4\!

i lÌHM^
ν
INSTITUTE FOR SYSTEMS ENGINEERING
AND INFORMATICS
Support activities for the Directorate­General for Environment, Nuclear Safety and Civil Protection
on the implementation of the Council Directive
on the major accident hazards of certain industrial activities

COMMUNITY DOCUMENTATION CENTRE

ON INDUSTRIAI RISK
Review of accidents involving chlorine

JOINT
RESEARCH
CENTRE
EUR 14444 EN COMMISSION OF THE EUROPEAN COMMUNITIES 1992
 INSTITUTE FOR SYSTEMS ENGINEERING
AND INFORMATICS
Support activities for the Directorate-General for Environment, Nuclear Safety and Civil Protection
on the implementation of the Council Directive
on the major accident hazards of certain industrial activities

COMMUNITY DOCUMENTATION CENTRE

ON INDUSTRIAL RISK
Review of accidents involving chlorine

G . Drogaris

PARL EUROP. Bibliolh.

N.C. éü^^vW
CI.
CDCIR reference No. 936-EAb42-IV. 1.2

JOINT
RESEARCH
CENTRE
EUR 14444 EN COMMISSION OF THE EUROPEAN COMMUNITIES 1992
Published by the
COMMISSION OF THE EUROPEAN COMMUNITIES
Directorate-General
Telecommunications, Information Industries and Innovation
L-2920 Luxembourg

LEGAL NOTICE

Neither the Commission of the European Communities nor any person

acting on behalf of the Commission is responsible for the use which might
be made of the following information.

Cataloguing data can be found at the end of this publication.

Luxembourg: Office for Official Publications of the European Communities, 1992

ISBN 92-82&4403-0
© ECSC-EEC-EAEC, Brussels · Luxembourg, 1992

Printed in Italy
Table of Contents

1. Introduction 5

2. Chlorine 6
2.1 Chlorine Production 7
2.2 Chlorine Uses 8
2.3 Chlorine Related Regulations 9

3. Accidents Involving Chlorine 10

4. Accident Data Comparison 10

4.1 Comparison with Other Accident Data Sources 11
4.2 Accident Data for Accidents Common in Various Sources 13

5. Accident Characteristics 15
5.1 Type of Accidents Involving Chlorine 15
5.2 Quantities Involved 17
5.3 Accident Consequences 17
5.4 Using the Experience for Accident Prevention 20

6. Conclusions 21

References 23

Tables 29

Figures 57

Appendix 1: Samples of STOER Output Files 71

Appendix 2: Samples of HEGADAS Input and Output Files 91

Acknowledgments

The subject for this study has been suggested by Mr. A. Amendola in 1989. Interrogations of FACTS,
MHIDAS and SONATA data bases have been performed under the coverage of the support to the
Commission activities for the implementation of the SEVESO-Directive.
Assistance in identifying material useful for this study by Mrs. K. Rasmussen is appreciated.
The contribution of Mr. Francocci in preparing the graphs for this publication and of Mr. P. Wiederstein for
assessing the relevant documents available in CDCIR is highly acknowledged.
1. INTRODUCTION

Chlorine is a chemical used widely in the process industries for manufacturing of chlorinated
lime, which is used in bleaching of synthetic rubber and plastics, chlorinated hydrocarbons,
and a large number of other chemicals, for purifying water and desinfecting. It has been also
used as a military poison gas under the name of bertholite in the first world war.
Due to its massive use, chlorine is often involved in accidents. Chlorine is the single sub-
stance that has been involved most frequently in accidents notified to the Commission of the
European Communities under the requirements of the SEVESO-Directive / 1 / . This does not
necessarily implies that chlorine is more dangerous than other hazardous substances
covered by this Directive but merely reflects the fact that accident frequency involving a
certain chemical substance is proportional to its frequency of use.
Therefore it is expected that a significant number of accidents involving chlorine should have
been adequately reported in the technical literature providing enough material for an acci-
dent review study.
The basic raw material for performing this study has been obtained by interrogating
industrial accident data bases that are accessible to the public for accidents involving
chlorine. FACTS, run by TNO in the Netherlands, MHIDAS, run by the U.K. A.E.A.-S.R.D. in
U.K. and SONATA, run by TEMA in Italy are such accident data bases identified in a previous
study performed for the Commission / 2 / . Other industrial accident sources such as the
Handbook Störfälle / 3 / , accident inventory of the French Environmental Ministry / 4 / a
special issue of the CDCIR bulletin / 5 / as well as various safety related scientific journals
have been also used. Documents and handbook from the CDCIR proved to be very useful
references in preparing this study.
Comparison of the accidents involving chlorine from these sources leads to identification of
the difficulties in collecting data on accidents and indicates the limitations of uses of accident
data from such sources. This underlines the importance of a structured accident reporting
system such as MARS / 6 / that has been established within the domain of the SEVESO-
Directive. Finally lessons to be learned from the accidents registered in these sources are
extracted and presented.
2. CHLORINE

