Societal Risk Assessment of Chlorine Release Scenario – A case study

Diptendu Das, Avimanyu Banerjee, K Ramprasad and Ramdas Bhattacharya

Industrial Plants Safety Division (IPSD), Atomic Energy Regulatory Board (AERB), Mumbai
Email: diptendudas@aerb.gov.in, avimanyu @aerb.gov.in, ramp@aerb.gov.in,
rbhattacharya@aerb.gov.in

Abstract
A societal risk assessment study has been carried out for recent chlorine gas release scenario
in Mumbai. Significant quantities (about 141 no) of chlorine gas tonners were stored in an
open yard, out of which one tonner leaked chlorine gas into the environment. Considering the
toxic and corrosive nature of chlorine gas a study has been carried out on chlorine leak
scenario and its subsequent dispersion (heavy gas dispersion) along with its effect distance.
Chemical Exposure Index (CEI) is calculated to find out Hazard distance (HD) for the release
for various levels of concern as per Emergency Response Planning Guidelines (ERPG-1,
ERPG-2 & ERPG-3).
The chlorine gas release scenario is simulated using Areal Location of Hazardous
Atmospheres (ALOHA) Software. Weather data has been considered based on the
atmospheric data on early morning (3:00 A.M.) 14th July 2010 (i.e. day of release incident)
obtained from meteorological data. Various Scenarios of releases are assumed and different
wind speeds and stability classes are considered to simulate the scenarios. Based on the site
map of the incident spot (point source of release) threat zones are generated. The effect
distance and postulated exposures on population and inhabitants around the vicinity of the
site of release is studied. The emergency preparedness and disaster mitigation measures to
handle such emergency situation are assessed from the above study. It is estimated from the
analysis that around 1.3Km is the most affected distance due to the release.
Key words: Societal Risk, Chemical Disaster, Chlorine Leak, Wind Stability

1. Introduction
Flammable / Toxic chemical release from storage facility is always hazardous. However
flammable release may not cause accident all the time because it may so happen that even
after leakage/ spillage of flammables it just disperses or it can be contained without any fire
accident due to absence of ignition source at the vicinity. Hence Flammable release is an
incident not an accident if fire is not occurred. Whereas toxic release is always an accident
because it has potential to pose a threat to human being because of its level of exposure.
Release of any stored chemical can be of two types:
a) A common type of leakage due to faulty valves or due to small hole in the cylinder.
b) A major release due to bursting or rupture in a cylinder, which is commonly termed as
catastrophic failure, which is most unlikely event.
It is necessary to estimate the distances where the effect of toxic chemicals pose detrimental
effect to the health of the exposed individuals due to toxicity.
Continuous leakages (plume) may be treated by using conventional atmospheric dispersion
model with continuous exposure to a person present nearby where as instantaneous release
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(puff) may cause short time Exposure with higher concentration. Again depending upon the
nature of gas released (dense/lighter than air) dispersion can be classified as Gaussian
dispersion (for lighter gases) and Heavy gas dispersion (for heavy gases).
The conventional Pasquill-Gifford model holds good results for gas dispersions for both
Plume and Puff release.
Table1. Meteorological Conditions Defining Pasquill-Gifford Stability Classes [CPQRA, 2000]

Daytime insolation Night time conditions Anytime

of 4/8 low
Surface wind Strong Moderate Slight Thin overcast <=3/8 cloudiness Heavy overcast
speed (m/s)
cloud
<2 A A-B B F F D
2-3 A-B B C E F D
3-4 B B-C C D E D
4-6 C C-D D D D D
>6 C D D D D D

Where, ‘A’ represents - extremely unstable conditions, ‘B’ represents - moderately unstable
conditions, ‘C’ represents - slightly unstable conditions, ‘D’ represents - neutral
conditions, ‘E’ represents - slightly stable conditions and ‘F’ represents - moderately stable
conditions [CPQRA, 2000]

