


vulnerability.

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API RP 752

100
Serious injury/fatality %

B1, B2, B4
10 B3
B5

1
0 200 400 600 800 1000
Overpressure mbar

Figure 7-1 Serious injuryfatality % versus overpressure, API RP 752

API RP 752 (/98/) is currently under revision, so the above may be changed in the
new version. Also note that API RP 753 (/99/) has superseded API RP 752 with
regard to locating portable buildings (building type B1). /99/) does not give any
overpressure-lethality relationship for such buildings, but the effects of overpressure
are given:

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Building Description Description Upper


Damage of Damage of Trailer Bound
Level construction Pressure

2A Trailer is Studs in the 41 mbar


damaged in reflected
localised wall (that (0.6 psi)
areas. facing the
Individual explosion)
components are expected
on walls to crack but
facing the remain in
blast sustain place
up to major
damage.
Other walls
and the roof
sustain up to
moderate
damage.
Window
breakage
and falling
overhead
items are to
be expected.

2B Trailer Studs on the 62 mbar


damage is walls that do
widespread, not face the (0.9 psi)
but explosion
structural are expected
collapse is to crack with
not more
expected. significant
Wall damage to
components the reflected
facing the wall
blast sustain

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major
damage and
may fail.
Wall and the
roof
components
not facing
the blast
sustain up to
major
damage.
Window
breakage
and falling
overhead
items are to
be expected.

Data from Pressure Levels for Siting Wood Trailers Using the API RP 752
Addendum Simplified Approach, BakerRisk Paper No 760-110-06 Sept 8 2006.

Note that the above effects are for VCEs with long durations (200 ms) and the weakest type of
wooden trailer construction likely to be encountered in processing facilities in the USA.
Metal trailers, wood trailers with wider studs or other wall construction may be stronger.

CIA guidance (/100//) gives relationships for four building types

CIA Category Description

1 Hardened structure building: special construction, no windows.

Typical office block: four storey, concrete frame and roof, brick block
2 wall panels.

3 Typical domestic building: two storey, brick walls, timber floors.

4 Portacabin: timber construction, single storey.

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1
Fatality Probability

CIA1
CIA2
0.1
CIA3
CIA4

0.01
0.01 0.1 1
Overpressure bar

Figure 7-2 fatality probability versus overpressure, WS Atkins report /101/

These curves have been taken from WS Atkins report (/101/) and are for screening purposes
only. It is recommended that /101/ is consulted for detailed analyses or for analyses of
building types not included in the graph.

Wilfred Baker Engineering, Inc. (BakerRisk) carried out work for the Industry Technology
Cooperative. Relationships have been produced for the following building types in terms of a
relationship between explosion parameters and damage severity levels.

Description BEAST Type

Steel framed structure with metal panels for roof and wall cladding 1

Steel framed structure with metal wall panels and a reinforced concrete roof. 2

Steel framed structure with unreinforced masonry (CMU or brick) infill walls (non-load 3
bearing) and a reinforced concrete or metal roof.

Steel framed structure with transite siding walls and a transite panel or metal deck roof. 4

Steel framed building with reinforced concrete walls panels and a reinforced concrete roof 5
deck.

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Pre-engineered metal structure 7

Steel framed building with reinforced masonry infill walls and a reinforced concrete roof. 8

Reinforced masonry building with load bearing walls and a reinforced concrete roof. 9

Unreinforced masonry building with load bearing walls and a reinforced concrete roof. 10

Reinforced concrete frame structure with unreinforced masonry infill walls and a reinforced 11
concrete roof.

Reinforced concrete frame structure with reinforced masonry infill walls and a reinforced 12
concrete roof

Trailer or modular building (light construction consisting of wood framing with steel or 13
aluminium cladding)

Wood frame structure 14

Unreinforced masonry building with load bearing walls and a wood roof. 15

A multi-story steel frame building constructed from wide flange steel beams that support heavy 16
equipment loads. Typically with walls constructed from light metal siding and girts and heavy
steel diagonal bracing members. Floors may be constructed from concrete or steel grating.

Description Severity Level

Light Moderate 2A

Heavy Moderate 2B

Major 3

Collapse 4

The latest information was published in 2006. This represents the latest thinking on building
vulnerabilities and supersedes previous information from Baker Risk. The 2006 information
is confidential to the members but it is likely that member companies will be using this

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information in the analyses they carry out. These vulnerabilities are likely to be more
accurate that the vulnerabilities given previously in this TN.

Tertiary Effects

Injury results from a person being displaced by the wind associated with the blast and a part
of the body impacting on a fixed/solid structure. The extent/seriousness of injury depends on
the velocity of impact, the hardness or shape of the structure and the part of the body involved
in the impact. The most critical body part is the base of the skull for which the threshold
value of velocity for fatality is 4m/s (velocities below 3m/s regarded as being safe).

For a VCE which has a positive phase duration of 100ms the threshold overpressure value is
approximately 0.7 bar. It is noteworthy that experience from VCE incidents (/78/) indicates
that prior to 1983 there had been no recorded fatalities for people outside the flammable cloud
as a result of primary/tertiary overpressure effects.

7.2.2 Overpressure Probits


Lees' quotes probits for fatalities due to lung damage and injury due to eardrum rupture from
work by Eisenberg (/65/). These probits are:

Y = -77.1 + 6.91 ln (Ps) for lung damage fatalities

and

Y = -15.6 + 1.93 ln (Ps) for eardrum rupture

where Ps is peak overpressure in Pascals (N/m2).

For eardrum rupture Hirsch (/79/) has also derived a probit

Y = -12.6 + 1.524 ln Ps

Probit functions for the probability of fatality after whole body impact are given as (/80/):

Y = 5.0 - 2.44 ln S

7,38 * 10 3 1,3 * 10 9
where S = +
Ρs Ρs i s

For probability of fatality after impact of the head:

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Y = 5.0 - 8.49 ln S

2,43 *10 3 4 *108


where S = +
Ρs Ρs i s

This probit is shown, assuming positive phase durations of 100 and 200m sec, in Figure 7-3.
Note this assumes whole body and head translation and impact onto a hard surface.

100

90

80

70
Percentage Fatality

60

Positive phase duration = 100msec


50
Positive phase duration = 200msec

40

30

20

10

0
0,5 0,6 0,7 0,8 0,9 1 1,1
Overpressure (bar)

Figure 7-3 Percentage Fatality for Impact of the Head from Overpressure

Probits for fatality because of secondary effects are dependent on building damage.

Eisenberg (/65/) presented probits for structural damage and glass breakage as
follows:

For structural damage Y = -23.8 + 2.92 ln (Ps)

and

For glass breakage Y = -18.1 + 2.79 ln (Ps)

where Ps is peak overpressure in Pascals (N/m2)

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The TNO report (/16/) presents probits for damage to houses and apartment buildings. For
houses and apartment buildings up to four storeys high, the probits are:

(a) for minor damage:

Y = 5 - 0.26 ln V

where

3,9 5
 4600   110 
V =  
 +  

 Ρs   is 

(b) for major structural damage:

Y = 5 - 0.26 ln V

where

8, 4 9, 3
 17500   290 
V =  
 +  

 Ρs   is 

(c) for collapse:

Y = 5 - 0.22 ln V

where

7, 4 11,3
 40000   460 
V =   +  
 Ρs   is 

This probit is shown in Figure 7-4 assuming (i) 20% fatality and (ii) 50% fatality in collapsed
two-storey buildings. Collapsed high rise buildings (eg. site offices as at Flixborough would
give worse results). It is of interest that the second term in the equation for V i.e (460/is)11.3 is
negligible compared with the first term for positive phase durations of 100 and 200ms i.e. the
term may be neglected.

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100

90

80

70
Percentage Fatality

60

20% of occupants fatally injured


50
50% of occupants fatally injured
40

30

20

10

0
0,1 1 10
Overpressure (bar)

Figure 7-4 Percentage Fatality for People in Collapsed Buildings

For apartment buildings over four storeys, the minor and major damage probits are the same
as those for houses given above. For collapse, the probit for a pressure wave is:

Y = 5 - 2.14 ln V

where

1,9 2, 5
 1,25  3
V =  + 
 Ρ  i 

and

Ρ
Ρ= Pst = static absorbable load (Pa)
Ρst

isω
i= ω = angular frequency (s-1)
Ρst

TNO give probits for window breakage as:

Y = -11.97 + 2.12 ln Ps for older buildings (pre-1975)

and

Y = -16.58 + 2.53 ln Ps for newer buildings (post-1975)

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HSC (/76/) used the following general probit for fatality:

Y = 1.47 + 1.37 ln Ps where Ps is the peak overpressure in psig.

This probit is based on fatalities in VI explosions in World War II, corrected to remove the
effects of bomb shelters, and hence takes account of the collapse of average brick-built
houses. Another probit for fatality used in the same study was:

Y = 2.47 + 1.43 log10 Ps

with Ps in psig.

These probits are shown in Figure 7-5.

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100

90

80

70
Percentage Fatality

60

50

40

30 Pr = 2,47 + 1,43lgPs
Pr = 1,47 + 1,37lnPs
20

10

0
0,1 1 10 100 1000
Overpressure (bar)

Figure 7-5 Percentage Fatality for People in Buildings Subjected to overpressure

100

90

80

70
Percentage Fatality

60

50

40

30

20 Upper limit
Mean
10 Mean
Lower limit
0
0,1 Overpressure
1 (bar) 10

Figure 7-6 Band of Fatality for People Inside Traditional Dwelling Houses

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Explosion consequence models for injuries and fatalities of people within buildings have been
reviewed (/82/). These models are based on analyses of World War II damage, subsequent
trials and recent exchange of information between NATO countries. The band within which
these predictions fall is given in Figure 7-6, and these data are applicable to people inside
housing built to traditional UK standards.

In Northern Belgium (/92/), the following probit is mandatory for calculations of fatalities due
to secondary effects of overpressure for people inside:

Y = -8,23 + 1,31 ln(P)

where P overpressure in Pa [K.U.Leuven, 1993]. For people outside the methodology


of the Green Book (/16/) is used,

7.3 Impact Criteria


7.3.1 Probabilistic Criteria
At the moment there is serious consistency problems associated with explosion probits. The
use of positive phase duration, while justifiable on theoretical grounds, does not take into
account the wide variability in such durations when obtained from well known different
explosion models (eg. TNO Multi-Energy Method, MicroFLACS, and CHAOS). A trial
conducted by DNV based on MicroFLACS results, which predicted long positive phase
durations, gave inconclusive results. If a probabilistic approach is warranted, then analysts
are advised to take considerable care and agree the basis with clients prior to a study.

For tertiary effects (people outdoors) the probit suggested by HSE for use is:

Pr = 5.0 - 8.49 ln S

2,43 * 10 3 4 * 108
where S = +
Ρs Ρs is

Ps = peak overpressure (N/m2)

is = impulse = ½ Ps tD

tD = positive phase duration (sec)

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For secondary effects (people indoors) the three probits identified and the range of predictions
given in Figure 7-6 also give a wide variation, (see Table 7.4) particularly at high
overpressures. At overpressures usually associated with offsite housing there is slightly less
variation between lowest and highest probits. None of these probits is specifically
recommended for use as the basis for them has not been reviewed by DNV.
Table 7-5 Percentage Fatality at Various Overpressures (From Probits)
Probit Overpressure (bar)
0.05 0.1 0.2 0.35 0.5 1 2 5
Y = 1.47 + 1.37 ln Ps <1 <1 2 10 21 55 86 100
Y = 2.47 + 1.43 log10 Ps <1 1 3 6 10 19 33 55
Y = 5 – 0.22 ln [40000/Ps]7.4 <1 1 7 23 32 47 50 50
Y = 5 – 0.22 ln [40000/Ps]7.4 <1 1 3 9 15 19 20 20
Figure 7.4 Lower Limit <1 <1 <1 2 3 8 14 (23)
Figure 7.4 Upper Limit <1 <1 9 36 55 100 100 100
Figure 7.4 Mean <1 <1 5 19 29 (54) (57) (62)

These fatality rates includes the effect of the explosion pressure only, No fatalities related to the VCE cloud it self (heat) or
effect of potentially secondary fires are included.