Chlorine ¡s a greenish-yellow highly toxic gas of a pungent odour. Its physical, chemical and
toxicological properties are given in Tables 1 through 3 respectively /7,14/.
The Chlorine toxicity monograph of the Institute of Chemical Engineers /14/ reviews care-
fully all toxicity data available (latest publication currently available in 1989). Latest experi-
mental data available suggest that for a healthy adult population a 50% lethal concentration
of 400 ppm (for 30 min. exposure) applies. The chlorine toxic load depends both on chlorine
concentration in the air (c) and exposure time (t) and may well be approximated by the
product ctV 2 (or c 3). Lethal concentration thresholds can be hardly established. There is
no indication for acute death hazard at concentrations lower than 50 ppm and the latest TNO
results indicate that LCQI would be in the range of 150 ppm to 200 ppm (10-30 min. expo-
sure time) /14/.
More detailed data on chlorine are available from the Chemical Data Sheets issued by the
Manufacturing Chemists Association /27/.
World production of chlorine was about 21 Mt in the beginning of '70 / 7 / and remains
around 25-27 Mt from 1973 to 1986 /7,8,12/.
Europe is the leading chlorine producer continent, accounting for approximately 47% of the
world production. U.S.A. is the bigger chlorine producing country (about 10 Mt/a), followed
by the EEC countries (7-8 Mt/a) and Japan (about 3 Mt/a) /7,8,12/. Chlorine is produced in
10 out of the 12 EEC Member Countries (all except Ireland and Luxembourg) /12/.
Chlorine is normally consumed on the producer site but large amount of chlorine has to be
liquefied to match production and consumption variations. Chlorine transport takes also
place in liquefied form / 7 / .
The most important uses of chlorine are /7.12/:
a) VCM production (25-30%).
b) Chlorinated hydrocarbons-solvents (20-25%).
c) Propylene oxide production (10-12%).

There is currently an environmental pressure for reducing the use of chlorine products.
Especially PVC creates major environmental concern since its burning in waste incinerators
produces HCl and dioxin /15.16/. Use of PVC as a packing material and in automobile
industry is gradually abandoned, in some areas (e.g. use of PVC for plastic bottles for bever-
ages in Switzerland) even prohibited /15/. However there are no indications for a reduction
in PVC production /17/. New applications (e.g. plastic windows /15/) or increase in con-
sumption /16/ indicate that PVC production will keep on growing during the beginning of
90S/17/.
Cellulose bleaching with chlorine is another significant chlorine application (at least in the
U.S.A., where it about 10% of chlorine production is consumed /If) that is environmentally
questionable.
Chlorine bleaching in the paper industry is responsible both for dioxin emissions and the
production of over 300 various halogenated substances that could be identified in paper
industry waste waters /18/. In six out of the eight paper industries of the FRG chlorine
bleaching has been substituted by other bleaching agents (oxygen, ozone, peroxides, etc.)
and the environmental pressure for abandoning chlorine bleaching in paper production is
expected to be increased /18/.
In general a reduction in chlorine production due to environmental reasons is within the pos-
sible branch development scenarios, according to some chlorine manufacture experts /19/.
Even if environmental concerns will prevail a substantial reduction in chlorine production will
not be achieved quickly. Development of alternative solutions takes always time. Therefore
chlorine will keep on playing an important role in the process industries and be a hazard for
the man and the environment due to its properties (see Tables 2 through 4).

