Results in Engineering 9 (2021) 100202

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Results in Engineering
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Quantitative risk analysis applied to refrigeration’s industry using

computational modeling
Ana Carolina Rosa a, Ivenio T. de Souza a, Alexandre Terra a, Ahmed WA. Hammad b,
Leandro Torres Di Grego
rio c, Elaine Vazquez c, Assed Haddad a, c, *
a
Programa de Engenharia Ambiental, Escola Polit
ecnica da Universidade Federal Do Rio de Janeiro, Av. Athos da Silveira Ramos, 149, Ilha Do Fund~ ao, Centro de
Tecnologia, Bloco D, 21941-909, Rio de Janeiro, Brazil
b
Faculty of Built Environment, UNSW, Sydney, Australia
c
Departamento de Construç~ao Civil, Escola Polit
ecnica da Universidade Federal Do Rio de Janeiro, Athos da Silveira Ramos, 149, Ilha Do Fund~
ao, Centro de Tecnologia,
Bloco D, Sala 207, 21941-909, Rio de Janeiro, Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: Ammonia has been used in refrigeration installations for years. It is a natural refrigerant and is replacing other
Quantitative risk analysis synthetic fluids as it has zero ozone depletion potential and no global warming potential; however, an ammonia
Environmental risk leak in a refrigeration plant can cause damage to the environment and human health as well. Here we evaluate the
Individual risk
quantitative risk analysis of using ammonia in real industrial refrigeration in Rio de Janeiro. This work’s
Societal risk
FN Curves
methodology used PHAST to achieve the assessment model of seven scenarios of ammonia leakage, which allowed
PHAST the understanding of quantitative risk for ammonia leakage. For each scenario, three ammonia concentrations
Industrial refrigeration were simulated, and the gas dispersion distances and their zone of influence were analyzed. Results indicated the
worst scenario reached 2677m and 665m and all accident scenarios showed that individual and societal risk were
above the limit allowed by the Rio de Janeiro environmental agency. To reach the limits tolerable by the agency,
two mitigation measures were proposed, guaranteeing a reduction in ammonia dispersion between 41 and 48%
and 100% for each measure. Although the use of environmentally friendly refrigeration fluid is desired, the
assessment needs to consider individual and societal risks to ensure that it will not affect the facility.

1. Introduction
Ammonia is a chemical substance used in several chemical industry
segments, such as the fertilizer, pharmaceutical, textile, and industrial
refrigeration industries. On the one hand, as a refrigerant, it has several
characteristics that make it extremely attractive. For example, it has
better heat transfer properties, the volumetric refrigerating effect is
higher than other fluids with similar vapor pressure, and has no ozone
depletion potential (ODP) and extremely lower GW. On the other hand, it
is toxic and combustible [1]. Besides, because it is a natural and envi-
ronmentally friendly refrigerant, ammonia has been used to substitute
halogenated hydrocarbons refrigerants such as CFC, HCFC, and HFC. The
first one had been banned under Montreal protocol (1987), and the other
two have been phased out as stipulated by the Kyoto Protocol (1997). For
those reasons, researchers have been studying alternative refrigerants [2]
and ammonia has widespread use as a refrigerant fluid in medium and
large food, beverage, and preservation industry [3]. Due to its small
molecular structure and molecular strength between molecules, it can
easily spread when released into the environment [4]. The leakage and
dispersion of ammonia can cause the surrounding population’s poisoning
and result in severe environmental pollution [5]. Despite being an
environmentally friendly refrigerant, it can cause massive damage to the
environment and human health if an accidental release occurs. Thus, it is
essential to develop a quantitative risk assessment (QRA) of the risk of
ammonia leakage in refrigeration installations.
The release and dispersion of ammonia have been studied frequently.
It mainly focuses on the toxic gas leakage and dispersion model, espe-
cially since it is one of the replacement refrigerants for the current
halogenated hydrocarbons fluids used, HCFC and HFC [6,7]. According
to Pandya et al. [7], the dispersion models can be classified into three

* Corresponding author. Departamento de Construç~ao Civil, Escola Polit
ecnica da Universidade Federal Do Rio de Janeiro, Athos da Silveira Ramos, 149, Ilha Do
Fund~
ao, Centro de Tecnologia, Bloco D, Sala 207, 21941-909, Rio de Janeiro, Brazil.
E-mail addresses: carolinarosa@poli.ufrj.br (A.C. Rosa), ivenio@poli.ufrj.br (I.T. de Souza), alexandreterra@poli.ufrj.br (A. Terra), a.hammad@unsw.edu.au
(A.WA. Hammad), leandro.torres@poli.ufrj.br (L.T. Di Greg
orio), elainevazquez@poli.ufrj.br (E. Vazquez), assed@poli.ufrj.br (A. Haddad).