7.3.2 Single Value Criteria Onshore


The PhastRisk program uses the TNO Correlation Model which utilises two fixed coefficients
to establish ranges to specified damage levels (these coefficients are 0.03 for heavy damage to
buildings and 0.06 for repairable damage to buildings - more details are given in PhastRisk
Theory Manual). These damage levels are not explicitly associated with overpressure levels
but are generally considered to be equivalent to 0.35 and 0.1 bar for heavy and repairable
damage respectively. The recommended values for use in PhastRisk QRAs for these damage
levels are given in Table 7-6 together with a range of values which have been used in
PhastRisk studies. The two levels used in /97/ are 0.3 and 0.1 bar, with 0.3 being virtually a
single criterion (fatality probability unity for > 0.3 bar and for pressures in the range 0.1 to 0.3
bar only people indoors are affected (2.5% fatality)).

For other explosion models it is suggested that single value criteria are derived as follows:
• For people outdoors use the probit given in section 7.3;
• For people indoors use the mean line on Figure 7-6 up to a value of 0.7 bar (the use of
the mean above this value is questionable).

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Table 7-6 Recommended criteria for overpressure for onshore studies


Overpressure Range of
Bar People Onsite People Offsite Fatality Probabilities
Used in SAFETI Studies
Outside Inside (+) Outside Inside (+) Outside Inside
0.5 1 1 0.5 1 - -
0.35 0.3 0.7 0.15 0.7 0.2-0.5 0.9-1.0
0.1 0.01 0.15 0.01 0.15 0.01-0.15 0.1-0.3

+ These figures are based on the fatality probability of a person in a typical brick dwelling (/100/). Special explosion rated
buildings ( e.g. control rooms, special process buildings etc) has to be evaluated separately with respect to indoor
fatality rates

Analysts are reminded that explosion models are an idealized representation of the real
situation. Impact criteria must be used to some extent to put back the reality into predictions.
Thus in a VCE, almost everyone in the flammable portion of the cloud will be expected to die,
due to flame contact, regardless of the overpressure generated. This effect is not included in
the table above. Neither is the effect of fatalities from secondary fires due to rupture of
equipment or piping containing flammable materials. These effects must be modelled in
accordance with the criteria given in section 6.3.

7.3.3 Single Value Criteria offshore structures.


As given in the previous sections, personnel have a rather high resistance capacity for the
explosion wave itself. Thus in a hazardous situation in dense offshore modules, radiation
exposure may make a much higher impact on the fatality rate in the initiating areas compared
to the overpressure generated. In general it is therefore the size of the fire that is the main
contributor to the fatality rate and not the explosion overpressures by it self.

In escalation scenarios when an explosion escalates to other equipment within the same area,
or to other areas, the fatality rates may increase dramatically to an increased flame volume.
The capacity of deck and firewall structures is usually given in the design basis and escalation
may be evaluated against these design accidental loads (DALs). In addition to the expanded
flame size, high explosion overpressures may make additionally fatalities for outside the
critical radiation level generated by the fire. The explosion capacity for process equipment is
however often not given. A common criterion of 0.3 barg6 is therefore used, meaning that
offshore process equipment designed in accordance with recognized codes will withstand a
pressure of 0.3 barg before escalation take place. This is an average value, associated with
large uncertainties and there will be variations from plant to plant depending on the specific
design

6
This figure is estimated by DNV explosion and structural experts,

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The main parts of the body directly susceptible to the damaging effects of overpressure are
normally the eardrums and lungs. Lung damage can be fatal and an example of the While
personnel offshore are typically out of doors, or inside the TR it would be expected that a
lower fatality expectation exists than for a domestic situation. However, there are significant
items of plant and equipment that would be available to provide missiles in the event of an
explosion and in a situation where an explosion has escalated to other equipment inside the
same area such items is expected to be fatal.

For offshore installations this means that the fatality probability due to explosions may be
split up into the following.
Table 7-7 Recommended criteria for overpressure, offshore structures
Hazard Fatality fraction
Explosion Pressure
overpressure Criteria Scenario Thermal effect effects
VCE with subsequent fire, no escalation,
< 0.1 bar low explosion load ref. sec. 6.3 N.A
VCE with subsequent fire, no escalation,
0.1 – 0.3 bar medium explosion load ref. sec. 6.3 0.01
Initial Area VCE escalated to other equipment,
Secondary large fire within initial area. Effect from an
> 0.3 bar High explosion load escalated fire 1
No escalated Fire. Flames from the initial
< wall area may impact neighbouring areas Potential effects
capacity giving potential fatalities
Neighbouring Escalated VCE , flames from the initial
areas7 > wall area may impact neighbouring areas
capacity giving potential fatalities 0.5-18

7
The effects related to neighbouring areas are very dependant on the physical layout of the installation and should be
subjected to a separate evaluation for each installation In many cases an area classed as neighbouring might not be
separated from the initial area by a barrier which reduces the overpressure to a point where it is negligible. Separate CFD
analysis could be used for this purpose. In the absence of CFD use can be made of TNO curves or simpler rule sets.
8
These are figure used in a number of DNV studies and should be used as indicative. There exists no specific reference to
this type of fatality fraction and the fraction should be subjected to a platform individual evaluation.

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8 SMOKE

8.1 Introduction
This section considers the effects of smoke on people by examining the effects, separately, of
the main constituents of smoke which can be harmful, i.e. carbon monoxide (CO), carbon
dioxide (CO2), oxygen starvation and high temperatures of inhaled gases.

For process accidents in most QRAs we perform, the fire is assumed to occur outside in well-
ventilated areas and smoke is a negligible contributor to fatalities. It is therefore common
practice not to calculate impact from smoke. For fires indoors, smoke is known to be a main
contributor to fatalities. For example, half of casualties in dwelling fires in the UK are in the
category “overcome by smoke and toxic gases” (/95/). Thus when modelling fires indoors,
one has to take smoke into account. In addition, smoke is a factor when calculating
impairment of safety functions offshore, see TN 8.

Below background information concerning smoke is given. A method for the evaluation of
lethal concentrations is given in Appendix F, and single value criteria for incapacitation
derived by using this method are presented below. It is recommended that this method is used
when examining the impact of smoke etc but the single value criteria given in Table 8-7 are
only for guidance. The method in Appendix F is the method presented in the SFPE Handbook
of Fire Protection Engineering (/95/) and in ISO standard ISO/TS 13571:2002.

8.2 Composition of Smoke


Combustion gases from burning hydrocarbons consist mainly of a mixture of nitrogen, carbon
dioxide (CO2), carbon monoxide (CO) and water vapour. Because of the high proportion of
nitrogen in the air, hot nitrogen forms by the largest proportion of the combustion products.

The proportion of toxic gases in the smoke depends primarily on the chemical structure of the
burning materials and the combustion conditions. For most hydrocarbons the chemical
structure is of far less importance than combustion conditions and in practical situations
modelled in QRAs ventilation has the main effect on combustion products. Fires in which the
ventilation is restricted or enclosed e.g. in modules or compartments, are called under-
ventilated or ventilation-controlled fires, because the availability of ventilation determines the
rate of combustion. Conversely, fires in well ventilated areas are fuel controlled, i.e. the rate
of combustion is determined by the availability of fuel. In general, reduced ventilation greatly
increases the percentage of CO, while the O2 and CO2 remains more or less unaffected.

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Typical gas concentrations close to the fire are given in Table 8-1 (collated by Bonn
(1993)(/83/), based on Johnson (1992)(/84/), Tewarson (1990)(/85/) and Wighus
(1991)(/86/)).
Table 8-1 Initial Gas Concentrations in Smoke (Bonn, 1993)
GAS CONCENTRATION IN SMOKE (%)
WELL VENTILATED FIRE UNDER VENTILATED FIRE
(fuel controlled) (ventilation controlled)
gas fire liquid fire gas fire liquid fire
CO 0.04 0.08 3 3.1
CO2 10.9 11.8 8.2 9.2
O2 0 0 0 0

The effects of smoke can be toxicity (CO2, CO), asphyxiation, high temperature and reduced
visibility. The combination of effects is complex and here assumed to be cumulative. Each
separate effect is discussed below.

8.3 Effects of Carbon Monoxide


Carbon monoxide is usually the main cause of death in fires. It combines with haemoglobin,
the oxygen carrier in the blood, to form carboxyhaemoglobin (COHb). CO has a much
greater affinity for haemoglobin than oxygen, thus reducing oxygen delivery to the body
tissues, causing "asphyxia", a choking fit which leads to death. The natural level of COHb in
the blood is 0-5%, and is greatest for smokers. The fatal level of COHb in the blood is
generally considered to be 50% (TIL, 1991)(/87/).

CO uptake and intoxication is extremely insidious, producing minimal effects until a critical
dose has been accumulated, which rapidly leads to collapse. Therefore, victims may not
realise the danger until it is too late to escape. The rate of uptake is greatly increased at
higher activity levels.

The effects of exposures to different levels of CO for different lengths of time are given in
Table 8. (Stensaas, 1991 /88/). The CO concentration causing unconsciousness or death is
inversely proportional to the exposure time. The critical toxic effect is therefore best
measures as a dose in the form of:

D = C *t

where

D is dose in ppm min

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C is concentration in ppm i.e. concentration in % x 10-4

t is exposure time in minutes

The time to unconsciousness can be represented approximately by a CO dose of 45,000 ppm


min. This is considered appropriate for conditions of light physical activity (Stensaas, 1991)
(/88/).

Table 8-2 Effects of Carbon Monoxide


CARBON MONOXIDE EFFECTS
CONCENTRATION (PPM)
1500 Headache in 15 minutes,
collapse in 30 minutes.
Death in 1 hour.
2000 Headache in 10 minutes,
collapse after 20 minutes.
Death in 45 minutes.
3000 Maximum `safe' exposure
limit for 5 minutes.
Danger of collapse in 10
minutes.
6000 Headache, dizziness in 1-2
minutes. Danger of death
in 10-15 minutes.
12800 Immediate effect,
unconsciousness in 2-3
breaths. Danger of death
in 1-3 minutes.

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Table 8-3 effect of CO increase in blood (B. Karlsson and J. Quintiere, Enclosure Fire
Dynamics)
% of COHb (carboxy- Volume concentration effect
haemoglobin) in blood [%] of CO present in
the air
0-10 <0.008 Indifferent phase:
None
10-20 0.008-0.015 Compensated phase:
Increased ventilation and heart rate, loss of
efficiency (fatigue, memory, judgement)
20-40 0.015-0.04 Dizziness, nausea, possible paralysis

40-50 0.04-0.06 Critical phase:


Prostration, asphyxiation, collapse
50-70 0.06-3 Critical phase:
Unconscious in minutes, possible death
70-100 >0.3 Critical phase:
Unconscious in seconds, death likely

8.4 Effects of Carbon Dioxide


Carbon dioxide occurs naturally in clean air at a concentration of 0.03% by volume. Humans
produce CO2 as waste from respiration. On average, 4.1% of the exhaled volume is CO2.
CO2 concentrations in air above 0.1% are experienced in a "stuffy" room.