The dense (heavy) gas dispersion or Gaussian (light) dispersion depends upon the following
factors the factors:
a) Molecular weight of the gas, b) Release temperature of the gas, c) Presence of spray
(minute droplets in gas) and d) Temperature and humidity of ambient air.
Chlorine (M.W.70.91) gives heavier than air cloud both at ambient temperature and its
boiling point (-34ºC). The droplets of liquid suspended in the gas vaporize by taking latent
heat of vaporization from the gas, thus cool it (making it heavier) while the effect of water
droplets condensing out from humid air by adding heat of condensation to the gas, making it
lighter. Thus, low air humidity (dry air) and a large flash-off of liquid droplets make it denser
than air cloud.
Other factors influencing gas dispersion are:
a. Atmospheric Stability
The atmospheric conditions have been divided into six classes of stability by Pasquill. Class
A represents unstable conditions of strong sunlight, clear sky and high level of atmospheric
turbulence conditions which promote rapid mixing and quick dispersion of any released
gases. Class F represents stable conditions occurring at night and consisting of light winds,
low level turbulence and inversion conditions. Class D is in between and known as the
neutral condition.
b. Effect of wind Meandering on Evacuation or Protection action zones
The direction of wind is rarely steady over any significant period of time and it tends to shift
back and forth between various directions. This shifting over time is referred to as
meandering. The practical significance of wind meandering is that an area larger than that
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predicted by the application of dispersion models may require evacuation or other means like
sheltering populations in place during an actual emergency.
Other influencing factors in gas dispersion are source geometry, elevated discharge, local
terrain, discharge velocity and Threshold Limit Value (TLV) for toxic gases and presence of
mists, fumes, aerosols, fine dusts etc.
The Britter and McQuaid (1988) [CPQRA, 2000] model has been used for heavy gas
dispersion study. The model is best suited for instantaneous or continuous ground level
release of dense gas. Following a typical puff release, a cloud having similar vertical and
horizontal dimensions (near the source) may form. The dense cloud slumps under the
influence of gravity increasing its diameter and reducing its height. Considerable initial
dilution occurs due to the gravity-driven intrusion of the cloud into the ambient air.
Subsequently the cloud height increases due to further entrainment of air across both the
vertical and horizontal interface. After sufficient dilution occurs, normal atmospheric
turbulence predominates over gravitational forces and typical Gaussian dispersion
characteristics are exhibited.
Joseph (2004) analyzed chlorine transfer hose catastrophic failure. In this study mainly
failure mechanism (corrosion) has been studied during loading and unloading time. However,
the atmospheric chlorine concentration has not been studied after release. Ruj et al. (2012)
studied offsite emergency planning aspects using Complex Hazards Air Release Model
(CHARM) software package. However, using fundamental principle of the heavy gas
dispersion is not carried out in this work. Dandrieux et al. (2002) carried out small scale
experiment on chlorine release and dispersion. However, the effect of release and dependency
of weather parameter is not studied. So there is a scope for studying chlorine accidental
release scenario using fundamental principle of heavy gas dispersion. In this paper, we have
investigated concentration of chlorine at various distances by using heavy gas dispersion
model (Britter and Mcquaid, 1988) and DOW’s Chemical Exposure Index (CEI) [Dow’s CEI,
AICHE, 1994] method. Subsequently, the effect distance results have been verified using
ALOHA software. Also emergency mitigating measures adopted during the release has been
outlined in this paper.

Fig. 1: Heavy Gas dispersion mechanism [CPQRA, 2000]

2. Dispersion Modeling
Atmospheric dispersion of vapors is key element for consequence analysis. Typically, the
dispersion calculations provide an estimate of the geographical area affected and the average
vapor concentrations expected.

3
The preliminary calculations require an estimate of the released rate of the gas based on
release temperature, pressure and release diameter and the atmospheric conditions (such as
wind speed, stability class), surface roughness etc.
For a continuous release of gas as per Pasquill-Gifford plume model [Pasquill et al., 1974]
 1  y 2    1  z  H 2   1  z  H  2  
C  x, y , z       
exp   exp      exp     
2 y z u  2   y     2   z    2   z   
G (1)
    

Where,
<C>(x, y, z) = average concentration (mass/volume)
G = continuous release rate (mass/time)
σ x, σ y & σ z = dispersion coefficient in the x, y and z directions (length)
u = wind speed in x direction (length/time)
y = cross-wind direction (length)
z = distance above the ground (length)
H = height of the source above the ground level plus plume rise (length)