2.1 Chlorine Production

Chloralkali electrolysis is the most important industrial chlorine production process /7,8/
today.
Chlorine has been initially produced in an industrial scale as a by-product of soda production
according to the Leblanc process. This has been abandoned in the second half of the 19th
century since Solvay process has been adopted for soda production / 7 / .
Electrolytic chlorine production was know as a process from the beginning of the 19th cen-
tury but could not be established on an industrial scale before the invention of big direct cur-
rent (D.C.) generators (W. v. Siemens), the development of the theoretical models for elec-
trolytic cells and the invention of diaphragms. Industrial scale electrolytic production of
chlorine started in 1890 in Germany (cement based diaphragms) and in 1892 in U.S.A.
(asbestos based diaphragms). This process is schematically shown in Figure 1 (source /8/).
After 1920 due to increased demand for pure caustic soda for the Rayon production the
mercury cells process has been introduced by I.G. Farben (see Figure 2; source /8/). Know
how of this process has been made widely available after the end of the second world war
/ 7 / . Mercury cells, traditionally the preferred approach in Europe and Japan, give a pure
chlorine product and concentrated caustic solution but pollute the environment with mercury
/7,21/. Diaphragm cells found favour in the U.S.A. where the energy needed to concentrate
the alkali was cheaper / 2 1 / .
Mercury released to the environment from chlorine production was as high as 25 g/tonne of
chlorine in the early 70 s /19/. The associated environmental problems forced the govern-
ment of Japan in 1973 to prohibit the mercury cell process. (Even soil contamination by
mercury has been recorded in areas of chlorine plants using mercury cells /20/). This
decision has been applied with various delays due to the investment cost required but at the
end of 70 s only 37% of the chlorine production capacity in Japan was based on the mercury
cell technology compared to 68% of the early 70 s.
In Europe stringent effluent specification have been applied so that mercury emissions are of
the order of magnitude of 0.1-0.2 g/tonne chlorine / 2 1 / . In FRG the average emission load
is estimated to only 0.06 g mercury per tonne of chlorine /19/.
Development of membranes that could be used instead of the asbestos based diaphragms
enabled the productions of highly pure chlorine and concentrated alkali solution not con-
taminated by chlorides (see Figure 3) without employing mercury /7,8,21,22/.
Therefore the mercury cell process is not considered as the "state of the art" in chlorine
production even if advanced pollution abatement systems are employed /18/. Chlorine pro-
ducers are now planning to abandon this technology by the year 2010 /18.23/, a project that
is estimated to cost about 6 billions dollars to the European chlorine production industry
/ 2 1 / (the investment cost for a new 300 kt/a chlorine capacity unit based on membrane
technology was estimated about 500 million DM in 1990 /19/).
Although the chloralkali electrolysis process accounts for most of the chlorine produced
today, a number of other commercial processes in current use make a significant
contribution to total chlorine production. Such processes include mainly electrolytic produc-
tion of potassium hydroxide, magnesium metal and sodium metal / 8 / . Chlorine can also be
recovered from hydrogen chloride /7,9/ (this was also the first industrial chlorine production
process). This process is mostly applied to the hydrogen chloride by-product from organic
chlorination processes. Two commercial processes are available / 8 / :
- Oxidation (Deacon, the oldest industrial chlorine production process / 7 / , Shell or Kel-
Chlor Processes).
- Electrolysis (De Nora, Krebs-BASF and Uhde electrolytic cells design).