Excess CO2 causes "hypercapnia", characterised at first by increased respiration. Since CO2
itself is not very toxic, the most important effect of CO2 in smoke is to increase the uptake of
other toxic gases, although CO2 may also have a beneficial effect by increasing the oxygen
uptake.

CO2 concentrations of 5% triple the rate of breathing (TIL, 1991) (/87/). At this
concentration, breathing becomes difficult for some individuals, although it can in general be
sustained for up to an hour without serious after-effects (Stensaas, 1991) (/88/). 5% is also
the IDLH concentration for CO2 (NIOSH, 1990), from which escape is considered possible in
30 minutes without any escape-impairing or irreversible effects.

CO2 concentrations above 10% cause loss of consciousness in times ranging from 30 minutes
at 10% to 1 minute at 15% (Stensaas, 1991) (/88/).

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The acute health effects that are seen following inhalation of high concentrations of CO2 are
presented in Table 8-4 and should be used as reference values for safety risk assessments [1],
[2]
.

Table 8-4 Acute health effects of high concentrations of inhaled CO2 /106/
CO2 Concentration
Exposure Effects on Humans
in Air (% v/v)

Loss of controlled and purposeful activity, unconsciousness,


17 – 30 Within 1 minute
convulsions, coma, death
1 minute to several Dizziness, drowsiness, severe muscle twitching,
>10 – 15
minutes unconsciousness

Few minutes Unconsciousness, near unconsciousness


7 – 10
Headache, increased heart rate, shortness of breath, dizziness,
1.5 minutes to 1 hour
sweating, rapid breathing
1 – 2 minutes Hearing and visual disturbances
6 ≤ 16 minutes Headache, difficult breathing (dyspnoea)
Several hours Tremors
Headache, dizziness, increased blood pressure, uncomfortable
4–5 Within a few minutes
breathing (Equivalent to concentrations expired by humans)
3 1 hour Mild headache, sweating, and difficult breathing at rest
2 Several hours Headache, difficult breathing upon mild exertion
0.5-1 8hrs Acceptable occupational hazard level

Guidance Note [1]: The reference source on which the above table was based /106// does not
provide specific details of the age, sex, fitness or general well-being of the people exposed.
But a conservative and reasonable assumption would be that people with underlying health
concerns would not have been selected as a volunteer in tests. Therefore the exposure limits
may need to be adjusted for use in risk assessment should the exposed population being
considered include vulnerable people (e.g. those with a respiratory illness).

The harm level expressed by a given substance in the air is influenced by two factors, the
concentration in the air (c) and the duration of exposure (t). The following expressions have been
defined by the HSE for CO2, ref. Figure 8-1[3]:

SLOT DTL: 1.5x1040 = c8.t


SLOD DTL: 1.5x1041 = c8.t

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25%

SLOD DTL
SLOT DTL
CO2 in Air at 1 Atmosphere (%)

20%

15%

10%

5%

0%
0 5 10 15 20 25 30 35 40 45 50 55 60

Exposure Time (mins)

SLOT DTL = Specified Level Of Toxicity Dangerous Toxic Load


SLOD DTL = Significant Likelihood Of Death Dangerous Toxic Load
Figure 8-1 SLOT and SLOD limits for CO2 //107/
Guidance Note [1]: Human respiration is controlled by the respiratory centre of the brain which keeps the basic
rhythm of respiration continuous. One of the most powerful stimuli known to affect the respiratory centre is CO2.
CO2 acts as both a stimulant and depressant on the central nervous system.

Guidance Note [2]: CO2 is not a chemical asphyxiant like hydrosulphide or carbon monoxide in that it does not
prevent the efficient transfer of oxygen via the blood.

Guidance Note [3]: With reference to Figure 8-1 the number of people injured (serious and minor) by the
release may be approximated by the number people estimated to be between the SLOD and SLOT DTL contours
(i.e. the SLOT DTL contour is taken as a pragmatic limit for human harm).

Guidance Note [4]: With reference to Figure 8-1 the number of fatalities caused by a CO2 release may be
approximated by the number people estimated to within the SLOD contour (i.e. the SLOD DTL contour is taken
as a pragmatic limit for fatalities).

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8.4.1 Occupational exposure limits for CO2

An occupational exposure limit (OEL) is an upper limit on the acceptable concentration of a


hazardous substance in workplace air for a particular substance or class of substances.

The OEL given in Table 8-5 should be applied as reference for evaluating occupational
hazards.

Table 8-5 Occupational exposure limits


Exposure % CO2 Comment Reference
Time
10 hours 0.50% Time weighted average NIOSH (US)
8 hours 0.50% Time weighted average OSHA (US)
0.50% Occupational Long Term Exposure Limit (LTEL) COSHH HSE (UK)
60 min 4% Emergency Exposure Level for submarine operations USA Navy
2.5% Emergency Exposure Level for submarine operations National (US) Research Council
5% Suggested Long Term Survivability Exposure Limit HSE (UK)
2% Maximum exposure limit Compressed Gas Association 1990
20 min 3% Maximum exposure limit Compressed Gas Association 1990
15 min 1.5% Occupational Short Term Exposure Limit (STEL) COSHH HSE (UK)
3% Short Term Exposure Limit (STEL) Federal occupational safety and
health regulations (US)
10 min 4% Maximum exposure limit Compressed Gas Association 1990
7 min 5% Maximum exposure limit Compressed Gas Association 1990
5 min 5% Suggested Short Term Exposure Limit (STEL) HSE (UK)
6% Maximum exposure limit Compressed Gas Association 1990
3 min 7% Maximum exposure limit Compressed Gas Association 1990
1 min 15% Exposure limit NORSOK (Norway)
<1 min 4% Maximum Occupational Exposure Limit Federal occupational safety and
health regulations (US)

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8.5 Effects of Oxygen Starvation


Oxygen constitutes 21% by volume of clean air. Decreases in oxygen concentration down to
about 15% are counteracted by the body increasing the flow of blood to the brain, and only
minor effects on coordination are apparent.

Oxygen concentrations below 15% by volume produce oxygen starvation effects such as
increased breathing, faulty judgement and rapid onset of fatigue.

Oxygen concentrations below 10% cause rapid loss of judgement and comprehension,
followed by loss of consciousness, leading to death within minutes (Stensaas, 1991)( /88/).
Concentrations down to 5% lead to death within few minutes (Sax, 1984) (/89/).

8.6 Effects of High Temperature


The effects of inhalation of gases at elevated temperatures are difficulties in breathing,
increased pulse rate and burn injuries. In general, the maximum air temperature which can be
tolerated by the human respiratory tract is approximately 203°C (Spieth 1982) (/90/). Effects
at other temperatures are shown in Table 8-6.

Table 8-6 Effects on Humans from Elevated Temperatures (Bryan, 1986) (/87/)
Temperature Physiological Response
(Celsius)
127 Difficult breathing
140 5-min tolerance limit
149 Mouth breathing difficult, temperature limit for
escape
160 Rapid unbearable pain for dry skin
182 Irreversible injury in 30 seconds
203 Respiratory systems tolerance time for less than
four minutes with wet skin

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8.7 Criteria
All of the above effects are important and should be taken into account when considering
smoke effects. Appendix F gives an approach for determining smoke incapacitation, but there
is no recommended single value criterion for smoke. Using the method in Appendix F and
the smoke compositions given in Table 8-1 produces the following values for smoke
concentrations for impairment within one minute (Table 8-7):
Table 8-7 Incapacitation Doses from Smoke
GAS WELL VENTILATED FIRE UNDER VENTILATED FIRE
(fuel controlled) (ventilation controlled)
gas fire liquid fire gas fire liquid fire
Lethal
concentrations 71% 70% 48% 45%
for 1 minute
exposure

The relatively high production of CO for ventilation controlled fires means that the effects of
smoke exposure to these fires are dominated by CO. For fuel controlled fires the production
of CO is very low, and the smoke works almost entirely as a simple asphyxiant (i.e. the lack
of oxygen being the dominant factor). The concentration of smoke causing fatalities in fuel
controlled fires is consequently quite high.

Temperature effects are not included in the above numbers and should also be evaluated along
the same methodology as the effects of the gases, see Appendix F.

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9 ASPHYXIANTS
A gas or vapour which is hazardous to health as a result of it displacing the oxygen in the air
is termed an asphyxiant. Asphyxiants are non-toxic and are typically inert gases, such as
nitrogen, although they could also be flammable gases, such as methane, propane etc. The
normal oxygen content in air is approximately 21%. Nitrogen is the other primary component
of air at 78%, with other trace components totalling approximately 1%. The presence of any
additional gas in the air, with the exception of oxygen, dilutes the oxygen concentration and
can create an oxygen-deficient atmosphere. As the oxygen concentration in the air diminishes,
the human body becomes oxygen deprived and asphyxiation occurs. Effects can range from
giddiness, mental confusion, loss of judgment, loss of coordination, weakness, nausea,
fainting to death.

9.1 Literature Review


There are various tables in the literature which relate effects and symptoms when a person at
rest is exposed to various degrees of oxygen deficiency. Table 9-1 is taken from /103/, Table
9-2 is taken from /104/ and Table 9-3 is taken from /105/

Table 9-1: Signs and Symptoms of Oxygen-Deficient Exposure

Oxygen Content of Air Signs and symptoms of persons at rest.


15% - 19.5% Decreased ability to work strenuously. May impair coordination and may include
symptoms in persons with coronary, pulmonary, or circulatory problems.
12% - 15% Respiration deeper, increased pulse rate, and impaired coordination, perception,
and judgement
10% - 12% Further increase in rate and depth of respiration, further increase in pulse,
performance failure, giddiness, poor judgment, and blue lips
6% - 8% 8 minutes, may be fatal in 50 – 100% of exposures; 6 minutes, may be fatal in 25-
50% of exposures; 4-5 minutes, recovery with treatment.
4% - 6% Coma in 40 seconds, convulsions, respiration ceases, death

Table 9-2: Effects of Oxygen Deficiency on the Human Body


Atmospheric
Oxygen
Possible Results
Concentration
(%)
20.9 Normal
19.0 Some unnoticeable adverse physiological effects
16.0 Increased pulse and breathing rate, impaired thinking and attention, reduced coordination
14.0 Abnormal fatigue upon exertion, emotional upset, faulty coordination, poor judgement
12.5 Very poor judgement and coordination, impaired respiration that may cause permanent
heart damage, nausea, and vomiting
<10 Inability to move , loss of consciousness, convulsions, death
Source: Compressed Gas Association, 2001

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Table 9-3: Effects and Symptoms of Oxygen Deficiency in Humans


Oxygen
Concentration Effects and symptoms
(%)
20.9 Normal air concentration
19.5 Minimum safe entry level
16-19 Poor coordination, fatigue
12-16 Rapid pulse, laboured respiration
10-12 Very fast and deep respiration, lips begin turning blue, headache
8-10 Fainting, unconsciousness, nausea, vomiting
6-8 Fatal in 8 minutes; 50% fatal in 6 minutes
<6 Coma in 1 minute, convulsions, respiratory and cardiac arrest, death

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10 CALCULATION OF FATALITIES FOR OFFSHORE FACILITIES

10.1 Immediate fatalities local to Event


The flame length for gas jet fires is normally based on the release rate. Using the flame length,
contours can be determined for different radiation levels using factors derived from the model
within e.g DNV’s PHAST software package.