https://doi.org/10.1016/j.rineng.2021.100202
Received 18 November 2020; Received in revised form 8 January 2021; Accepted 11 January 2021
2590-1230/© 2021 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
A.C. Rosa et al.
main categories, ranging from less to more complex: Gaussian models,
integral-type models, and 3D or computational fluid dynamics (CFD)
models. The first one is based on the diffusion equation and observations
in experimental studies. The second one is a simplification of the con-
servation equations for mass, momentum and energy. ALOHA (Areal
Locations of Hazardous Atmosphere), DEGADIS (DEnse GAs DISpersion),
HEGADAS, and PHAST (Process Hazard Analysis Software Tool) are the
most popular dispersion integral-type models and widely used in safety
engineering applications, which provide relatively easy and fast disper-
sion estimations. The last one has been developed for years and allows
the users to have a three-dimension analysis. Some standard CFD codes
are CFX, FLACS, FDS, and FLUENT [7].
Among all the models presented, ALOHA, PHAST and CFD codes are
the most commonly used to study the gas dispersion. Orozco et al. [8]
used ALOHA to quantify the effects of ammonia release and the results
showed the worst scenario was the toxic vapor cloud. For instance, Zhang
et al. [9] combine scenario set and computational fluid dynamics (CFD)
to evaluating the individual risk due to the ammonia release. Rajeev et al.
[10] evaluated and mapped the population vulnerability using the
ALOHA software package and geographical information system (GIS).
PHAST is a software that gathers a set of comprehensive models and
allows the study of an accident sequence. It analyzes from the release of
chemical material to the explosion and/or the toxic dispersion. Although
it does not require large amounts of input data and calculation time is not
time-consuming, it still generates the required data and information for
evaluating the risk and safety [11]. PHAST software is among the most
popular and widely used in safety engineering applications. Besides, it is
one of the most comprehensive computer programs for modeling acci-
dental releases, used by companies and the competent authorities [7].
Many researchers have been using it to predict the gas dispersion of
hazardous material. For instance, Zhang et al. [12] used PHAST to study
the dispersion and toxic effect of liquefied ammonia in the case of an
instantaneous release. Qu et al. [13] also adopted PHAST to analyze the
liquefied ammonia leakage accidents quantitatively. However, in both
works, it was evaluated only one scenario of leakage in a tank filled with
ammonia.
In order to achieve a quantitative risk analysis, many researchers and
engineers have been adopting the QRA method. It is a common tool used
for planning and approval of high-risk process facilities globally. The
QRA results are analyzed using individual risk contours and societal risk
contour or F–N curve [14]. Avasthy and Siddiqui [15] estimated the risk
of fatality due to an operational ammonia loading facility surrounded by
a residential population. Although this study considers the risk contours,
it only considers three scenarios with one ammonia concentration for
each one. Zolt
an et al. [16] discussed the potential threats posed by
ammonia in cold storage facilities and described an example of a po-
tential event involving ammonia dispersion and depicts it on a map
together with the solution. Nevertheless, this work did not evaluate the
risk contours effectively.
This article aims to feature a quantitative risk analysis (QRA) method
in industrial facilities with toxic gas release hazards that combine the
scenarios and PHAST software. Based on the subject matter experts
(SME’s) opinions, seven potential equipment failures, and toxic gas
release scenarios are constructed. The individual and societal risk of each
release scenario are estimated. Furthermore, three ammonia concentra-
tion levels are simulated, and the dispersion features and impacted dis-
tance of ammonia are predicted. These outcomes are compared with the
tolerable limits from the regulator agency – environment state institute
(INEA) – in Rio de Janeiro. Besides, we propose mitigation measures to
reduce the distance of ammonia dispersion and reduce individual and
societal risk. In this study, a real case of a cold storage unit containing
ammonia as refrigerant fluid is provided to illustrate this method. A food
factory industry located in an industrial area at Campos, Rio de Janeiro,
Brazil, is selected as an empirical field of application.
This article aims to fill the gaps found in other articles and provide a
complete analysis of a real industrial facility, which uses ammonia as a
2
Results in Engineering 9 (2021) 100202
refrigerant. This article’s novelty is the quantitative analysis of ammonia
throughout the refrigeration process, which takes into account different
incident scenarios and three levels of ammonia concentration.
2. Theoretical foundation
Ammonia is a chemical material composed of one nitrogen atom and
three hydrogen atoms, represented by the chemical formula NH3. Ac-
cording to Reyes [17], ammonia has chemical advantages for its use in
refrigeration installations due to its light molecular weight (17.03 g), low
boiling point (
28  F), and high latent heat of vaporization (1371.2 J).
Another advantage is that many researchers have studied ammonia since
the 19th century, which provides a vast domain over its properties and
management experiences.
According to the document provided by the INEA [18], ammonia
qualifies in almost all concepts of a good refrigerant gas despite its
toxicity. The main concepts that make a gas a good refrigerant are shown
in Table 1.
To facilitate the transport and storage of ammonia, it is pressurized to
achieve the state of liquefied ammonia. When a leakage occurs, the liq-
uefied ammonia is quickly vaporized. Ammonia in its gaseous state is not
flammable, but if it is in large quantities and the presence of an intense
energy source, it can be ignited and cause an explosion. However, the risk
of flammability of ammonia manifests itself only in extreme fire condi-
tions and in confined places. Additionally, if in contact with water, an
exothermic reaction is produced, producing heat that, in contact with
other gases, can cause fire or explosion. It has toxic characteristics con-
cerning human health if inhaled, causing burns and severe injuries to the
skin and eyes. Therefore, an ammonia leakage can have serious conse-
quences depending on the concentration released and the extent of the
vapor cloud.
Although ammonia is not considered a flammable substance, con-
centrations in a volume of around 15% and 28% can form a flammable
mixture capable of igniting or exploding [7]. Ammonia vapor is difficult
to be ignited in the air atmosphere because of its high Minimum Ignition
Energy (MIE ¼ 680 mJ) [4]. However, the presence of oils or other
combustible materials increases the risk of fires and explosions.
Furthermore, ammonia is toxic, combustible, possesses a pungent odor
and aggressiveness to copper alloy [1]. However, compared to other
refrigerants, ammonia presents no damage to the ozone layer and does
not intensify the greenhouse effect.
Regarding the toxicity, the regulatory agency argues that ammonia is
a base with many affinities for water, which can cause irritating effects on
the eyes, skin, respiratory tract, and mucous membranes of the nasal
passages and lungs. Nevertheless, ammonia has a powerful characteristic
odor, making it easy to recognize when breathed by humans. Small
concentrations starting at 10 ppm, ammonia is already noticeable. In the
ranges between 150 and 400 ppm, it already causes irritation and
discomfort in the nasal mucous membranes, and it is very toxic in con-
centrations above 1500 ppm and can destroy tissues of the nasal cavities.
The biggest concern of companies that use ammonia as a refrigerant
should be related to leaks that trigger the formation of toxic clouds, and
that can cause explosions. According to INEA, the most common causes of
accidents are failures in the design of the cooling system and damage to
the equipment caused by heat, corrosion, and vibration, as well as due to
Table 1
Main characteristics to be a refrigerant.
1 Be volatile
2 High latent heat of evaporation
3 Have a minimum of power for its compression at condensation pressure
4 Display critical temperature well above the condensation temperature
5 Produce relevant refrigeration for a given volume of steam
6 Have a reasonable cost
7 Exist in abundance for its commercial use
8 Enable leaks to be detectable
A.C. Rosa et al.
Table 2
Main causes of ammonia leakage.
1 Inadequate supply of vessels
2 Relief valve failure
3 Damage to equipment or accessories, caused by external impact from mobile
equipment, such as forklifts
4 External corrosion, faster in conditions of high heat and humidity, especially in
the low-pressure portions of the system
5 Internal cracks in the vessels, which tend to occur at or near the weld points
6 Trapping of liquid inside the pipes, between shut-off valves
7 The excess liquid inside the compressor
8 Excessive vibration in the system, which can lead to premature failure
improper maintenance or lack of maintenance of its components, such as
relief valve pressure, compressors, condensers, pressure vessels, purging
equipment, evaporators, pipes, pumps and instruments in general. INEA
lists some of the causes that usually generate ammonia leaks, as shown in
Table 2.
Ammonia has an ODP and GWP corresponding to zero, which means
no damage to the ozone layer or contribution to global warming.