2.2 Chlorine Uses

Chlorine has a variety of uses. It is a basic raw material for various inorganic and organic
substances that are used as bleaching agents, producing pharmaceuticals, pesticides, dyes,
plastics, fire fighting agents, etc. Further it can be used directly as disinfecting and sanitizing
agent. Principal chlorine applications are indicated schematically in Figure 4 (source /8/).
Hydrogen chloride, which can be produced from chlorine and hydrogen, has also numerous
uses (see Figure5). ECDIN /12/ contains 118 different processes, where chlorine finds
applications.
Vinylchloride (VCM), propylene oxide and chlorinated solvents account for 55-60% of chlo-
rine consumption /7,12,24/. There are other few substances that account for 1% up to 5% of
the chlorine consumption but in any type of statistics about 25% of the total chlorine produc-
tion finds applications in various chemical processes.
Chlorination reactions are not very selective. Hence chlorine applications are associated with
the creation of undesired by-products hazardous for the environment (e.g. perchlorides,
trichlorides, methylenchloride, Polychlorinated phenyls (PCBs), Pentachlorophenol (PCP),
hydrogen chloride or even dioxines and furanes) /24/.
In some processes an enormous amount of chlorine ends up in such undesired products.
Extreme examples are the catalytic synthesis of p-chlorotoluene (intermediate for dyes and
pesticides) and the toluenediisocyanate (TDI) synthesis. In the first case (catalyst iron
chloride and sulphur) about 50% of the chlorotoluenes produced is in the form of the
undesired by-product o-chlorotoluene; in the latter case 11 TDI production creates 0.851 of
hydrogen chloride by-product /24/.
Increased cost of handling/treating these hazardous wastes in environmental acceptable
ways has initiated various process modifications and new inventions that try to avoid or
minimize such waste production /22/. By-product recycling becomes also attractive. A
BASF process combines the high pressure incineration of halogenated substances with the
VCM production /24,25/. Hydrogen chloride produced from the incineration is reused in the
VCM synthesis. Simultaneously emission of various other hazardous substances produced
during the incineration (dioxine, furans, PCB) to the atmosphere is avoided since these
substances are also recycled in the process together with the hydrogen chloride.
Simultaneously chlorine free products are also developed /26/.
2.3 Chlorine Related Regulations

Because of its properties chlorine is considered as a hazardous substance classified as a

toxic substance /28,29/, poison /10.11/ or extremely hazardous substance /10.11/. It is
listed in at least in the following regulations:
a) CEC Council Directive 82/501 /EEC on the Major Accident Hazards of Certain Industrial
Installations /28/, known also as SEVESO- or post-SEVESO-Directive.
b) CEC Council Directive 67/548/EEC on classification, packaging and labelling (CPL-
Directive) of dangerous substances, and its revisions /29.30/.
c) In EPATSCA (Toxic Substance Control Act) inventory, in EPA Extremely Hazardous
Substances List and the Community Right to Know List (SARA - Superfund Amendments
and Reduthorization Act of 1986 - Title III) /10/.
d) In OSHA rule on Process Safety Management of Highly Hazardous Chemicals /31 /.

Other EEC regulations applicable to chlorine specify /12/:

- Maximum chlorine chlorine levels of 25 mg/l (measured titrimetrical by the Mohr's
method) in potable water.
- Prohibition for use in cosmetics (76/768/EEC).
- Maximum acceptable chlorine residues in fish water (0.005 mg HCIO/I) and surface water
(200 mg/l).
- Emission limits from titanium oxide plants (see also national regulations e.g. T.A. Luft /32/
for some process plants).

In U.S.A. there are also maximum chlorine or chlorine equivalent limits (100-200 ppm) if used
for disinfection of equipment handling food /12/.
The hazard associated with the handling and storage of chlorine have been early identified
/ 8 / and there are safety related guidelines issued by the manufacturers associations already
in late 50 s /33,34/. Public concern for major accidents involving dangerous chemicals
forced the relevant competent authorities to revise or even issue new safety related
guidelines. CEOC made an attempt to summarise mandatory and non mandatory or
recommended regulations applicable to hazardous substances in EEC Member Countries
and the U.S.A., however the list issued /35/ is not complete.
Chlorine safety related guidelines may be specific /36-39/, giving details on materials of
construction, type of equipment and safety devices to be used, hazards to be considered
etc., or can be covered by more general regulations /8,40/ making reference to safety
guidelines, technical instruction guidelines, standards, etc. (see also /41/for a complete list
of safety related regulations applicable for liquefied gases).
SEVESO-Directive requirement for compilation of safety reports for installations handling a
certain amount of dangerous substances (e.g. more than 251 of chlorine /28/) boosted the
compilation of pilot safety studies for typical installations (see e.g. /42,43/ for chlorine).
Check lists for the main hazards are also available in the literature (e.g. /8/) and safety
related guidelines (e.g. /36,39/).
Most of the documents mentioned above have been already included in the CDCIR as well
as a series of safety studies for European installations that are available to the public (see
/42-51/ safety studies of installations handling chlorine). Safety reports in turn increased
awareness on the hazards associated with handling and storing dangerous substances and
the ways that risk of major accidents can be minimized /52/. Pilot risk analysis studies for
fixed installations /53/ and liquefied chlorine transportation /54/ are also available.