100% fatality rate is assumed for personnel inside the 20 kW/m radiation contours. The
2

fatality rate for a given hydrocarbon event source area is assumed to be equal to the ratio of
the area of the 20 kW/m2 radiation contour to the area of the module. Personnel outside of the
contour are assumed to survive.

 A 
I initial = min rad ,1 × N i (1)
 Ainitiation 

Where:

I,initial = number of fatalities


Ni = number of persons within the module/area.
Arad = Area of critical radiation
Ainitation = Area of module of initiation

10.2 Ignited Releases – Delayed Ignition and explosions


Delayed ignition events are events that after a gas cloud has been built up by the release.
Delayed ignition is expected to result in a flash fire or explosion.

Fatalities due to the explosion overpressure may be as a result of ingestion of hot combustion
products, the effects of overpressure on the body, or impacts with solid objects following full
body translation.

Explosions escalating to other area through an explosion barrier


For these events the fatality fraction in the area where the explosion occurs is normally set to
100%.

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Explosions escalating to equipment


For events with explosion pressures (Pexp) 0.3 bar < Pexp < P explosion barrier design load the fatality
fraction is set equal to 100% within the area where the explosion occurs.

Flash fires or explosions < 0.3 barg

Delayed ignition events, considered as flash fires also including explosions not escalating to
equipment, (Pexp < 0.3 bar), 100% fatalities within the LFL gas cloud.

10.3 Immediate fatalities in other areas


In some situations, the user may want to allow for areas of the source module being shielded
or for the possibility that for some release directions the flame may be directed outwards from
the module. The various possibilities are shown in Figure 10-1. The analyst is permitted to use
their judgement to apply a suitable factor. In this case the fatality rate is modified by the
formula;

FRsource area = FRsource area,O(1 – Freduction) (2)

Where Freduction is a reduction factor to take account of directional and shielding effects. A
value has to be determined for “adjacent” modules and other “modules”.

Flame Wholly Within Module Area Shielded by Obstruction Flame Directed Outward From Module

Module Boundary Module Boundary Module Boundary


Flame Flame Flame

Source

Source Source

Wall Providing Shielding


Shielded Area

Figure 10-1 Flame/Module Scenarios

This process will result in the estimated fatalities within the following categories

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• an area adjacent to the source area (i.e. sharing a common boundary).


• TR: temporary refuge.
• any other area (neither the TR nor adjacent to the event source).

10.4 Escape fatalities

Persons surviving the initial fire or explosion may be killed when escaping to a temporary
safe area. Proper escape from the process areas onboard a facility is provided by the
dedicated escape ways. The fatality fraction estimated for escape takes into account personnel
not able to find their way around the vessel due to smoke, heat and physical obstructions
within the escape routes.

After the estimation of immediate fatalities, calculation of the fatalities during escape shall be
determined based on the following logic:
o Personnel killed by the immediate effects of the event itself are immediate fatalities.
o Those not killed by the immediate event will attempt to muster (escape) to the TR.
o Fatalities during escape to TR is calculated as follows:
o Heat radiation above 12.5 kW/m2.

To accommodate the fact that personnel may be shielded from the fires by large structures and
equipment the calculated theoretical fatality fractions is reduced to 50%. The criterion shall be
evaluated together with the potential for incapacitation due to smoke exposure.
Incapacitation due to smoke

Using the methodology as presented in appendix F, Incapacitation for 1 minute exposure


(30m escape distance inside smoke) for the following smoke concentrations is said to cause
100% fatality rate, given a smoke temperature below 37 oC

Well ventilated fire


o Gas: 71%
o Liquid: 70%
Under ventilated fire
o Gas 48%
o Liquid: 46%

Incapacitation due to temperature has to be evaluated in addition to the above given criteria

A smoke temperature of 230 oC will with 1 minute exposure cause incapacitation (see
appendix F)

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10.5 Evacuation fatalities

The evacuation fatalities are related to scenarios where the evacuation is impaired and
personnel cannot use the evacuation means. Scenarios where the evacuation means fail on
demand and rescue and recovery of personnel becomes relevant are also included here.
Fatalities during evacuation may be due to:
o Collapse of the vessel hull leading to the vessel capsize or sinking prior to the
completion of evacuation
o Unavailable evacuation means
o Failures/ accidents during launching of the evacuation bridge, lifeboats or tertiary
evacuation means.
o Evacuation fatalities is evaluated within the 500 zone, and does not include transfer
from evacuation means to rescue vessel or other safe location.

Fatalities during evacuation are estimated based on the evacuation fatality rate for the
different evacuation scenarios and probability for unsuccessful evacuation, which is taken
from the EER study. For personnel in the TR, there will be no fatalities if the TR remains
unimpaired.

Full evacuation is normally assumed to be initiated by:

o All fires and explosions escalation through a fire separation or explosion barrier
o Loss of TR integrity
o Hull failure

A separate escape, evacuation and rescue (EER) study is normally performed, and will
provide input to the assessment of evacuation fatalities. The EER study will consider integrity
of escape ways, evacuation and rescue systems to meet requirements from operations in arctic
conditions, taking into consideration sea ice, icing, low temperatures, long period of darkness
and remoteness.

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/79/ Academy of Sciences, 1968.
Baker W.E., Cox P.A. and Westine P.S. et al, Explosion Hazards and Evaluation,
/80/ Elsevier Scientific Publishing Company, 1983.
Hazards of Chemical Rockets and Propellants Handbook, Volume 1, General Safety
/81/ Engineering Design Criteria, AD 889763, CPIA/194, May 1972.
Merrifield, R, Simplified Calculations of Blast Induced Injuries and Damage.
/82/ Specialist Inspector Report no. 37, HSE, 1993.
Bonn (1993): Smoke & Gas Detectors for Temporary Refuges, R. Bonn, BP
/83/ Exploration, 4th International Conference on Offshore Loss Prevention - A Systematic
Approach, Aberdeen, Scotland, 3-5 March 1993, published by the BHR Group.
Johnson (1992): Airborne Observations of the Physical and Chemical Characteristics of
/84/ the Kuwait Oil Smoke Plume, D. W. Johnson et al, Nature vol 353, pp. 617-621.
Tewarson (1990): Generation of Heat and Chemical Compounds in Fire, A. Tewarson,
/85/ The SFPE Handbook on Fire and Protection Engineering, NFPA, 1990.
Wighus (1991): Smoke Hazard in Offshore Platform Fires, R. Wighus, Ø. Meland and
/86/ B. Vembe, SINTEF report STF25-A91007, 1991.
TIL (1991): Conditions Within the Muster Station on the Alba Development,
/87/ Confidential Report to Chevron, DNV Technica Indecone Project I671, October 1991.
Stensaas (1991): Toxicity, Visibility and Heat Stresses of Fire Effluents - Human
/88/ Tenability Limits, SINTEF Report STF25-AP1022, May 1991.
Sax (1984): Dangerous Properties of Industrial Materials, 6th edition, N. Irving Sax,
/89/ Van Nostrand Reinhold Company Inc, 1984.
Spieth (1982): A Combined Hazard Index Fire Test Methodology for Aircraft Cabine
/90/ Materials, Spieth, Gaume, Luoto and Klinch, vols I and II, DOT/FAA/CT-82/36-1 and
DOT/FAA/CT-82/36-11, Department of Transportation, Atlantic City, April 1982.

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HSE, Assessment of the Dangerous Toxic Load (DTL) for Specified Level of Toxicity
/91/ (SLOT) and Significant Likelihood of Death (SLOD),
http://www.hse.gov.uk/hid/haztox.htm, 24. September 2008.
Departement Leefmilieu, Natuur en Energie Afdeling Milieu-, Natuur- en
/92/ Energiebeleid, VR-richtlijnenboek -Omgevingsveiligheidsrapport - OVR, Revision 3,
January 2006.
Raj (2007): A review of the criteria for people exposure to radiant heat flux from fires,
/93/ Journal of Hazardeous Materials 159 (2008) 61-71, September 2007
Raj (2008): Field tests on human tolerance to (LNG) fire radiant heat exposure, and
/94/ attenuation effects of clothing and other objects, Journal of Hazardous Materials 157
(2008) 246-259, December 2007.
Purser (2002): Toxicity Assessment of Combustion Products, D. A. Purser, The SFPE
/95/ Handbook of Fire Protection Engineering 3rd edition, Chapter 2-6, NFPA, 2002.
Handleiding Risicoberekeningen Bevi Module B Algemeen Versie 3. 1 Jan 2008
/96/ (English version Reference Manual Bevi Risk Assessments version 3.0 Jan 2009).
Guidelines for Quantitative Risk Assessment. “Purple Book”, CPR 18E. VROM.
/97/ Publication Series on Dangerous Substances (PSG 3). Dec 2005.
American Petroleum Institute Recommended Practice 752. Management of Hazards
/98/ Associated with Location of Process Plant Buildings. Second Edition, Nov 2003.
American Petroleum Institute Recommended Practice 753. Management of Hazards
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Chemical Industries Association. Guidance for the Location and Design of Occupied
/100/ Buildings on Chemical Manufacturing Sites. (Nov 2003).
W S Atkins Science and Technology. Derivation of Fatality Probability Functions for
/101/ Occupants of Buildings subject to Blast Loads. Phase 4. Contract Research report
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/105/ InterScience. Published by Wiley-Interscience, 2006. ISBN 0471787655,
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/106/ February 2000 (http://www.epa.gov/Ozone/snap/fire/co2/co2report.pdf)
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Appendix A
Issued for RiskNet. Ref: T15 Revision No. 03

APPENDIX A:
PROBIT ANALYSIS

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A.0 PROBITS
The range of susceptibility in a population to a harmful consequence can be expressed
mathematically using a criterion in the form of an equation which expresses the percentage of
a defined population which will suffer a defined level of harm (normally death) when it is
exposed to a specified dangerous load. This is a `Probit' equation which has the form:

Y = A + B Ln (Cn.T)

Where Y is the probit (or probability measure), A, B and n are constants, C is a concentration
and t is time. The probit, Y, can be related to percent fatalities using published tables. The
most commonly used table is given as Table A.1. The probit is, in statistical terms, a single
tailed, normal distribution with the values increased by a value of 5 to maintain positive
values of the probit function over the sensible fatality range.

The relationship between a probit and the normal distribution is shown in Figure A.1. Here, a
number of probits have a common intersection at the LC50 (this is shown by following the
dotted line down to the lower, fatality curve and reading across to the 50% fatality value) but
would predict very different toxicological behaviour at other toxicity values. All the lines are
based on the equation given above but with different values for A and B. As can be seen, for
a given LC50, the effect of B is only to change the LC90/LC10 ratio. Similarly, if the
concentration-time units of the dose (CnT) are altered, the probit relationship is affected only
in the A parameter.

The sensitivity of a risk analysis to the choice of probit function can be illustrated by
reference to toxicity probits for chlorine. Table A.2 illustrates the concentrations predicted by
three probits for increasing durations of exposure:
Table A- 1 Chlorine Probit Comparison
TIME LC50 (ppm)
(min)
IChemE, Withers and Zwart and ten Berge et al
Lees Woutersen (Dutch)
10 433 1,931 775
20 306 1,172 602
30 250 690 520

It can be seen that the choice between the IChemE and Zwart and Woutersen probits could
significantly change the predicted risk levels and is likely to produce marked differences in
the number of fatalities calculated as a result of any release.