Assumptions:

i. Chlorine tonners were placed in open yard i.e. on ground. So, it is assumed that it is a
ground level release (H = 0).
ii. We are interested in ground level (z = 0) concentration at different downwind
distances (x) and also for a particular downwind distance what is the concentration in
various cross-wind locations (y) (as at lower wind speed, wind movement is very
erratic).
So, as per the assumptions equation (1) reduces to
 1  y 2 
C  x, y , z  
(2)
exp   
 y z u  2   y  
G

 

Fig.2: Atmospheric dispersion showing plume release

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Two release scenarios are considered for the chlorine dispersion study as discussed below
Chlorine Release scenario Case 1- Spillage of liquid chlorine from 2 mm hole located at
the bottom of the tonner
Chlorine cylinder (72% filled with 650 Kg of liquid chlorine) was stored in open yard.
Assuming a hole size of 2 mm circular diameter at the bottom of the tonner was developed
over a period time due to corrosion. Following models are used to analyse chlorine
dispersion
i. DOW’s Chemical Exposure Index (CEI) model :
The Chemical Exposure Index provides a method of rating the relative hazards potential
based on the chemical release . It considers threshold concentration as emergency response
planning guidelines (ERPG) There are three levels of emergency response planning
guidelines (ERPG-1, ERPG-2 and ERPG-3) for 1hr exposure: i) For level 1: experience of
something more than a mild transient health effect or odor ; ii) For level 2: serious or
irreversible health effects iii) For level 3: life-threatening effects.
The schematic diagram of a chlorine tonner is shown in Fig. 3

Fig.3: Schematic of Chlorine Tonner (Internal pressure 9 atm, 30oC)

Fig.4:Handling of chlorine tonner from bay

Fig.4: Handling of Chlorine Tonner

5
Table 2: Input Data used for chlorine release

Pressure inside tonner (abs) (Pa) 912 KPa

Storage temperature (T) 30ºC

Molecular weight of chlorine (MW) 70.91

Diameter of hole (D) 2 mm

Normal boiling point (Tb) -33.97ºC [at atmospheric pressure]

Liquid density in bullet (ρL) 1358.4 Kg/m3

Heat of vaporization (Hv) 275,030 J/Kg

Heat capacity of liquid (Cp) 943.8 J/Kg/°C [at average temperature]

Height of liquid in tank, ∆h 0.504 m [as 72% is filled initially. So, 0.72×0.7]
Ambient temperature 30ºC (303.15 K)
Ambient pressure 1 atm
Gravitational acceleration (g) 9.81 m/s2
Initial density of chlorine released (ρ0) 3.71Kg/m3 [at the atmospheric boiling point]
Density of ambient air (ρa) 1.2Kg/m3
Wind speed (u) [at an elevation of 10 m] 5.25 m/s [at 3:00 A.M. on the day of incident]

For Cl2 ERPG levels are 3mg/m3 (ERPG-1) 9mg/m3 (ERPG-2) 58 mg/m3(ERPG-3)

Chlorine release scenario leakage from 2mm hole

Liquid chlorine release rate (L) =

1000  Pg
L  9 . 44  10  7  D 2   L   9 .8   h
L
(3)

= 0.126 Kg/s
Flash fraction, FV  C P / H V  (T  T b ) (4)

= 0.22
The amount of material staying in the vapor is five times the quantity flashed.
Therefore,
Airborne Quantity (AQ) = 0.126 Kg/s [Dow’s CEI, AICHE, 1994]

CEI  655 . 1 
AQ
ERPG  2
(5)

6
 = 77.5

6551 
Hazard Distances (HD) = AQ (6)
ERPG

For ERPG-1, HD = 1.3 Km

Similarly, for other ERPG concentration levels HDs are tabulated blow.

Table 3: Hazard distances for different ERPG values

ERPG Conc. Conc. Hazard
3
level Value (mg/m ) Value (ppm) Distance (HD) (Km)
1 3 1 1.3
2 9 3 0.8
3 58 20 0.3

ii. Britter and McQuaid model:

The Britter and McQuaid Model (1988) model uses dimensional analysis to correlate data on dense
cloud dispersion , Since chlorine is heavy gas and the release is in ground level therefore this model
is applicable for the given scenario
Table 4: Determination of dense gas model applicability
For continuous
g ( 0   a ) q   g 0q0  release, uR d  2 . 5
g0  Dc   0   3 
1/ 2 1/3

a  u  u D 
 
x
c
Rd therefore,
x
uR d
2 .5

0.4 > 0.15, So, it is

20.52 0.08 a dense cloud 3600 x  7560
release

Where,
g0 = initial buoyancy factor (m/s2)
Dc = characteristic source dimension for continuous release (m)
q0 = volumetric discharge rate (m3/s)
Rd = release duration (s)
C = effective concentration (volume %)
Cm = original concentration of air-vapor mixture at a particular value of x w.r.t. the initial
concentration of pure chlorine gas C0 (= 1.0), Cm/C0 = C* (assumed)
T0 = source temperature (K) = Tb

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At a given distance , x m from the source , the concentration of the chlorine dense plume can be
determined using the following graph

Fig. 5: Britter-McQuaid dimensional correlation for dispersion of dense cloud plumes[CPQRA, 2000]

Using the above graph the following chlorine dispersion results are tabulated
Table 5: Chlorine concentration at different distances

 
 g 20q0   C 
C
C   1  C  T a / T 0 
x x
   q0 
1/5

 u5   
1/ 2

 
x (m) 0 . 08 Cm/Co = C* C (ppm)
 u  (Vol. fraction)

0.32 5 62.5 0.0750 0.0600 60000

10 125.0 0.0260 0.0200 20000

20 250.0 0.00750 0.0060 6000

30 375.0 0.00320 0.0025 2500

Concentration profile (using Britter and Mc Quaid Model) of chlorine as a function of distance from
the source is represented in Fig.6

x 10
4 Chlorine Concentration vs.Downwind distance
7
Chlorine concentration, C (ppm)

C vs. x (release from 2mm hole at bottom)

6
Model fit

5
3 C=1.66X10 exp(-0.2047x)

0
5 10 15 20 25 30
Downwind Distance , x (m)

Fig 6 : Model fit for Britter-McQuaid result for the release scenario(2mm hole leak)
8
 iii. ALOHA Simulation

Simulation of chlorine release has been done using ALOHA 5.4.1.2. It allows the user a choice of
several accident scenarios, then uses an appropriate source algorithm to inject the material into the air
over a limited time. A flat homogeneous earth surface is assumed. It provides several source points
like Direct, Puddle, Tank etc.

Stability class D is considered for release analysis , Wind direction taken based on windrose
diagram Wind speed = 13.0487 miles/hour from WNW at 10 meters

Ground Roughness: open country

Air Temperature: 30° C Stability Class: D

No Inversion Height Relative Humidity: 61%

Release Duration: ALOHA limited the duration to 1 hour

Concentration profile (using ALOHA simulation) of chlorine as a function of distance from the
source is represented in Fig.7

Fig.7: ALOHA study result showing an effect distances for different levels of concern (2mm hole leak)

9
The Chlorine concentration results are superimposed on geographical location of the point of release
as describe below

Fig.8: Areal view during dispersion showing elliptical cloud

Table 6: Comparison of different simulation method results

Simulation Method Concentration of chlorine (ppm) Chlorine effect distance (Km)

ALOHA 1 1.3

Britter and McQuaid 0.01 0.3

DOW’s CEI 1 1.3

For chlorine liquid release from 2 mm hole at tonner bottom

Britter and McQuaid model is best suited for ground level release of heavy gas for flat
terrain. The open yard area where the chlorine tonners were stored is almost flat and
obstructions are far apart from release point. So, the result obtained from this model is much
more practical than the other two simulation method (ALOHA and DOW’s CEI) used in this
paper. Therefore for the second release scenario we have only considered the Britter and
McQuaid model.

10
 Chlorine Release Scenario 2: Release of chlorine gas from 15 mm tubing connected to
tonner

Chlorine Gas Release Rate Calculation

P trans = transition pressure

Patm = atmospheric pressure (101.325 KPa)

Heat capacity ratio ( k  C P ) = 1.33

Cv

 k  1  k 1
 Patm 
k


 2 
Pt (7)
rans

Ptrans = 187.512 KPa

Ptrans < Pressure inside the tonner, Pa (912 KPa). So, it will be choked/sonic flow.

k 1
 kg M  2  K 1
Wg (sonic)  Cd AP  c  
 RT  k 1
(8)

Cd = discharge coefficient (for gas Cd = 0.85 to 1)