Therefore, ammonia is an ideal gas to be used in refrigeration systems
considering only the environmental risk requirements.
3. Methodology
The work methodology adopted in this study is composed of four
phases, as indicated in Fig. 1. As an initial step, the refrigeration plant’s
installation and process need to be specified by analyzing its constructive
and operational aspects. Besides, the vicinity description is also essential
to identify any aspect that may interfere in any accidental scenario.
The second step herein is the identification and description of the
accidental scenarios of ammonia leakage. After completing the hazards
identification step, in the third step, a criterion must be established for
selecting accidental hypotheses that will be studied in detail in the next
steps of the AQR. The criterion must be established, considering the
severity of the damage resulting from the identified failure. The selected
accidental hypotheses will be studied in terms of their consequences, that
is, their impacts and damages caused due to a possible materialization of
the accidental scenarios. This part is performed by using Probit function
that it defines the ammonia concentration that will reach the probabili-
ties of 1% and 50% of deaths. Then, due to the complexity of the cal-
culations involved, PHAST’s computational models are run in order to
estimate the consequences of accidental scenarios. In this part, it is
Fig. 1. Work methodology.
3
Results in Engineering 9 (2021) 100202
possible to observe the effects and the vulnerability of the region when it
is exposed to a toxic cloud. The estimation of the frequencies of the
accidental scenarios requires the use of frequency calculation methods
and models. This study is based on the use of the event tree and
component failure rates in accidental scenarios.
The last step consists of calculating and comparing the risk with the
previously established criterion. The risk assessment results are
expressed in terms of individual risk (IR) and societal risk (SR), which are
compared with the limit required by the Rio de Janeiro environmental
agency, INEA. Its guidance for risk analysis [19] establishes a method to
develop a risk analysis study. The development of a quantitative risk
assessment in terms of IR and SR is based on the relation between the
inventory of toxic material and the distance to a residential area. The
final project must exhibit lower IR and SR; if either fails, mitigation
measures must be proposed [14].
In this work, we analyzed seven possible scenarios of ammonia
leakage in a refrigeration installation in Rio de Janeiro and evaluated the
extent of dispersion of the generated ammonia plume, the societal and
individual risk. We used PHAST Risk software (version 7.01) to assess
these scenarios’ effects and evaluate the region’s vulnerability around
the refrigeration installation.
3.1. Estimation of consequences
Estimation of consequences considers the impact analysis, which is
applied to estimate the potential for damage or injury from specific ac-
cidents. It allows calculating human exposure to a cloud of toxic gas.
Then, outcomes can be compared with guidelines or standards to esti-
mate the probability of harm to an exposed individual or population. The
probability of fatality is calculated using the appropriate probit function
to estimate the probability of damage for each exposure type.
Probit functions (Equation (1)) exist for almost any hazardous
chemical but are typically available for thermal radiation, toxic gas
release, and blast overpressure effects. It estimates the percentage of
injured persons living in the impacted areas [8]. In this study, the
probability of fatality is calculated using the appropriate Probit function,
described as [20]:
Y ¼ K1 þ K2 :ln ðC n :tÞ (1)
Where Y is the value corresponding to the probability of death; C is the
concentration of the toxic material (ppm); t is the time of exposure
A.C. Rosa et al.
(minutes); and n, K1, K2 are constants, which are exclusive and depend
on the type of chemical substance evaluated.
In this study, the equation finds the concentration of ammonia that
will reach the points with a probability of 1% and 50% of deaths around
the refrigeration plant.
3.2. Estimation of frequencies
Frequency estimation of accidental scenarios can be obtained either
from historical records made available by SME’s or from analyzes of
previous accidents. This direct technique provides the incident frequency
for the main event without the need for detailed frequency modeling.
However, most accidents analyzed in an AQR are so rare that it is
necessary to use frequency calculation methods and models.
Event trees are typically used in risk assessment studies to quantify
the frequency of different possible scenarios. It consists of a technique to
analyze the consequences of an unwanted event by describing the tem-
poral sequence of the facts. To determine the frequency estimation of a
final event’s occurrence, it is necessary to perform the product of all the
probabilities of the branches previously covered. Therefore, a simple
event tree of the refrigeration plant was developed to calculate the fre-
quency of accidental scenarios related to the ammonia release. This work
used the equipment failure rates to calculate the frequency of initiating
events, as shown in Table 3.
3.3. Estimation of individual and societal risk
Individual risk (IR) is defined as the probability of death per year if an
individual is exposed to a hazard in the vicinity of an installation [10,22].
IR is a useful criterion to understand and manage the risk for a specific
person or group of people according to the geographic location of the
source of the toxic substance released and the people around the facility.
The total individual risk at a geographic location close to an industrial
plant with coordinates x, y assumes that is equal to the sum of the indi-
vidual risks at that point. Then, this information is used to generate in-
dividual risk contours. According to CCPS [23], the total individual risk
can be calculated by Equation (2) and Equation (3):
X
n the separator vessel at a temperature of
35  C (V-03). From the sepa-
IRx;y ¼ IRx;y;i (2)
i¼1
Where, IRx;y is the total individual risk of fatality at a geographic location
x, y and IRx;y;i is the individual risk of fatality at geographic location x, y
from the scenario i; n is the total number of individual outcome scenarios
selected for analysis.
The inputs to Equation (2) are obtained from Equation (3):
IRx;y;i ¼ fi :pf ;i (3)
Where, fi is the frequency of each incident and pf ;i is the probability of the
incident that will result in fatality.
Societal risk considers the individual risk to estimate the population
density around the source of the released hazardous material. Its signif-
icance is in describing the severity of the accident, showing the rela-
tionship between the accumulated probability and the expected number
of deaths, the number of people affected for each of the risk areas. The
societal risk is usually represented by F–N curves, which is a type of risk
indicator that plots the variables F (annual frequency of accidents
involving n and more fatalities) and N (the number of fatalities) in a two-
Table 3
Equipment failure rate [21].
Equipment Failure rate
Vessel 2  10
6
Pipe 3  10
7
4
Results in Engineering 9 (2021) 100202
dimensional coordinate system to express the relationship between them.
Usually, risk curves are shown in a log-log plot with the annual frequency
on the ordinate axis and the number of fatalities on the abscissa axis [24,
25]. To assess the severity of fatal accidents in ammonia leakage, the
most commonly used method is to plot the F–N curve, showing the
relation between the accumulated probability and the number of deaths,
which can be provided as follows [26]:
Z∞
1
FN ðxÞ ¼ PðN > xÞ ¼ fN ðxÞdx (4)
x
Where, fN ðxÞ is the probability density function of the annual fatalities;
FN ðxÞ represents the cumulative probability distribution function of the
annual fatalities, representing the probability of less or equal to x fatal-
ities per year. In real-world practice, the probability of accidents is usu-
ally replaced by the frequency, and the accidents are grouped according
to the number of deaths.
4. Case study
This work’s case study is a refrigeration installation located in Rio de
Janeiro, whose refrigerant used is ammonia. The installation is located
500 m west of a populated area with a population uniformly distributed
over 452 occupations, including residential occupations and small com-
mercial establishments. Therefore, this work aims to assess individual
and societal risks given seven scenarios of liquefied ammonia leakage. To
estimate the number of people present in the vicinity of the facility, this
work considered the presence of 3.24 inhabitants per residence in the
studied region.
4.1. System description
Fig. 2 shows the process diagram of the refrigeration installation
using ammonia as the refrigerant fluid. The main reservoir (V-01) has a
storage capacity of 7700 L of NH3. The flow of NH3 in the liquid phase
leaves the main reservoir and then feeds the separator vessel at a tem-
perature of
10  C (V-02) and the intermediate cooler, which will supply
rator vessels, the liquefied ammonia is pumped into the rooms of
refrigerated products at
10  C and frozen products at
35  C. After the
heat exchange between the ammonia and the rooms, NH3 returns to the
separator vessels. From the separator vessels, NH3 is aspirated into the
compressor system, consisting of two compressors for the system with a
temperature of
10  C and two for the system with a temperature of
35