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Appendix A
Issued for RiskNet. Ref: T15 Revision No. 03

A.1 PROBIT ANALYSIS METHODOLOGY


The fundamental assumption underpinning this form of analysis (indeed injury-insult
modelling as a whole) is that the variation in a response of any population will, as some
function of the causative factor, be approximately Gaussian (see Figure A.2). This
assumption is reasonably well supported by the data available on a range of animal and
human studies of toxic effects.

For toxic effects a logarithmic relationship generally gives rise to a normal distribution.
Consequently the cumulative response curve is generally a normal sigmoid shape (see Figure
A.3). It is the transformation of this sigmoid curve to a straight line relationship that is at the
centre of the probit methodology.

In 1933, Gaddum proposed to measure the probability (P) of response on a transformed scale,
the normal equivalent deviate (NED), defines as:

z
1
P=
2π ∫ exp(-0. 5
-∞
u2
) du

Thus the NED (z) of any value of P between 0 and 1 is defined as the abscissa corresponding
to a probability P in a normal distribution with a mean of 0 and a variance of 1. The NED
however, is a negative if P is less than 0.5 (i.e. 50%). To avoid these negative values Bliss2
proposed a slightly different formulation. He proposed the probit of P as y where:

Y-5
1
P=
2π ∫ exp(-0. 5
-∞
u2
) du

The probit is thus simply the NED increased by 5 with the effect that the probit remains
positive unless P is exceedingly small. The relationship between the probit and percentage (or
probability) of response1 is illustrated in Figure A.4 and Table A.1 and the effect of the probit
transformation on the cumulative response curve is illustrated in Figure A.5.

The linear equation relating probit to toxic load is commonly written:

y = A + B lnx

Where the toxic load function comprises more than one variable the equation becomes:

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Appendix A
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y = A + B1 ln x1 + B2 ln x2 etc.

where A, B1, B2, etc are regression coefficients. For most toxic substances the variables under
examination are the concentration (c) and the time (t), so the equation becomes:

y = A + B1 ln C + B2 ln t

or this may be re-written as:

y = A + B2 ln Cnt

where

n = B1
B2

To obtain the parameters from experimental data a graphical method may be employed but
more rigorous determinations usually involve such as the maximum likelihood estimation
(MLE) method or the method of minimising x2 (x2 is the weighted sum of squares of the
difference between the experimental and expected probit values).

The MLE method1 involves an iterative process which is usually carried out by means of
successive weighted linear regressions. Such regressions generally rapidly converge with the
limit being the maximum likelihood estimate of the probit values. The weighting of the
regression involves an expression of the form nw where n is the number of animals in a
sample and w is a weighting coefficient, values of which are symmetrical about y = 5 and
decrease towards y = 0 and y = 10 (see Table A.3).

A measure of the limits within which the true parameter lies is generally of value and the
method of fiducial limits (usually the 95% fiducial limit) is the one usually adopted. In this
method there is said to be a fiducial probability (F) that the true value of a parameter lies
between upper and lower limits which would not be contradicted by a significance test at the
1-F probability level. To a reasonable approximation the fiducial limits can be calculated as:

+_t V

where t is the normal deviate for the probability to be used (eg 1.96 for 95% probability, see
Table A.4) and V is the variance. For example:

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2
11 (m- X )
V(m) = 2 [ + ]
b ∑ nw ∑ nw(x- x )
2

where m = exposure dose under evaluation.

A more rigorous analysis would give the limits of parameter m as:

2
g t 1- g (m- x )
m+ (m- x ) + _ [ + ]
1- g b(1 - g) ∑ nw ∑ nw(x- x )2

where

t
g=
b ∑ nw(x- x )
2 2

If g < 0.1 the approximation based on the variance formula does not give rise to significant
error.

If the fiducial limits are plotted as bands along a probit regression line they will form two
hyperbolic curves, convex to the line and approaching most closely at 50% response (eg. see
Figure A.6).

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Appendix A
Issued for RiskNet. Ref: T15 Revision No. 03

A.2 REFERENCES
/108/ . Finney DJ (1971), Probit Analysis, 3rd Edition, Cambridge University Press

/109/ Bliss CI, Estimating the Dosage-Mortality Curve, J Econ Ent 28 (1934) 646-7
Table A- 2 Transformation of percentages to probits
% 0 1 2 3 4 5 6 7 8 9
0 - 2.67 2.95 3.12 3.25 3.36 3.45 3.52 3.59 3.66
10 3.72 3.77 3.82 3.87 3.92 3.96 4.01 4.05 4.08 4.12
20 4.16 4.19 4.23 4.26 4.29 4.33 4.36 4.39 4.42 4.45
30 4.48 4.50 4.53 4.56 4.59 4.61 4.64 4.67 4.69 4.72
40 4.75 4.77 4.80 4.82 4.85 4.87 4.90 4.92 4.95 4.97
50 5.00 5.03 5.05 5.08 5.10 5.13 5.15 5.18 5.20 5.23
60 5.25 5.28 5.31 5.33 5.36 5.39 5.41 5.44 5.47 5.50
70 5.52 5.55 5.58 5.61 5.64 5.67 5.71 5.74 5.77 5.81
80 5.84 5.88 5.92 5.95 5.99 6.04 6.08 6.13 6.18 6.23
90 6.28 6.34 6.41 6.48 6.55 6.64 6.75 6.88 7.05 7.33

- 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
99 7.33 7.37 7.41 7.46 7.51 7.58 7.65 7.75 7.88 8.09

Table A- 3 Weighting Coefficient, w =Z2/PQ


Y 0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9
1 0.001 0.001 0.001 0.002 0.002 0.003 0.005 0.006 0.008 0.011
2 0.015 0.019 0.025 0.031 0.040 0.050 0.062 0.076 0.092 0.110
3 0.131 0.154 0.180 0.208 0.238 0.269 0.302 0.336 0.370 0.405
4 0.439 0.471 0.503 0.532 0.558 0.581 0.601 0.616 0.627 0.634
5 0.637 0.634 0.627 0.616 0.601 0.581 0.558 0.532 0.503 0.471
6 0.439 0.405 0.370 0.336 0.302 0.269 0.238 0.208 0.180 0.154
7 0.131 0.110 0.092 0.076 0.062 0.050 0.040 0.031 0.025 0.019
8 0.015 0.011 0.008 0.006 0.005 0.003 0.002 0.002 0.001 0.001

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Table A- 4 Distrubution of t
Degrees Probability
Of .90 .70 .50 .30 .10 .05 .02 .01 .001
Freedom
1 .16 .51 1.00 1.96 6.31 12.7 31.8 63.7 637.
2 .14 .44 .82 1.39 2.92 4.30 6.96 9.92 31.6
3 .14 .42 .76 1.25 2.35 3.18 4.54 5.84 12.9
4 .13 .41 .74 1.19 2.13 2.78 3.75 4.60 8.61
5 .13 .41 .73 1.16 2.02 2.57 3.36 4.03 6.86
6 .13 .40 .72 1.13 1.94 2.45 3.14 3.71 5.96
7 .13 .40 .71 1.12 1.90 2.36 3.00 3.50 5.40
8 .13 .40 .71 1.11 1.86 2.31 2.90 3.36 5.04
9 .13 .40 .70 1.10 1.83 2.26 2.82 3.25 4.78
10 .13 .40 .70 1.09 1.81 2.23 2.76 3.17 4.59
12 .13 .40 .70 1.08 1.78 2.18 2.68 3.06 4.32
14 .13 .39 .69 1.08 1.76 2.14 2.62 2.98 4.14
16 .13 .39 .69 1.07 1.75 2.12 2.58 2.92 4.02
18 .13 .39 .69 1.07 1.73 2.10 2.55 2.88 3.92
20 .13 .39 .69 1.06 1.72 2.09 2.53 2.84 3.85
22 .13 .39 .69 1.06 1.72 2.07 2.51 2.82 3.79
24 .13 .39 .68 1.06 1.71 2.06 2.49 2.80 3.74
26 .13 .39 .68 1.06 1.71 2.06 2.48 2.78 3.71
28 .13 .39 .68 1.06 1.70 2.05 2.47 2.76 3.67
30 .13 .39 .68 1.06 1.70 2.04 2.46 2.75 3.65
40 .13 .39 .68 1.05 1.68 2.02 2.42 2.70 3.55
60 .13 .39 .68 1.05 1.67 2.00 2.39 2.66 3.46
120 .13 .39 .68 1.04 1.66 1.98 2.36 2.62 3.37

∞ .126 .385 .674 1.036 1.645 1.960 2.326 2.576 3.291

In this example several probits (with A values of -40, -30, -25, -20, and -10) all give
the same LC50 value as the B coefficients have compensated.

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Appendix A
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Figure A-1 Example of the Relationship Between a Probit Function and the Percentage
Fatality Curve

In this example several probits (with A values of -40, -30, -25, -20, and -10) all give the same
LC50 value as the B coefficients have compensated.

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Figure A- 2 Normal Frequency Distribution for the Logarithms of the Tolerance


Concentrations

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Figure A- 3 Normal Sigmoid Curve Derived from Figure 1, Showing Percentage of


Subjects with Log Tolerance Less than a Specified Value

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Figure A- 4 Relation between percentages and probits

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Figure A- 5 Effect of the probit transformation

The normal sigmoid curve in Figure A.2 is transformed to a straight line when the ordinates
are measured on a scale linear in probits instead of in percentages

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Issued for RiskNet. Ref: T15 Revision No. 03

Figure A- 6 Probit Regression Line and 95% Fidual Band

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Appendix B
Issued for RiskNet. Ref: T15 Revision No. 03

APPENDIX B:
ERPG VALUES

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Appendix B
Issued for RiskNet. Ref: T15 Revision No. 03

B1 ERPG VALUES
Toxicity data of some form exist for a wide range of substances and it would be, clearly,
impractical to present data for each of them here. Consequently data are presented on
substances which are more commonly studied by DNV. ERPG values published by the AIHA
are provided in Table B-1
Table B-1 Extract from Current AIHA ERPG values (2008)
Chemical MW
Name CAS Number g/mol ERPG-1 ERPG-2 ERPG-3
1,2-dichloroethane 107-06-2 99 50 ppm 200 ppm 300 ppm
1,2-propylene oxide 75-56-9 58.1 50 ppm 250 ppm 750 ppm
2,4-Toluene diisocyanate 584-84-9 174 0.01 ppm 0.15 ppm 0.6 ppm
Acrolein 107-02-8 56.1 0.05 ppm 0.15 ppm 1.5 ppm
Acrylonitrile 107-13-1 53.1 10 ppm 35 ppm 75 ppm
Allyl Chloride 107-05-1 76.5 3 ppm 40 ppm 300 ppm
Ammonia 7664-41-7 17 25 ppm 150 ppm 750 ppm
Arsine* 7784-42-1 78 NA 0.5 ppm 1.5 ppm
Benzen* 71-43-2 78.1 50 ppm 150 ppm 1000 ppm
Benzyl Chloride 100-44-7 126.6 1 ppm 10 ppm 50 ppm
Bromine 7726-95-6 159.8 0.1 ppm 0.5 ppm 5 ppm
Carbon Disulfide 75-15-0 76.14 1 ppm 50 ppm 500 ppm
Carbon Monoxide* 630-08-0 28 200 ppm 350 ppm 500 ppm
Carbon Tetrachloride 56-23-5 153.8 20 ppm 100 ppm 750 ppm
Chlorine 7782-50-5 70.9 1 ppm 3 ppm 20 ppm
Crotonaldehyde 4170-30-3 70.1 0.2 ppm 5 ppm 15 ppm
epichlorohydrin 106-89-8 92.5 5 ppm 20 ppm 100 ppm
Ethylene Oxide 75-21-8 44.1 NA 50 ppm 500 ppm
Fluorine* 7782-41-4 38 0.5 ppm 5 ppm 20 ppm
Formaldehyde* 50-00-0 30 1 ppm 10 ppm 25 ppm
Hydrazine 302-01-2 32.05 0.5 ppm 5 ppm 30 ppm
Hydrogen Chloride* 7647-01-0 36.5 3 ppm 20 ppm 150 ppm
Hydrogen Cyanide 74-90-8 27 NA 10 ppm 25 ppm
Hydrogen Fluoride** 7664-39-3 20 2 ppm 20 ppm 50 ppm
Hydrogen Peroxide* 7722-84-1 34.01 10 ppm 50 ppm 100 ppm
Hydrogen Sulphide 7783-06-4 34.1 0.1 ppm 30 ppm 100 pmm
Methanol 67-56-1 32.04 200 ppm 1000 ppm 5000 ppm
Methyl Bromide 74-83-9 95 NA 50 ppm 200 ppm
Methyl Isocyanate 624-83-9 57.5 0.025 ppm 0.25 ppm 1.5 ppm
Methyl Mercaptan 74-93-1 48.1 0.005 ppm 25 ppm 100 ppm
Nitrogen dioxide 10102-44-0 46 1 ppm 15 ppm 30 ppm
perfluoroisobutene 382-21-8 200 NA 0.1 ppm 0.3 ppm
Phenol 108-95-2 94.1 10 ppm 50 ppm 200 ppm