A = release area
Pa = upstream pressure
R = universal gas constant
T = upstream/storage temperature

Using Cd = 0.9,

  15  2
A=   m,
2

4  1000

Pa= (912x103) Pa,

R = 8.314J/mol/K,
T = (30 + 273.15) K
Wg= 0.52 Kg/s

11
Table 7: Determination of dense gas model applicability
g ( 0   a ) q   g 0q0 
g0  Dc   0   3 
1/ 2 1/3
Rd For continuous
a  u  u D  release, uR d  2 . 5
 c 
x
therefore,
x
uR d
2 .5

20.52 0.16 0.5 > 0.15, So, it is 3600 x  7560

a dense cloud
release

Table 8: Chlorine concentration at different distances

 g 20q0  
 
1/5
x (m) x x Cm/Co = C* C (ppm)
 u5   q0 
   
1/ 2
0 . 16
 u 

0.43 10 62.5 0.08500 68000

20 125.0 0.03200 25000

30 187.5 0.01550 12000

50 312.5 0.00725 5700

80 500.0 0.00200 1600

4
x 10
9

8
C vs. x for Chlorine leak from 15 mm gas line
Chlorine Concentration , C(ppm)

7 model fit
6

4 5
C=2.06*10 exp(-0.0893x)
3

0
10 20 30 40 50 60 70 80
Downwind distance , x (m)
Fig 9: Model fit for Britter-McQuaid result for the release scenario (15 mm gas pipe line failure)

3. Probit for (% fatality) Calculations

During ground level dispersion of chlorine it will pose threats like injury and fatalities
depending upon concentration levels and duration of exposure.
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Determination of the percentage fatalities due to the release of chlorine vapour:
For single exposure, the probit (i.e. probability unit) method is suited. An analytical general
form of probit function is,
Y  a  b  ln( C n t e ) (9)
Where,
Y (Probit) = measure of the percentage of the variable resource which sustains injury or
damage
C = chlorine concentration in ppm
te = time of exposure in minutes
The natural logarithmic term in equation [CPQRA, 2000] arises from the fact that in most
populations there are some subjects who can tolerate a rather high level of the harmful
causative factor. Natural logarithm of V fits a normal distribution (i.e. skew).

 [CPQRA, 2000]
The probit equation for fatality due to chlorine release is (given by World Bank (1988)),
Y   5 . 3  0 . 5  ln C 2 .75  t e (10)
Using concentration of chlorine vapour (ppm) for different directly down-wind distances (x
(m)) obtained from dense gas dispersion model (Britter McQuaid), the following probit
calculations have been performed using equation (8) and shown in Table 6 for probits values
of fatalities. Subsequently, it is converted to % of fatality using transformation chart
[CPQRA, 2000] for probits to percentage.
Table 9: Percentage fatality at different down-wind distances

Chlorine conc., Duration of Percentage

x (m) Probit (Y)
C (ppm) exposure (min) Fatality (%)

5 60000 60 11.87 100.0

10 20000 60 10.36 100.0

20 6000 60 8.71 100.0

30 2500 60 7.50 99.4

4. Societal risk assessment

Societal risk is expressed by F-N curve i.e. a plot between frequency (F) of fatality upto N or
exceeding N with the no. of actual fatality for a particular event. For every field there is a
specific risk criterion (F-N curve). If the system risk is within that or upto the criterion then
only it is acceptable. Otherwise system design has to be modified or extra precaution has to
be taken.
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Table 10: Inputs for F-N curve

Failure frequency of 15 mm chlorine gas pipeline

6.5×10-4 / yr.
connected to chlorine tonner (OREDA, 2002 )

Exposure angle at a distance of 30 m from

36° = 36°/360° = 10%
chlorine release point

Probability of wind speed & direction affecting

towards the Land side (based on 2010 wind rose 33%
diagram)

Probability of wind speed & direction affecting

towards the Land side (based on 2010 wind rose 20%
diagram)

Probability of Wind speed and directions are calculated based on the Windrose diagram of
Mumbai for the year 2010

Fig. 10: Windrose Diagram of Mumbai (Source Environmental Data 2010)