C. Then, NH3 leaves the compressors and is sent to the condensation
system composed of one condenser. Finally, NH3 leaves the condenser,
goes to the cooling tower, and then returns to the main reservoir.
4.1.1. Accidental scenarios and weather conditions
As stated previously, seven accidental scenarios were defined based
on the opinions of SME’s. SME’s is made up of refrigeration plant workers
with experience in the refrigeration system. Table 4 shows the accidental
scenarios taking into account the different failure modes in the cooling
system. In typical cases, accidental release of ammonia is usually due to
releases in vessels, such as continuous leakage or catastrophic ruptures
[22,27] or due to broken pipe or equipment, and so on [28]. It is assumed
that ammonia escapes into the atmosphere in different situations in all
scenarios, i.e., ammonia leaks due to rupture of the vessel or hole-
s/rupture in the pipe or equipment. Furthermore, when an accident oc-
curs, it is assumed that 100% of the amount of ammonia in the pipes or
vessels is released into the atmosphere.
To run the PHAST software, each leak scenario can be defined by the
amount of hazardous substance, storage pressure, hole diameter, the
height of the leak, and weather conditions. Therefore, a large number of
release scenarios can be generated by varying these parameters [29].
A.C. Rosa et al. Results in Engineering 9 (2021) 100202

Fig. 2. Process flow diagram of the installation.