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Appendix B
Issued for RiskNet. Ref: T15 Revision No. 03

Chemical MW
Name CAS Number g/mol ERPG-1 ERPG-2 ERPG-3
Phosgene 75-44-5 98.9 NA 0.2 ppm 1 ppm
Phosphine 7803-51-2 34 NA 0.5 ppm 5 ppm
Sulphur dioxide 7446-09-5 64 0.3 ppm 3 ppm 15 ppm
3 3 3
sulphuric acid 7664-93-9 98.1 2 mg/m 10 mg/m 30 mg/m
Toluene 108-88-3 92.14 50 ppm 300 ppm 1000 ppm
Vinyl Chloride 75-01-4 62.5 500 ppm 5000 ppm 20,000 ppm

Reference temperature: 25.0°C

NA: Not appropriate

*: Under review or consideration by the AIHA ERPG Committee in 2008


** Addendum published in 1999 with new 10 min values for HF (ERPG-1: 2 ppm;
ERPG-2: 50 ppm; ERPG-3: 170 ppm)

Note: this information is correct as of January 1 2008. It is possible that an ERPG under
review by the Committee will be balloted and approved in 2008, making it eligible for
inclusion in the 2009 ERPF Document Set.

To convert ERPG values from ppm to mg/m3 use the following equation:
ERPG(mg/m3) = ERPG(ppm) MW / 24.45

Where MW is the molecular weight.

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Appendix B
Issued for RiskNet. Ref: T15 Revision No. 03

B2 REFERENCES
/110/ American Industrial Hygiene Association web page,
http://www.aiha.org/1documents/Committees/ERP-erpglevels.pdf, 29 September 2008

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Appendix C
Issued for RiskNet. Ref: T15 Revision No. 03

APPENDIX C:
GENERATION OF TOXICITY
PROBITS

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Appendix C
Issued for RiskNet. Ref: T15 Revision No. 03

C1 GENERATION OF TOXICITY PROBITS


Two descriptions of methods of probit generation are available and each is summarised in the
following sections. Full descriptions are, obviously, given in the original references.

The `HSE' approach has the advantage of using data points at several mortality levels to
produce `real' probit constants whilst the second, TNO, approach may be useful if only a
single LC50 datum exists for a particular substance.

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Appendix C
Issued for RiskNet. Ref: T15 Revision No. 03

C2 THE `HSE' APPROACH

C2.1 Toxicological Data


It is necessary to attempt to relate the estimated atmospheric concentrations and durations of
exposure following a release to the level of toxicity produced within the surrounding
population. The data used should therefore be principally those contained in reports of
accidental single exposure of humans to the airborne substance, or generated in single
exposure inhalation studies in animals. Almost all the data available in this area relate to
toxic effects which become apparent soon after exposure.

Other effects, including mutagenicity, carcinogenicity and teratogenicity, may also arise as a
result of a single exposure. However, for most Major Hazards substances, single exposure
dose-effect data are not available for effects such as these.

Experience has shown that commonly used secondary sources of information may be
unreliable, in that the toxicological values given may be inaccurate representations of the
original results, or that the primary sources of such values are either difficult to verify or of
doubtful quality. Therefore, all the data used in the assessment of individual substances
should be obtained from the original reports.

However, for most substances, existing reliable data on acute effects arising from a single
exposure in humans are sparse.

For a few substances some information is available from their use in warfare (eg, chlorine,
phosgene). Nevertheless, for most substances the data are limited to a few reports of
accidental exposures, often involving only a few people and rarely containing accurate
measurements or even estimates of exposure concentrations and times.

Consequently, heavy reliance has to be placed on the results of experiments on animals, in


attempting to predict the responsiveness of a human population.

In general, extrapolation from laboratory animals to humans with any degree of accuracy and
reliability is fraught with difficulties, principally because of the inadequate information /2/.

Even so, for most substances it is be necessary to make the assumption that results from
animal experiments will be representative of effects on the human population, in terms of both
the nature of the effects produced and the dose-effect relationships observed.

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Appendix C
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In some cases the paucity of data on certain substances will make any analysis extremely
tenuous, and in these situations further experimental work by manufacturers or their trade
associations would be advisable if important decisions depend on the results.

C2.2 Probit Generation


For the vast majority of Major Hazard substances the most readily available information on
the toxic effects of the airborne substance is the atmospheric concentrations and exposure
times producing deaths in laboratory animals. For certain substances there may be more
complete details relating exposure conditions to both death and to more specific toxicological
end-points, particularly where studies have been conducted to current internationally agreed
protocols3.
Therefore, the first stage in the process will be the gathering of animal LC50 values, each
with an associated exposure time. Most animal experiments involve the use of small group
sizes, and the response of the group will most accurately reflect the likely response of the
population from which the group is drawn, at the 50% mortality level.

From the available data, the most sensitive animal species and strain would normally be used
to represent the prediction of human responsiveness, ie the lowest LC50 value and associated
exposure time will be taken as the corresponding values for the human population, unless
there is information indicating that other animal results will serve to model human
responsiveness more reliably.

As exposure conditions producing a low mortality level within a population cannot, in


practice, be observed directly because of the very large groups of animals required, the
conventional method of deriving such parameters is by probit analysis.

Occasionally, substances may be encountered where the only available information is a


tabulated LC50 value, with an associated exposure time. In such cases a possible approach is
to estimate, for the species and strain under consideration, the ratio between the LC50 and the
LCx, where x is a lower percentage of deaths, for instance around 1-5% in the case of the
SLOT used for land-use planning. The slope of the dose-effect curve, and hence this ratio,
will vary, depending on the substance and on the heterogeneity of the test animals.
Nevertheless, in a study of the acute toxicity of a large number of pesticides in rats of the
same strain, sex and age, examined under fixed experimental conditions, many pesticides had
an LC50/LC1 ratio of between 1.5 and 44. Ratios of a similar magnitude have also been
obtained in studies with various lung irritant gases. However, ratios of this type should be
used to extrapolate from 50% mortality to another SLOT only in the absence of any other
useful data.
Theoretical considerations indicate that there are several forms of expressions relating the
toxic load to a function of C and t. The manner in which c and t are functionally related
should only be examined within a collection of data for the same substance, animal species
and type of toxic effect. If data from different animal species are combined in a single

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Kenich
Appendix C
Issued for RiskNet. Ref: T15 Revision No. 03

analysis, then species variation will also exert an unknown degree of influence on the derived
relationship between C and t.

Acute inhalation toxicity experiments in laboratory animals, performed in the early years of
this century on a limited number of gases, obtained mortality results suggesting the following
relationship:-

toxic load = C x t (/111/)

More recently, a literature survey of more than 30 substances, for which LC50 values had been
determined in the same species for at least three different exposure periods, suggested two
groups of substances, showing empirical relationships of:-

(i) toxic load = Ct

(ii) toxic load = C2t.

Overall, experimental observations suggest that in many cases the following general
relationship may hold for acute lethality:-

toxic load = Cnt


A recent review of acute inhalation studies on various substances, using lethality as an end-
point, derived n values ranging from 0.8 to 4.9 for individual studies on particular substances
and animal species. Values outside this range are also known to exist.

The requirement at this stage is, therefore, knowledge of the value of n which will relate
variations in C and t to a constant, experimentally observed level of mortality within an
individual animal species. The most suitable reference point is usually 50% mortality, since
exposure conditions relating to this level of mortality are most readily available. A plot of 1n
c against 1n t, each pair of c and t values relating to the production of 50% mortality, will
permit derivation of n from the slope of the resulting line (-1/n) since

Cnt = constant, k

can be rearranged to:- ln C= -1/n ln t + 1/n ln k

In some cases the data available on a substance may be insufficient to permit the derivation of
n. In such situations risk analyses using the two values of n commonly observed, 1 and 2,
should be compared. Using the value of n and concentration/time combinations for two
different mortality levels, the values for `A' and `B' can be determined.

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Kenich
Appendix C
Issued for RiskNet. Ref: T15 Revision No. 03

C3 THE `TNO APPROACH


For locally acting substances the most important parameter is the inhalation dose per unit lung
area

C t (Va )
D"=
Ar

where

C = concentration (mg/m3)

t = exposure duration (min)

Va = breathing rate (litres/min)

Ar= lung area (m2)

Lung area and breathing rate can be derived from body weight7

Va = u W0.7

Ar = v W0.92

where W is body weight (kg) and u, v are constants.

From this, TNO arrive at

D" = (u/v) W-0.22

This is only valid for conditions of rest.

To account for variations in absorption efficiencies of the nasal passages of test animals and
the mouth of humans (humans breathe more through the mouth) an arbitrary safety factor of 5
is introduced. This is then multiplied by 2 to account for the fact that the test animals would
be at rest whereas humans, exposed to an accidental release of gas, would not.

For systemically acting substances the breathed in dose is expressed in terms of body weight

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Kenich
Appendix C
Issued for RiskNet. Ref: T15 Revision No. 03

D1 = u W-0.3

Because of increased uncertainties in the effects of systemically acting substances, a safety


factor of 10 is introduced which is, again, further multiplied by 2.

Using average body weights for several different test animals species and humans, and the
factors determined above, extrapolation factors are produced for both locally acting and
systemically acting substances. The conclusion is drawn by TNO /112/ that there is no
significant difference between the two.

It is our opinion, however that this is a tenuous conclusion to draw when the data are based on
arbitrarily chosen safety factors which have no proven basis.

The probit used is of the normal form

Pr = A + B ln (Cnt)

The interspecies differences are assumed to affect only the `A' term and not the `B' or `n'
terms. The `n' term is either known or assumed to be 2. The `B' term is known to lie between
1.1 and 6.1 although values outside this range are given in tables later in the TNO report. A
value of B = 1 is chosen for all probits for all substances. This is described as conservative
below LC50 concentrations since it takes into account the greater spread in sensitivity in a
human population as compared to laboratory animals.