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Population density of Mumbai 20500 person/Km2
Maximum affected distance = 100m
Affected area = 3.14× 0.1×0.1/10 = 3.14X10-3 Km2
PPE weightage factor = 0.5
Average probability of death within 100 m = 0.5
Affected Population Land Side= 3.14X10-3 Km2 × 20500×0.5×0.5 person/Km2 = 17 person
Sea Side affected person=3 person (20% of Land side assumed)
Assume only 1% of total population was outdoor

Therefore Land side Probability of Fatality/Year =6.5×10-4  0.33  0.01 =2.14×10-6

Fatality/year

Therefore Sea side Probability of Fatality/Year =6.5×10-4  0.2  0.01 =1.3×10-5 Fatality/year
The Societal risk for Chlorine release for the case study is shown below Fig. 11.

1E-4
Frequency of fatalities , F (per year)

B Chlorine Release Risk

D Acceptable Risk
1E-5 F Tolerable Risk

1E-6

1E-7

1E-8
1 10 100 1000 10000
Number of Fatalities (N)

Fig. 11: F-N curve showing acceptability of risk criteria, ( The red curve with the line is from the tolerable risk
and green line shows risk acceptance criteria and the blue line obtained from chlorine release estimation)

15
From the societal risk (F-N) curve results showed the chlorine risk from the leakage is
well below the acceptance criteria
5. Disaster Management:

Emergency Response made in the incident was the immediate evacuation of the affected
inhabitants from the threat zone. Police and ambulance (was informed at first) made the
rescue and evacuation possible. Fire safety, rescue and relief officials and other experts,
teams from adjacent chemical industries identified, sealed and clamped the leaked cylinders,
National Disaster Response Force (NDRF), other emergency responders neutralized the
process for the remaining chlorine cylinders using caustic soda and water. Mitigation
undergone by NDFR degassed cylinder, dumped 6 cylinders to sea, 100 cylinders cleaned up
and 5 cylinders had residual chlorine and managed 1cylinder which returned to sea shore.
The actual leaked tonner was clamped by NDRF.

6. Conclusion

In this paper chlorine dispersion study has been carried out using ALOHA, DOW’s CEI and
Britter and McQuaid model. From the study, it has been observed that for ALOHA the effect
distance for 1 ppm chlorine concentration is exactly matching with the Hazard Distance using
DOW’s CEI for ERPG-1. However, the Britter and McQuaid model is most suited for the
cases those have been taken care of in this study because of ground level release of chlorine
from tonner and flat terrain for heavy chlorine dispersion. Though it shows that within 100 m
the concentration comes down to negligible range. Actually, it gives the practical value
whereas the other two provides conservative one. Finally, from the trend of chlorine
concentration vs. downwind distance shown in the paper, models have been developed for the
two particular scenarios. Those models follow exponential decay of chlorine concentration
with downwind distance. Finally, as per our analysis the societal risk is acceptable from
Fig.10.

Acknowledgement:

The authors like to thank Shri Lakshman N. Valiveti and Miss Sadhvi Srinivasan for providing
inputs for frequency analysis of the release scenario.

References:

[1] Dow’s Chemical Exposure Index Guide, First Edition American Institute of Chemical
Engineers (AICHE), 1994

[2] Guidelines for Consequence Analysis of Chemical Releases, Centre for Chemical Process
Safety, American Institute of Chemical Engineers, 2000.

[3] Guidelines for Chemical Process Quantitative Risk Analysis, Centre for Chemical Process
Safety, American Institute of Chemical Engineers, 2000

[4] Giby Joseph, Chlorine transfer hose failure, Journal of Hazardous Materials, Volume 115,
Issues 1–3: 119–125(2004)

16
[5] Biswajit Ruj, Pradip Kumar Chatterjee, Toxic release of chlorine and off-site emergency
scenario – A case study, Journal of Loss Prevention in the Process Industries, Volume 25,
Issue 3: 650-653(2012)

[6] Aurélia Dandrieux, Gilles Dusserre, James Ollivier, Small scale field experiments of chlorine
dispersion Original Research Article, Journal of Loss Prevention in the Process Industries,
Volume 15, Issue 1: 5-10 (2002)

[7] Pasquill, F., Atmospheric Diffusion: The Dispersion of Windborne Material From Industrial
and Other Sources, 2nd ed., New York: Halsted (1974)

[8] OREDA, Offshore Reliability Data Handbook, 4th Edition, 2002

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