3. ACCIDENTS INVOLVING CHLORINE

FACT, MHIDAS and SONATA accident data bases have been interrogated for accidents
involving chlorine at the end of 1989. There is a significant number of accidents registered in
all 3 data bases (342 in FACTS, 232 in MHIDAS and 167 in SONATA). Handbook Störfälle
/ 3 / covering the period of up to 1980 contains also 120 accidents involving chlorine.

4. ACCIDENT DATA COMPARISON

A comparison of the accidents from all these four sources shows (see Table 5) that the
number of accidents commonly recorded in all of them is rather small (only 36 accidents).
Accidents recorded commonly in at least 2 accident data sources are about 50% of the
smallest accident population and accidents commonly present in at least 3 accident sources
are about 1 /3 of the smallest accident population (the situation is slightly better between
Handbook Störfälle and MHIDAS and SONATA).
This is a first indication that various data sources are rather complementary to each other.
Similar observations have been made in reviewing accidents involving ammonia recorded in
FACTS and MHIDAS /55/ but also to literature sources of accident data /56/.
The distribution of number of accidents in each source and those commonly recorded ver-
sus the year of occurrence is given in Table 6. This table shows that almost all older acci-
dents are common in all accident collection. Since these accidents occurred much earlier
than the time accident data collection started, it is most probable that all accident collections
started by collecting well documented accident reports utilizing more or less the same
sources.
Table 7 gives the distribution of number of accidents recorded in the various sources (either
in one only or in more than one) versus the country of origin. Significant differences are
evident for the countries where the accident data collection are operated. The bigger number
of accidents recorded in U.K. appears in MHIDAS, while the same applies for
The Netherlands in FACT, FRG in Handbook Störfälle and Italy (and Brazil) in SONATA.
Though there are 28 accidents in U.K. recorded in MHIDAS and only between 6 and 10 in
the other sources, there are still 6 accidents in U.K. recorded in FACTS and not found in
MHIDAS, 5 and 4 accidents in U.K. recorded in SONATA and Handbook Störfälle respec-
tively not recorded in MHIDAS. The same applies more or less to all other cases. There are
82 accidents involving chlorine in The Netherlands recorded in FACTS and only 3 in
MHIDAS; one out of these 3 could not be found in FACTS. Handbook Störfälle contains 24
accidents in FRG, FACTS 22, MHIDAS 13 and SONATA 6 only. There are 14 accidents in
FRG recorded in FACTS but not appearing in Handbook Störfälle and the same applies for 2
and 1 accident in FRG recorded in MHIDAS and SONATA respectively. Another interesting

10
observation ¡s related with the accidents occured in Brasil and recorded in SONATA. 10 out
of these 11 accidents occurred in 1985 and the eleventh one in 1984. This can not be
interpreted that brasillan industry is absolutely safe and no accident occurred except this
specific time period. Most probably this indicates a time period in which TEMA (SONATA
operator) had access to information from Brasil. These differences indicate that collection of
data of all accidents is rather difficult even in the country where an accident data base is
operated.