Using the above assumptions, the determination of a probit is reduced to the determination of
the `A' term. This is achieved using the figure reproduced here as Figure C.1. A table of
probit functions derived for a selection of materials is given in Table C.1. Please note that the
units of concentration employed are mg/m3 not ppm.

It should be noted that this mechanistic treatment, although attractive to engineering studies,
is not at all supported by toxicologists. In fact it should only be adopted in extremes where
there is very little data available. The great uncertainty under these circumstances must be
noted in the study report.

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Kenich
Appendix C
Issued for RiskNet. Ref: T15 Revision No. 03

Figure C- 1 TNO Calculation Procedure for Probit Constants (/112)

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Kenich
Appendix C
Issued for RiskNet. Ref: T15 Revision No. 03

C4 REFERENCES
/111/ Haber F., Funf Vortrage aus den Jaren 1920 - 1923, Springer - Verlag, Berlin 1924.

/112/ TNO, Methods for the Determination of Possible Damage to People and Objects
Resulting from Releases of Hazardous Materials, CPR 16E, Voorburg, December 1989.

/113/ ten Berge W.F. and Guldemond C.P., Required Knowledge for the Evaluation of Health
Hazards from Acute Inhalatory Exposure of Humans, International Process Safety
Group, Cannes, September 1986.
- o0o -

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Kenich
Appendix D
Issued for RiskNet. Ref: T15 Revision No. 03

APPENDIX D:
CONVERSION OF PROBITS
FOR DIFFERENT UNITS
(MG/M3 AND PPM)

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Kenich
Appendix D
Issued for RiskNet. Ref: T15 Revision No. 03

D1 CONVERSION BETWEEN PROBITS EXPRESSED IN MG/M3


AND THOSE EXPRESSED IN PPM
A number of authorities and authors have published probit functions in terms of a
concentration expressed in mg/m3 whereas, in DNV, the current standard practice is to
express concentration in ppm. Clearly, a standard method of converting from one to the other
is desirable.
If a reference temperature of 25°C is chosen then the following analysis may be performed.

At 25°C and 1 atmosphere pressure, 1 kg mole occupies

298
volume = 22.4 x = 24.45 m3
273

If the concentration is X mg/m3 then:

X kg 24.45 X m3 24.45 X
Concentration = 6 3
= 6 3
= ppm
10 m MW 10 m MW

or

MW mg
1 ppm =
24.45 m3

Therefore;

Pr = B ln (C n t) + A C as mg/ m3

  MW  n 
Pr = B ln (Cn t) + B ln   +A C as ppm
  24.45  
 

   MW  n  
Pr = B ln (C n t) + B ln   
 + A C as ppm
   24.45   
   

Consequently, only the effective value of A changes since B, n and MW are constants. In
PhastRisk and Phast, a reference temperature of 9.85°C is used at which temperature a kg mol
occupies 23.21m3. - o0o -

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Kenich
Appendix E
Issued for RiskNet. Ref: T15 Revision No. 03

APPENDIX E:
PROBITS OF MIXTURES

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Kenich
Appendix E
Issued for RiskNet. Ref: T15 Revision No. 03

E1 PROBITS FOR MIXTURES OF TOXIC AND NON-TOXIC GASES


It is not uncommon for toxic gases to be mixed (either deliberately or otherwise) with non-
toxic gases (eg. carrier gases or hot nitrogen in smoke). Clearly, the effect of the non-toxic
gas will have an effect on the toxicity of the mixture and it is appropriate to derive a probit
function which reflects this.

If a mixture at concentration Cmix in air contains a mole fraction, X, of toxic gas (C1) and the
standard probit for the toxic gas is:

Pr = A1 + B1 ln(C1n t)

The revised probit for the mixture is:

Pr = A1 + B1 ln ([X.Cmix]n t)

Pr = (A1 + B1 ln (Xn)) + B1 ln (Cmixn t)

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Kenich
Appendix E
Issued for RiskNet. Ref: T15 Revision No. 03

E2 PROBITS FOR MIXTURES OF TOXIC GASES


Mixtures of toxic gases occur in many circumstances (products of combustion, etc.) and a
probit to predict the toxicity of the mixture is desirable. However, no published methodology
currently exists to do this and there is disagreement amongst toxicologists as to how the
situation should be modelled. It is not straightforward to generate a single mixture Probit as
the Cnt relationship means that the dominant toxic agent can change in a mixture depending
on the power of n and the time of exposure.

One approach is to add the concentrations of the toxic elements of the mixture together and
treat this new concentration as the concentration of the most toxic component. This technique
is thought to be conservative and works tolerably well when the most toxic element of the
mixture is also the most abundant. However, if the more toxic element makes up only a small
proportion of the mixture, then the results can be overly conservative.

An alternative approach is to assume that the toxicities of the individual elements of the
mixture are not additive and to treat them as separate sources of toxicity. This however may
understate the extent of hazard of a toxic mixture.

If single point toxicity criteria are being used (eg TLV, ERPG) then the toxic criteria for the
mixture has been modelled as:

1 X1 X2 Xn
= + + ........... +
Toxicity mix Toxicity1 Toxicity 2 Toxicity n

where X1, X2 etc are mole fractions.

This approach is considered unsuitable for use with probits.

For conservatism, the method of adding concentrations is recommended until a more rigorous
method is published.
- o0o -

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Kenich
Appendix F
Issued for RiskNet. Ref: T15 Revision No. 03

APPENDIX F:
SUGGESTED APPROACH TO
IMPAIRMENT AND
INCAPACITATION DUE TO SMOKE

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Kenich
Appendix F
Issued for RiskNet. Ref: T15 Revision No. 03

F1 INTRODUCTION
This appendix contains a suggested approach for calculation of cumulative effect from smoke,
both with respect to impairment and incapacitation. The approach attempts to take account of
the synergetic effect between CO and CO2 as well as additive effects from toxic gases,
oxygen depletion and high temperature.

Equations combining fractions of dose for each smoke components and temperature to a
cumulative dose have been developed in section 8 above. These are in the following used to
generate suggested criteria for typical smoke compositions.

A similar approach is suggested for incapacitation (and subsequent death), i.e. the fraction of
the incapacitation doses are added up to form a total dose. The basic complication here is that
the available equations for dose fractions expresses relationships between concentrations and
impairment, but not for incapacitation. This is suggested allowed for by introducing
reduction factors for the individual dose fractions. The reduction factors are fixed so that
lethal doses give dose fractions equal to 1.0 for each individual contributor.

Refer to Section 8 for descriptions of smoke effects and limits for exposure causing death.

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Kenich
Appendix F
Issued for RiskNet. Ref: T15 Revision No. 03

F2 APPROACH
The effects of toxic gases depend on the dose of product effectively received . The method
described in this Appendix is documented in the SFPE Handbook for Fire Protection
Engineering (/94) and in the ISO/TS 13571:2002 technical specification. It is used in the
DNV software SOQRATES (an excel based tool for offshore QRA) for impairment of TR
calculations.

It is based on the use of the fractional effective dose (FED) method which assumes that the
different components of fire work in an additive way and also that the effect is additive over
time. For this method, the received doses for small periods of time during a fire are expressed
as a fraction of the dose causing the toxic effect, and these FEDs are added together to give an
estimation of the combined effect. When the dose causing the toxic effect becomes greater
than 1 impairment is assumed to occur

Here a breathing rate corresponding to light activity is assumed.

F2.1 Carbon Monoxide


Incapacitation

The following equation gives the FED for CO gas taken into account the increased breating
rate due to increased CO2 levels. This approximation is only valid for exposure up to one
hour.

ISO/TS 13571:2002 gives the following relation for the fraction of the incapacitating dose:

FEDnarcotics = ∑  +
(
 C CO in * 10 4 exp C HCN in * 10 4 / 43 )  * ∆t * V
 60 CO 2 F1
∆t  35,000 220 
Neglected
Where
∆t = time increment [s]
CCO in = average concentration of CO [%] over the time increment ∆t
( C HCN in = average concentration of HCN [%] over the time increment ∆t )
VCO 2 = frequency factor due to hyperventilation,
C 
VCO 2 = 1 if C CO 2 in < 2%, VCO 2 = exp CO 2 in  if C CO 2 in > 2%
 5 

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Kenich
Appendix F
Issued for RiskNet. Ref: T15 Revision No. 03

C CO 2 in = volume concentration of CO2 [%]

Therefore, the rate of variation with time [ s −1 ] during ∆t is:

CCO * 104 1
FCO = * VCO 2 * * t F2
35000 60

Where

C CO is concentration of carbon monoxide in smoke/air mixture in %

t Is time in seconds

VCO2 = 1 if CCO2 ≤2%

CCO 2
= exp( ) if CCO2 >2%
5

The toxicity of CO can be related to the concentration of COHb in the blood.

For short exposures at high concentrations when the blood concentration is well below saturation
level, the Stewart-Peterson equation has been derived from experimental human exposures (Stewart et
Al, 1973):

∆t
( ) (
%COHb = ∑ 3.317 * 10 −5 * C CO in * 10 4 )
1.036
( )
* Bactual * 60 * 10 3 *
60
F3
∆t

Where:
%COHb = approximate concentration in blood of carboxyhaemoglobin [%]
C CO in = average concentration of CO [%] over the time increment ∆t
Bactual = Bnominal * VCO 2 , actual breathing rate [m3/s]

Where:
Bnominal = nominal breathing rate supplied [m3/s]
C 
VCO 2 = 1 if C CO 2 in < 2% , VCO 2 = exp CO 2 in  if C CO 2 in > 2%
 5 

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Kenich
Appendix F
Issued for RiskNet. Ref: T15 Revision No. 03

∆t = time increment [s]

[L/min] [m³/s]
Rest 8.5 0.000142
Light effort 25 0.000417
Heavy effort 50 0.000833

Table F.1 typical breathing rates (B. Karlsson and J. Quintiere 1999)

Hence,
∆t
( )( 
)
%COHb = 3.317 *10 −5 * 60 *103 * Bnominal *  CCO in *10 4( )1+ 0.036
*

*VCO 2  F4
 60 

(
%COHb = (3.317 * 10 −5 )* (60 * 10 3 )* Bnominal * (35,000 * FEDnarcotics ) * CCO in *10 4 )
0.036

F5

%COHb ≈ 95,000 * Bnominal * FEDnarcotics F6

Therefore, the fraction of the incapacitating dose at time t can be related to the
concentration of carboxyhaemoglobin present in blood at time t :

%COHb(t )
FEDnarcotics (t ) ≈ F7
95,000 * Bnominal

Where:
%COHb = approximate concentration in blood of carboxyhaemoglobin [%]
Bnominal = nominal breathing rate supplied [m3/s]

Equation F7 is used as basis for the smoke integrity model in SOQRATES. Equation
F2 may be used as they give approximately the same answer see section F3
EXAMPLE Calculation

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Kenich
Appendix F
Issued for RiskNet. Ref: T15 Revision No. 03

F2.2 Carbon Dioxide


Incapacitation

The impairment dose for carbon dioxide is expressed as a fraction of the smoke impairment
dose:

exp(0.5189 * C CO2 ) 1
F CO 2 = * *t F8
475 60

Where

CCO2 is concentration of carbon dioxide in smoke/air mixture in %

t is time in seconds

F2.3 OXYGEN STARVATION


Impairment

The impairment dose for oxygen starvation is expressed as a fraction of the smoke
impairment dose:
Equation F3

exp(0.54 * (20.9 − C O 2 )) 1
F O2 = * *t F9
3395 60

Where

O2 is concentration of oxygen in
smoke/air mixture in %

t is time in seconds

Concentrations greater than 14% are considered to have no effect.