Table 4 Table 6
Accidental scenarios considering different modes of failure in the refrigeration Weather conditions.
plant. Air Temperature 23.7  C
1 NH3 leakage in the path between the condenser and the main reservoir
Atmospheric Pressure 1 atm
2 NH3 leakage in the main reservoir (V-01)
Humidity 79.1%
3 NH3 leakage in the separator vessel (V-02)
Wind speed 2.0 m/s
4 NH3 leakage in the separator vessel (V-03)
5 NH3 leakage in the path between the main reservoir and the separator vessels (V-
02 and V-03)
6 NH3 leakage in the path between the separator vessel (V-02) and the room of
dispersion of toxic gas over a greater distance from the release source.
refrigerated products
7 NH3 leakage in the path between the separator vessel (V-03) and the room of 4.1.2. Ammonia concentrations
frozen products This work takes into account three ammonia concentration levels.
The first level corresponds to the concentration Immediately Dangerous
to Life or Health (IDLH) that, according to the National Institute for
Table 5 presents the seven potential accident scenarios with ammonia
Occupational Safety and Health (NIOSH), is 300 ppm. The other two
leakage. In each scenario, the conditions are specified, which was later
levels consider the probabilities of death of 1% and 50% of the popula-
inserted into PHAST to perform the modeling. The calculation of the
tion around the installation for 30 min of exposure. Table 7 shows the
mass of ammonia released took into account some factors, such as the
ammonia concentration levels for IDLH and the death probabilities of 1%
volume within the line (scenario 1), the total volume of the main reser-
and 50%. We evaluated a scenario of a toxic cloud formation after the
voir V-01 (scenario 2–5) or the volume of the separator vessel V-02 and
V-03 (scenario 6–7).
Then, as previously indicated in the flowchart (Fig. 2), the individual Table 7
risk (IR) around the installation needs to be estimated after selecting the Ammonia concentration levels.
scenarios. PHAST software was used to calculate the population’s CODE Type Conc. Conc. Scenario Effect
vulnerability levels if one of the seven release scenarios occurred. (mg/ (ppm)
m3 )
The meteorological input for the modeling was made using the
average of climatological data gathered from Campos meteorological A IDLH – 300 Toxic cloud Toxic
station and is depicted in Table 6. Dispersion calculations are executed B Death 1.693 2.435 formation concentration
Probability
assuming a stability class D. The stability classes are based on Pasquill’s
1%
six stability classes, classes A to F, to depict different atmospheric tur- C Death 5.428 7.807
bulence levels [30]. In this study, class D characterizes a condition of Probability
neutral stability, which means that the wind turbulence may cause 50%

Table 5
Parameters to define the mass of ammonia released from each accident scenario.
Parameter Accidental scenarios

1 2 3 4 5 6 7

Physical state Saturated liquid Saturated liquid Subcooled liquid Subcooled liquid Saturated liquid Subcooled liquid Subcooled liquid
Pressure (kgf/cm2) 18 18 15.69 15.69 18 18 18
Temperature ( C) – –
10
35 –
10
35
Leak height (m) 3 1 1 1 3 3 3
Pipeline diameter (in) 5" – – – 1 ½” 2 ½” 2”
Volume (m3) 0.38 3.86 3.86 3.86 3.86 1.4 1.4
Released ammonia (kg) 215 2185 2185 2.185 2185 2185 2185

5
A.C. Rosa et al. Results in Engineering 9 (2021) 100202

Table 9
Distances reached by three ammonia concentrations.
N Accidental events Distances (m)

A B C

1 NH3 leakage in the path between the condenser and 440 292 241
the main reservoir
2 NH3 leakage in the main reservoir (V-01) 643 299 174
3 NH3 leakage in the separator vessel (V-02) 674 321 219
4 NH3 leakage in the separator vessel with (V-03) 772 195 137
5 NH3 leakage in the path between the main reservoir 845 534 400
and the separator vessels (V-02 and V-03)
6 NH3 leakage in the path between the separator vessel 2677 665 428
(V-02) and the chamber of refrigerated products
7 NH3 leakage in the path between the separator vessel 2034 518 302
(V-03) and the chamber of frozen products

Table 10
Distances corresponding to the individual risk.

Fig. 3. Ammonia leakage event tree. Individual risk (/year) Distance (m)

1.00 E
05 479

Table 8 1.00 E
06 644
1.00 E
07 667
Ammonia release frequency estimation.
Accidental scenarios Frequency

1 3.38 E
06
2 7.50 E
07
3 7.50 E
07
4 7.50 E
07
5 1.13 E
05
6 5.63 E
05
7 5.63 E
05
ammonia leakage inside the plant for each level. The physical effect
developed is the toxic concentration of this cloud that can lead to death if
the population is exposed for a long time.
4.1.3. Ammonia dispersion frequencies
The frequency of occurrence of accidental scenarios was estimated by
applying the event tree technique (Fig. 3). The estimation is made from
the composition of the frequency of occurrence of the initiating events
and the different possibilities for the evolution of accidents. The fre-
quency estimation takes into account the equipment failure rate and the
wind direction towards the residential area. Table 8 shows the frequency
estimation of accidental scenarios.
5. Results and discussion
5.1. The distance achieved of the ammonia cloud
probability of an individual death located in the influence area of the
accidental scenarios’ effects postulated. The calculation of each acci-
dental scenario’s contribution to the total individual risk related to the
release of ammonia was made based on the results obtained previously
for its frequency of occurrence and the reach of the levels of physical
effects corresponding to the different probabilities of people death
exposed.
Table 10 presents the calculated distances that correspond to the in-
dividual risk levels with one order of magnitude variation. The individual
risk profile achieved is shown in Fig. 4. The refrigeration installation’s
respective iso-risk contours are illustrated, where the projection of the
iso-risk contours was elaborated from the machine room since this area is
associated with the most critical accidental scenarios.
The observation of the iso-risk contours indicates that the individual
risk level of 1.00 E
06/year, considered by INEA as the tolerable limit
for new installations, reaches sensitive residential occupations around
the installation.
As previously indicated, the calculation of societal risk is made from
the frequency of each accidental scenario and the estimate of the number
of deaths among the exposed population. The results are presented in an
F–N curve, which provides the cumulative frequency of accidents with N
or more fatalities. The estimate of the number of deaths among the
population exposed to these scenarios’ effects was based on the estimate
of the number of people present in the installation surroundings.