4.1 Comparison with Other Accident Data Sources

Most of the accidents recorded in these four accident data bases occurred in the U.S.A.
(between 33.5% of the accidents recorded in SONATA and 50% of the accidents recorded in
MHIDAS); almost 50% of the accidents that are commonly recorded in more than one
sources occurred also in the U.S.A.. However there is no indication at all that the level of
safety in installations handling/storing or transporting chlorine in the U.S.A. is substantially
lower that in other parts of the world. This is also a first indication of limitations in using
accident data bases for performing statistical analysis.
US EPA has collected and analysed 3,121 accidental releases of hazardous substances
combining two federal reporting systems in the Acute Hazardous Events Data Base /57/.
Because of sampling, these accident records represent a larger population of 6,928 events
covering different portions of the 1980 to 1985 time period. Emphasis is mainly given to toxic
substances release than accidents involving flammable substances. The report available
/57/ contains also a list of the 468 events associated with the reported 4,717 injuries and
138 deaths. There are 46 out of these 468 events involving chlorine and most of them are
also recorded in FACTS, MHIDAS or SONATA (Handbook Störfälle covers the period up to
1980) (see Table 8). Though the number of major events recorded in the EPA data base is by
2.5 to 7.5 greater than the one included in the other data bases, there are still accidents
involving chlorine having casualties to man in the U.S.A. recorded in FACT (13 accidents), in
MHIDAS (7 accidents) and in SONATA (3 accidents) that are not included in the EPA data
base.
Up to the end of 1991 a total of 121 accidents have been notified in MARS. In 16 out of these
121 accidents chlorine has been involved. One of these accidents occurred in 1990 and
another in 1989 / 1 / . From the 14 remaining accidents 2 have been recorded in FACTS and 1
in MHIDAS only.
There are two other list of accidents involving chlorine available in the literature /53,85/. The
Cremer and Warner report /53/ contains 47 accidents. Only 1 out of these 47 is not included
in any of the four accident data collections. 25 out of the 47 are included in all 4 accident
data collections, 16 accidents in 3 accident data collections, 4 accidents in 2 of them and the
last one in SONATA only. The 46 out of the 47 accidents are included in SONATA, 39 in
MHIDAS and 36 in FACTS and Handbook Störfälle. These accidents cover the period up to
1979.
F.P. Lees /85/ gives two lists of accidents involving chlorine from AlChE and The IChem
respectively containing altogether 37 accidents. Only 2 out of them are not included in any of
the four accident collections (one of them is the accident in /53/ not included in any of these
sources). 16 out of the 37 are included in all 4 accident data collections, 18 accidents in 3
accident data collections, 6 accidents in 2 of them and the remaining 3 in SONATA only.

u
 30 out of the 37 are included in SONATA, 29 in MHIDAS, 28 in FACTS and 22 in Handbook
Störfälle. The accidents in these list cover the period up to 1974 (AlChE) and 1977 (IChem)
respectively. There are also some interesting case histories of accidents involving chlorine
given in the Appendix 3 of /85/.
The Loss Prevention Bulletin contains mainly accident case histories. A review of the Nos. 1
through 96 (up to December 90) gave a total of 19 accident case histories. There are also 6
accidents involving chlorine in the list of accidents in 1987. Most of the case histories are
very detailed but do not contain indications on the place (most probably U.K.) and the date
of the accident. The date is known in only 6 out of the 19 accidents. For these 6 accidents 3
are not included in none of the four data bases (FACT, MHIDAS, SONATA and Handbook
Störfälle), 2 are included in all of them and 1 accident in FACTS, MHIDAS and SONATA.
With reference to the 6 accidents of 1987, 4 of them are included in MHIDAS; 1 out of these
4 is also included in FACTS and none of them in SONATA.
Bulletin No. 4 of the CDCIR / 5 / contains selected accident case histories from the literature.
There are three papers referring to accidents involving chlorine. All three accidents described
in two papers are included in Handbook Störfälle, 2 of them in MHIDAS and 1 in FACTS and
SONATA.
Inventories of accidents having consequences to man and the environment of the French
Ministry of Environment / 4 / contain 4 accidents involving chlorine release in 1987 and 6 in
1988. None of them is included in any of the three accident data bases (FACTS, MHIDAS
and SONATA). Furthermore these French publications ¡4/ contain list of various major acci-
dents such as:
a) A list of 24 major accidents world wide. This contains only one accident involving chlo-
rine release in The Netherlands in 1987, which is included in FACTS only.
b) A list of 48 major accidents causing more than 50 fatalities, which, occurred up to 1985.
There is only one accident out of this 48 involving chlorine (1939 in Roumania), which is
included in all four accident data collections (there are however differences in the number
of fatalities and injuries reported).
c) A list of 43 major accidents causing evacuation of more than 5000 persons. Four acci-
dents involving chlorine are included in this list. All four are included in FACTS, 3 out of
these 4 in MHIDAS and SONATA and all 3 occurred before 1981 in Handbook Störfälle.