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Kenich
Appendix F
Issued for RiskNet. Ref: T15 Revision No. 03

F2.4 High Temperature


Incapacitation

The effect of inhalation of gases at elevated temperatures is expressed as a fraction of the


impairment (smoke) dose:

t
F Temp = (5.1849 -0.0273xC)
F10
60 x e

Where

C is temperature in smoke/air mixture in Celsius

t is time in seconds

Temperatures less than 37 C are not considered to cause impairment.

F2.5 CUMULATIVE EFFECT


Impairment or incapacitation (and subsequent death) could be taken to occur when the
cumulative dose (FTot) fraction for CO, CO2, O2 and temperature exceeds 1.0 :

F Tot = F CO + F CO 2 + F O 2 + F Temp F11

Relevant equations for impairment and incapacitation are used to calculate the respective dose
fractions.

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Kenich
Appendix F
Issued for RiskNet. Ref: T15 Revision No. 03

F3 EXAMPLE CALCULATION
The approach to calculate impairment or incapacitation from smoke is to:
• Determine smoke composition near fire
• Calculate details of dispersion of smoke (concentrations at points of interest)
• Calculate dose fraction for each component
• Add dose fractions and compare to criteria of 1.0

In the following, example compositions for smoke are presented, and calculations of
impairment and incapacitation doses are shown as examples

Case

Example calculations: Fuel controlled liquid fire


smoke concentration: 71.%
exposure duration: 1 minute.
Nominel breathing rate : 17.7 l/min ( 2,95 E-4 m3/sec)

Table F- 1Error! AutoText entry not defined. Initial Gas Concentrations in Smoke (Bonn,
1993)
GAS WELL VENTILATED/ UNDER VENTILATED/
FUEL CONTROLLED VENTILATION CONTOLLED
Gas fire Liquid fire Gas fire Liquid fire
%CO 0,04 0,08 3 3,1
%CO2 10,9 11,8 8,2 9,2
%O2 0 0 0 0
Particulates 15 47 29 70
(dB/m)

Table F- 2Error! AutoText entry not defined. Gas Concentrations in Smoke of 71 %


Fuel controlled Liquid fire
%CO 0.0568
%CO2 8.378
%O2 6.06%

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Kenich
Appendix F
Issued for RiskNet. Ref: T15 Revision No. 03

VCO 2 = 1 if C CO 2 in < 2% ,
C 
exp CO 2 in  if C CO 2 in > 2%
 5 

 8.38 
This gives VCO 2 = exp  = 5.34
 5 

∆t
( )( )

%COHb = 3.317 *10 −5 * 60 *103 * Bnominal *  CCO in *10 4 ( )
1+ 0.036
*

*VCO 2 
 60 

( ) ( ) 
(
%COHb = 3.317 * 10 −5 * 60 * 10 3 * 2.94 * 10 − 4 *  0.0568 * 10 4 )
1+ 0.036
*
60 
* 5.34 
 60 

%COHb = 2.39

%COHb(t )
FED narcotics (t ) ≈
2.39
= = 0.08
95,000 * Bnominal 95,000 * 2.95 E − 4

Using Equation F2 instead we get the following:

C CO * 10 4 1 0.0568 * 10 4 1
FCO = * VCO 2 * * t = * 5.34 * * 60 = 0.087
35000 60 35000 60

Using the above equation for different exposure times we get the graph as presented in Figure
F-1. Implementation of the equations for CO CO2 and O2 for a 37oC smoke the total FED for
different smoke concentrations are given in Figure F-2 and F-3
Please note that the temperature comonent is not included in figure F-2 and F-3 and the effect
of high smoke temperature must be evaluated separatey. The incapasitation dose as a function
of smoke temperatre is given in Figure F-4

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Kenich
Appendix F
Issued for RiskNet. Ref: T15 Revision No. 03

0.9

0.8
60sec. FC gas
300sec. FC gas
0.7
900sec. FC gas

0.6 3600sec. FC gas


1800sec. FC oil
F total

0.5 60sec. VC oil


180sec. VC oil
0.4 300sec. VC oil
900sec. VC gas
0.3 1800sec. VC oil

0.2

0.1

0
0 0.1 0.2 0.3 0.4 0.5 0.6
Smoke concentration ( fraction)

Figure F- 1 Fractional effective dose Co (Fco)

1.2

60sec. FC gas
60sec. FC oil
0.8 300sec. FC gas
300sec. FC oil
900sec. FC gas
F total

0.6 900sec. FC oil


1800sec. FC gas
1800sec. FC oil

0.4 3600sec. FC gas


3600sec. FC oil

0.2

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Smoke concentration ( fraction)

Figure F- 2 Fractional effective dose for exposure of 37oC smoke from fuel controlled
fires (Fco +Fco2 + Fo2) ( effect of high smoke temperature is not included

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Crossthwaite, A. Falck, K. CRITERIA
Kenich
Appendix F
Issued for RiskNet. Ref: T15 Revision No. 03

Fractional effective dose (FED) VC fires

1.2

60sec. VC gas
60sec. VC oil
0.8 180sec. VC gas
180sec. VC oil
300sec. VC gas
F total

0.6 300sec. VC oil


900sec. VC gas
900sec. VC oil

0.4 1800sec. VC gas


1800sec. VC oil

0.2

0
0 0.1 0.2 0.3 0.4 0.5 0.6
Smoke concentration ( fraction)

Figure F- 3 Fractional effective dose for exposure of 37oC smoke from ventilation
controlled fires (Fco +Fco2 + Fo2) ( effect of high smoke temperature is not included
1

0.9

60 sec exposure
0.8
30 sec exposure
120 sec exposure
0.7
Fractiopn of incapasitation

0.6

0.5

0.4

0.3

0.2

0.1

0
0 50 100 150 200 250 300
Temperature (C)

Figure F- 4 The effect of inhalation of gases at elevated temperatures


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Crossthwaite, A. Falck, K. CRITERIA
Kenich
Appendix G
Issued for RiskNet. Ref: T15 Revision No. 03

APPENDIX G
DERIVING SINGLE VALUE CRITERIA FROM PROBITS

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Crossthwaite, A. Falck, K. CRITERIA
Kenich
Appendix G
Issued for RiskNet. Ref: T15 Revision No. 03

G1 INTRODUCTION
This Appendix describes the approach used to derive single value criteria in this TN. The
approach is also recommended for application to deviations from the single value criteria in
the main report.

A single value criterion refers to the level of exposure (concentration, heat load etc.) which
cannot be sustained for a defined period of time, without causing death, (or alternatively
another defined level of harm).

The methodology is as follows:


• Choose a probit
• Estimate/calculate an escape time
• Define the vulnerability
• Define the incapacitation dose
• Calculate the level of exposure

The above steps are discussed in more detail below.

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Kenich
Appendix G
Issued for RiskNet. Ref: T15 Revision No. 03

G2 METHODOLOGY

G2.1 Choice of Probit


Choice of probits should follow the recommendations in this TN.

G2.2 Time to Escape


The duration of exposure equals the time to escape from the affected area. The time needed
for escape is the time taken to react and move from the exposed area to a shelter/place of
safety (from the radiation, toxic gas etc.). The following factors should be taken into account:
• Initial confusion/time taken to make a decision of where to escape to and to possibly
raise the alarm.
• Congestion due to other people using same escape way.
• Time taken to cross exposed areas, including climbing/descending stairs etc. This
could be affected by (depending on the nature of the hazard):
• Poor visibility due to smoke
• Poor visibility due to glare/heat from flame
• Impaired mobility due to inhalation of smoke or toxic gas
• Impaired mobility due to inhalation of heated air and combustion products
• Impaired mobility due to pain
• Difficulties due to heated metal equipment, hand rails etc.
• Whether or not an H2S alarm is installed (for H2S releases)
• The odourless nature of H2S at hazardous concentrations (for H2S releases)

The time taken to escape should be the average time taken for a person to escape from the
areas studied. Large differences in escape time may warrant several criteria to be developed.

G2.3 Define Vulnerability


The probit function gives the lethal dose (combination of time and exposure) for a person of a
given vulnerability (e.g. average vulnerability, corresponding to LD50). This is, for offshore
societal risks calculations, sometimes approximated to the percent of population killed by the
dose. However, individual risk calculations must, by definition, relate to a certain individual,
i.e. the risk to an individual of a given lethality.

The single value criterion developed in this TN relates to the risk to a person with a 50-
percentile vulnerability, i.e. a person who would be killed by the LD50 dose.

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Kenich
Appendix G
Issued for RiskNet. Ref: T15 Revision No. 03

It may be argued that personnel on offshore platforms are relatively young and fit, have better
health and health care etc. compared to an average group of people in society. If this
argument is applied, they should be more resistant to the exposure of hazards and a higher
lethal dose may consequently be chosen, e.g. LD75 or LD90.

G2.4 Definition of Incapacitation Dose


Inserting the escape time and lethality level into the probit function results in a level of
exposure which causes death (in the period of time and for a person with a defined
susceptibility). The human body will, if subjected to a lower level of exposure for the same
period or the same level of exposure for a shorter time period, be able to recover.

Using this level of exposure as the fatality criterion may however be optimistic, because the
methodology takes little account of the synergy between time to escape and effects of
exposure. Incapacitation (inability to escape from exposed area) will occur for lower levels of
exposure and/or shorter exposure times than the lethal dose would imply. Thus in reality,
although survival would be the result if escape had been completed, incapacitation could
occur, thereby causing extended exposure and a dose in excess of lethal dose.

The fatal level of exposure should therefore reflect the dose which causes incapacitation (and
thereby death) within the time to escape. It may be assumed that immediate rescue of
incapacitated personnel within the affected zone is not practicable. In reality, this may
depend on the severity of the accident and the availability of rescue equipment.

Unfortunately, no probit relationships for incapacitation are available, so appropriate


assumptions must be made. It is assumed that the incapacitation dose is expressed as a
percentage of the lethal dose (as found by the probit).

G2.5 Calculate Lethal Level of Exposure


The most straightforward method of calculation is:
1. Estimate the fatal dose (not taking account of incapacitation - here taken as LD50).
2. Reduce the dose and calculate the corresponding level of exposure. The equation for dose
used in the probit may be solved with respect to the level of exposure, taking account of
the estimated/assessed reduced lethal dose due to incapacitation. Note that the dose
equation often incorporates the level of exposure raised to some power.
Example:
LD50 is found from the probit. For radiation exposure the dose equals I4/3 t, I being
intensity (kW/m2) and t time in seconds. If it is assumed that the incapacitation dose is
75% of the LD50, the incapacitation level of radiation becomes 0.753/4=0.81 of the lethal
radiation.

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Crossthwaite, A. Falck, K. CRITERIA
Kenich
Appendix G
Issued for RiskNet. Ref: T15 Revision No. 03

G2.6 Important Assumptions


The assumptions and simplifications used above may need to be re-assessed for a more
detailed study. The following notes are appropriate:
• The approach assumes a constant source of heat load over the exposure period. In
reality, most fires will initially expand and then decay with time, and thus the
radiation received at any given point will also be a function of time. A full
integration of the received dose may be performed.
• Recovery from radiation burns is dependent on the speed and quality of medical
treatment. Large casualty rates or remote locations will generally involve larger
delays before full medical attention should be given. Credit or otherwise to local
conditions can be given.

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