Based on the data presented above, accidental scenarios were char-

acterized by modeling and calculating the scope of the harmful physical
effects of a toxic ammonia cloud. Table 9 shows the distances reached by
the ammonia concentrations specified for the accidental scenarios
postulated.
From the analysis of the results, it can be seen that the greater range of
lethal concentrations is related to the occurrence of ammonia release in
the section between the separator vessel containing liquid ammonia at

10  C and the cold rooms due to a hole or a line break, scenario 6. In this
case, the level of ammonia concentration corresponding to the 1%
probability of fatality of the exposed population reaches 665 m, and 50%
of fatality reaches a distance of 428 m.
It appears that there are sensitive occupations within the rays of the
cloud for the different levels of ammonia concentration.

5.2. Individual and societal risk

As previously stated, the individual risk (IR) reflects the annual Fig. 4. Individual risk profile achieved.

6
A.C. Rosa et al. Results in Engineering 9 (2021) 100202

an accident due to the ammonia release that would cause more than the
number of victims. The graph’s observation shows that the curve repre-
senting the societal risk is located above the acceptability limit for new
installations, according to the criterion adopted by INEA.

5.3. Risk tolerability

Fig. 5. F–N curve plotted for the model selected.
The estimated number of deaths was obtained by considering the
following probabilities:
 75% probability of death for people located in the area corresponding
to the perimeter of the circle, for each direction considered, delimited
by the scope of the concentration regarding the probability of death of
50% of the exposed population;
 25% probability of death for people located in the area corresponding
to the circle perimeter, relative to each direction considered,
delimited by the range of concentrations referring to the probabilities
of death of 50% and 1% of the exposed population.
Fig. 5 shows the respective F–N curve. The horizontal axis shows the
number of deaths and the vertical axis shows the probability per year for
Fig. 6. Iso-risk curve concerning to distance of 644 m
The calculation of the individual risk indicated that the level of 1.00
E
06/year, considered by INEA as the limit of acceptability for new
installations, reaches areas with the presence of sensitive residential
occupations. The calculation of societal risk indicated that the accept-
ability limit considered by INEA for new installations is exceeded. Fig. 6
illustrates the 1.00 E
06/year radius plotted in Google Earth for the
refrigeration plant. Therefore, due to individual and societal risks, it will
be necessary to reassess the risks after the implementation of preventive
and mitigating measures.
5.4. Mitigating measures
After investigating the distances reached by the toxic ammonia cloud,
two mitigating measures were proposed to reduce the extent of the
cloud’s radius of influence over the habitable part near the installation
boundary. The first mitigation measure (MM1) represents the imple-
mentation of leak containment valves. Table 11 shows the seven possible
scenarios of ammonia release accidents with the implementation of the
MM1 measure. For the elaboration of these scenarios, some factors were
considered, such as the release pressure, the amount of total ammonia
and ammonia released.
The pressure of release of the toxic ammonia cloud took into account
the shutdown of pumps and compressors, reaching a value of 1 kgf/cm2.
The total ammonia amount was considered the total mass of ammonia in
the refrigeration system, which corresponds to 3700 kg. To calculate the
ammonia released in each scenario, the volume quantity was calculated
according to the specifications of the pipeline and the vessels’ size.
After describing the new scenarios with the implementation of MM1,
the new toxic ammonia clouds were modeled, and the distance reached
by each of the scenarios was obtained, as can be seen in Table 12. From
the analysis of the results, it can be seen that the greater range of lethal
concentrations after MM1 is related to the occurrence of NH3 (l) release
in the section between the separator vessel at
10  C and the cold rooms
due to a hole or line break. In this case, the ammonia concentration level
corresponding to the 1% probability of fatality of the exposed population
reaches a distance of 395 m, and the 50% fatality reaches a distance of
255 m. The presence of sensitive occupations is verified within the
ammonia concentration levels’ reach after the implantation of MM1.
The second mitigation measure 2 (MM2) consists of enclosing the
installation using a gas abatement system. After the implementation of
MM2, the accidental scenarios were remodeled. Some premises were
considered for the application of MM2, such as shed dimensions of 9000
m3, exhaust rate of 3000 m3/h, exhaust fan diameter of 1200 , exhaustion
of the absorption tower for the abatement system, and the release of the
ammonia will only occur if the abatement system fails. As in applying the
first mitigating measure, Table 13 presents the properties considered for

Table 11
Parameters to define the mass of ammonia released from each accident scenario applying MM1.
Parameter Accident scenarios
1 2 3 4 5 6 7
Physical state Saturated liquid Saturated liquid Subcooled liquid Subcooled liquid Saturated liquid Subcooled liquid Subcooled liquid
Initial Pressure (kgf/cm2) 18 18 15.69 15.69 18 18 18
Release Pressure (kgf/cm2) 1 1 1 1 1 1 1
Temperature ( C) – –
10
35 –
10
35
Pipeline Diameter (in) 5" – – – 1 ½” 2 ½” 2”
Ammonia available for release (kg) 3700 3700 3700 3700 3700 3700 3700
Volume (m3) 0.38 3.86 1.4 1.4 0.114 1.57 1.00
Released Ammonia (kg) 215 2185 910 954 64.5 1023 684

7
A.C. Rosa et al. Results in Engineering 9 (2021) 100202

Table 12 Table 14
Distances reached by three ammonia concentrations applying MM1. Distances reached by three ammonia concentrations applying MM2.
N Accidental events with MM1 Distances (m) N Accidental events with MM2 Distance (m)

A B C A B C

1 NH3 leakage in the path between the condenser and 440 292 241 1 NH3 leakage in the path between the condenser and the 17 – –
the main reservoir main reservoir
2 NH3 leakage in the main reservoir (V-01) 545 229 136 2 NH3 leakage in the main reservoir (V-01) 155 48 27
3 NH3 leakage in separator vessel (V-02) 407 188 130 3 NH3 leakage in separator vessel (V-02) 149 46 28
4 NH3 leakage in separator vessel with (V-03) 34 20 16 4 NH3 leakage in separator vessel with (V-03) 147 45 28
5 NH3 leakage in the path between the main reservoir 290 193 154 5 NH3 leakage in the path between the main reservoir and 139 41 26
and the separator vessels (V-02 and V-03) the separator vessels (V-02 and V-03)
6 NH3 leakage in the path between the separator vessel 1474 395 255 6 NH3 leakage in the path between the separator vessel (V- 137 40 26
(V-02) and the chamber of refrigerated products 02) and the chamber of refrigerated products
7 NH3 leakage in the path between the separator vessel 237 77 35 7 NH3 leakage in the path between the separator vessel (V- 136 40 26
(V-03) and the room of frozen products 03) and the room of frozen products

modeling in PHAST using MM2. Table 15

Table 14 shows the distances reached by the toxic ammonia cloud for Distances corresponding to individual risk levels applying MM1 and mitigation
the accidental scenarios postulated considering the abatement system’s percentage.
failure. From the analysis of the results of the distances reached with the Individual risk (/year) Distance (m) Mitigated risk (%)
implementation of MM2, it was found that the greatest reach of the level 1.00 E
05 251 48
of ammonia concentration corresponding to the 1% probability of fatality 1.00 E
06 382 41
of the exposed population (B) reaches the distance of 48 m and 50% 1.00 E
07 396 41
fatality (C) reaches a distance of 28 m. With this, it appears that there is 1.00 E
08 479 100
no presence of sensitive occupations within the rays of reach of the levels
of ammonia concentration.

5.5. Reassessment of individual and societal risk with MM1 and MM2
measures

After implementing the mitigating measures MM1 and MM2, the in-
dividual and societal risks were reassessed considering the imple-
mentation of these measures in the refrigeration system. Table 15
presents the distances corresponding to the individual risk levels with an
order of magnitude variation and their percentages related to the amount
of risk mitigated by MM1. It can be seen that the individual risk profile
shown in Fig. 7 is in a certain part above the level of tolerance adopted by
the environmental agency in Rio de Janeiro. The observation of the iso-
risk contours indicates that the individual risk level of 1.00 E
06/year,
considered by INEA as a limit of acceptability for new installations,
reaches sensitive occupations around the installation.
A new model for societal risk was made according to the accidental
scenarios’ frequencies implementing the MM1 measure. The number of Fig. 7. Individual risk profile applying MM 1.
deaths estimation was made from the number of people present in the
range of accidental scenarios, considering the probabilities of 25% and tolerance criterion adopted by INEA. Comparing the individual risk
75%. Fig. 8 shows the respective F–N graphs with the implementation of profile, it is observed that it is well below the adopted criterion of 1.00
MM1. The graph’s observation shows that the curve representing the E
06; the limit of acceptability for new installations was not reached.
societal risk is located below the acceptability limit for new installations, Therefore, the percentage of mitigation for the values found in the in-
according to the criterion adopted by INEA. The calculation of societal dividual risk’s initial profile was 100%. The societal risk after MM2 was
risk after MM1 indicated that the acceptability limit considered by INEA not calculated due to the absence of sensitive occupations within reach of
for new installations is not exceeded. toxic ammonia clouds.
After the implementation of MM2, the individual risks were reas- This work carried out an ammonia leak QRA based on three different
sessed and are shown in Table 16, which presents the distances corre- concentrations of it and took into account the individual and societal risk
sponding to the individual risk levels with an order of magnitude as indicators of the level of risk that the population near the area of the
variation. Fig. 9 presents the individual risk profile with MM2 and the

Table 13
Parameters to define the mass of ammonia released from each accident scenario applying MM2.
Parameter Accident scenarios

1 2 3 4 5 6 7

Physical state Saturated liquid Saturated liquid Subcooled liquid Subcooled liquid Saturated liquid Subcooled liquid Subcooled liquid
Initial Pressure (kg/cm2) 18 18 15.69 15.69 18 18 18
Temperature ( C) – –
10
35 –
10
35
Pipeline Diameter 5" – – – 1 ½” 2 ½” 2”
Ammonia available for release (kg) 3700 3700 3700 3700 3700 3700 3700
Released Ammonia (kg) 3700 3700 3700 3700 3700 3700 3700

8
A.C. Rosa et al. Results in Engineering 9 (2021) 100202

latter only took into account the toxic effect distances of three concen-
trations of ammonia. Although Zolt
an et al. [16] described an example of
a potential accident involving ammonia in a cold-storage facility, their
work did not perform a complete quantitative risk analysis. This study
presented the advantage of analyzing a greater number of accident sce-
narios and three ammonia concentrations to assess the effects of toxic
cloud dispersion, which demonstrated that the toxic ammonia cloud
reached the residential area without mitigating measures.
In this study, it was proposed two mitigating measures, which are
based on a preliminary risk analysis carried out by SME’s in refrigeration
plants. Both are common measures and easily achievable by Brazilian
companies that use some type of gas in their process. The proposed
mitigating measures aimed to reduce the IR and SR. If the SR is above the
intolerable boundary, it is necessary to adopt measures to reduce the risk.
The responsible environmental agency - INEA defines the limits of both
Fig. 8. F–N curve graph applying MM1. IR and SR. Observation of the iso-risk contours indicates that the indi-
vidual risk level of 1.00E-06/year, considered by INEA as the limit of
acceptability for new installations, reaches the residential area. If there is
Table 16
any sensitive occupation within the 1.00E-06/year iso-risk boundary, the
Distances corresponding to individual risk levels applying MM2 and mitigation
percentage.
risk is considered unacceptable by INEA, and measures to reduce the risk
are mandatory.
Individual risk (/year) Distance (m) Mitigated risk (%)
Comparing the three graphs referring to individual risk, we verified
1.00 E
09 32 100 that only the simulation using MM2 presents values below the intolerable
1.00 E
10 39 100 boundary stipulated by INEA. The other two simulations without any
1.00 E
11 44 100
1.00 E
12 47 100
measurement and using MM1 presented acceptable values only with
distances greater than 644m and 382m, respectively. Therefore, the only
acceptable condition is the case using MM2, as it presents all values
below the tolerance limit. Regarding the societal risk indicated by the
F–N curve, it is observed that only the first simulation indicated values
above the limit stipulated by INEA. The use of MM1 and MM2 reduced
the extent of the risk, ensuring the absence of sensitive occupations
within the radius of distance reached by the toxic ammonia cloud.

6. Conclusions

This work aimed to evaluate the risk of ammonia leakage, used as a

Fig. 9. Individual risk profile applying MM 2.
facility was exposed to. First, seven possible ammonia leak scenarios
were evaluated, which indicated the possibility of exposing the popula-
tion to a toxic ammonia cloud if one of the accidents occurred. Although
ammonia is a natural refrigerant, exposure of people to ammonia clouds
in certain concentrations can have serious health consequences. Some
studies using QRA to assess the risk of accidents involving ammonia can
be found in the literature. For instance, Avasthy and Siddiqui [15]
applied QRA to identify the accident scenarios of an ammonia loading
facility surrounded by a residential population, and the consequences of
the predictions were compared with accepted international criteria.
Other work also applied QRA to evaluate the dispersion and the effects of
liquefied ammonia tank in the case of an instantaneous release [12]. Both
works demonstrate that this refrigeration plant study is in line with the
procedures carried out in other works with toxic materials, such as
ammonia. The former showed the maximum IR to which the general
public is exposed was estimated as 4.03E-06/year, and SR fell mostly
above and near the intolerable region. This study indicated that the
maximum IR to which the residential area is exposed was estimated as
1.00E-05/year, and SR fell mostly above the intolerable boundary. The
refrigerant in an industrial facility located in Rio de Janeiro. The analysis
used PHAST computational modeling, where seven ammonia leak sce-
narios with three different concentrations were described for the simu-
lation. After calculating the risk analysis, it was found that the risk of
leakage and formation of toxic ammonia cloud among the seven sce-
narios is above the tolerance limit for individual risk and societal risk
stipulated by INEA. The most critical scenario, indicating sensitive oc-
cupations within the radius of the toxic cloud, was the accidental sce-
nario with leakage between the separator vessel V-02 and the
refrigerated products room. This scenario reached a distance of 2677 m
(IDLH), 665 m (1% probability death), and 428 m (50% probability
death). The individual risk tolerance limit stipulated by the INEA of
1.00E-06/year achieved a distance of 644 m, indicating that it reached
occupations close to the installation. Besides, the societal risk graph also
showed that the F–N curve was above the acceptable limit.
Thus, two mitigating measures were proposed (MM1 and MM2) to
reduce the risk up to the specified tolerability limit and were simulated
again in PHAST. MM1 also reached the residential area close to the
installation, which achieved the distances of 1474 m (IDLH), 395 m (1%
probability death), and 255 m (50% probability death). The IR limit for
this case reached a distance of 382 m, and it also reached the residential
area. Nevertheless, the SR indicated that the F–N curve was below the
required limit. On the other hand, MM2 showed a more significant risk
reduction and did not reach the residential area around the installation;
the most critical scenario was the scenario with the leakage in the main
reservoir and indicated the distances of 155 m (IDLH), 48 m (1% prob-
ability death) and 27 m (50% probability death). Besides, IR and SR
indicated values way below the tolerance limits. Therefore, MM2 met the
limits of INEA and ensured that even in possible ammonia leakage sce-
narios, toxic ammonia clouds did not reach the residential area close to

9
A.C. Rosa et al.
the factory, which indicated greater safety for the use of this refrigerant
in the installation.
This paper does not present an analysis of uncertainty in the analysis
of QRA, therefore it presents limitations related to a sensitivity analysis,
which can generate great uncertainty. For future work, the authors
suggest applying a sensitivity analysis or considering the use of other
tools for the analysis of toxic cloud dispersion, such as CFD.
Funding
The authors want to acknowledge the financial support from CNPq
(Brazilian National Council for Scientific and Technological Develop-
ment) and CNE FAPERJ (Fundaç~ao de Amparo a Pesquisa do Estado do
Rio de Janeiro) 2019-E
26/202.568/2019 (245,653).
Credit author statement
Ana Rosa: Formal analysis, Investigation, Validation, Data curation,
Writing – original draft. Ivenio Teixeira: Formal analysis, Investigation,
Validation, Data curation, Writing – original draft. Alexandre Terra:
Formal analysis, Investigation, Validation, Data curation. Ahmed WA
Hammad: Supervision, Validation, Writing – review & editing. Leandro
Torres Di Greg
orio: Supervision, Writing – review & editing, Project
administration. Elaine Vazquez: Supervision, Project administration,
Funding acquisition. Assed Haddad: Conceptualization, Methodology,
Project administration, Funding acquisition.
Declaration of competing interest
The authors declare no conflict of interest. The funders had no role in
the study’s design; in the collection, analyses, or interpretation of data; in
the writing of the manuscript, or in the decision to publish the results.
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