The OECD ad hoc Group of Experts on Accidents Involving Hazardous Substances has also
compiled a list of accidents involving hazardous substances which caused at least 25 deaths
or 125 injuries or 10,000 evacuees or 10,000 persons deprived of water or 10 million dollar of
damage to third parties using mainly MHIDAS, FACTS, Handbook Störfälle as well as other
accident data collections (SEI, SIGMA) and OECD own data. This list of 178 accidents, that
could be classified as catastrophic according to the Industrial Accident Gravity Scale used
by the Competent Authorities for implementing the SEVESO-Directive (see / 1 / ; EEC thresh-
olds for a catastrophic accident are more than 20 deaths, more than 200 injuries, more than
50,000 evacuation mandays or more than 200,000 person deprived of potable water),
contains 18 accidents involving chlorine. 15 out of these 18 are included in both FACTS and
MHIDAS, another one in FACTS, another one in MHIDAS and there is one not recorded in
anyone of the accident data bases (but described in the Loss Prevention Bulletin). SONATA
includes 10 out of the 16 accidents recorded also in FACTS and MHIDAS; while 6 out of the
8 accidents occurred before 1980 are included in Handbook Störfälle, too.

12
Hence there is an indication that the bigger the accident consequences the higher the prob-
ability that this accident will be recorded in more accident data collection, though that there
might be even accidents with catastrophic consequences missing from some or even all
accident data bases.
The Committee of the Competent Authorities for the implementation of the SEVESO-Direc-
tive has developed an Industrial Accident Gravity Scale that has been adopted for a two-year
trial period by the Council /59/. This scale is also used by the ad hoc group of experts of the
OECD /60/. This scale is composed of three gravity indices ranging from scale 1 (worth of
note accident) up to 5 (catastrophic accident), referring respectively to:
a) Index (D), the actual or potential danger (based on the amount of hazardous substances
involved).
b) Index (C), the extent of the consequences of the accident.
c) Index (M), the extent of intervention measures external to the establishment.

In this scale, index C is defined by the number of fatalities/injuries and the extent of envi-
ronmental or other property damages. This index C can be calculated for most of the acci-
dents recorded in the four accident collection based only on consequences to man
(fatalities/injuries). Since even 1 injury classifies the accident as an important one and even 1
fatality as a severe one no worthy of note accident could be identified (see Table 9). Further
the output of FACTS does not contain the relevant casualties field if the number of
deaths/injuries is equal to zero. Consequently, it is not possible to distinguish between acci-
dents for which value of C can not be assessed and those with none or negligible conse-
quences.
Table 9 shows also that for accidents involving chlorine the probability of an accident to be
recorded in more than one accident collections increases with the severity of accident con-
sequences but there are still catastrophic accidents that might be missing from some acci-
dent data bases.

4.2 Accident Data for Accidents Common in Various Sources

The comparison of accidents involving chlorine from various data bases indicates that there
are big difficulties in identifying and recording accident data. These difficulties should also
affect the quality of basic data of the accidents recorded. Table 9 gives already an indication
of discrepancies on consequences of accidents that are recorded in more than 1 accident
data bases.
An analysis of uncertainty and quality aspects of accident case histories readily available in
the literature /56/ found that only data on date and place can be considered of high quality
and that only number of fatalities, being of a medium quality could be eventually used for
statistical analysis. An even lower quality of data for accident data bases has been therefore
postulated /56/.
The quantity of chemical involved has been reported in very few cases (35-40%) (see
Table 10) of all accidents revealing that the quality of such type of data is very low /56/.
Table 11 summarizes the differences in basic accident data (such as country, date, conse-
quences) for accidents recorded in more than 1 accident data base.

13
Most of the differences regarding place, date and other data (e.g. chemical quantity, acci-
dent description, etc.) is due to missing/not known entries of the relevant field in one or
more data collections. Differences in number of fatalities is rather low (4-5% in comparison to
41% in /56/).
Differences in the number of injuries is more frequent but in almost half of the cases the
differences are minor so that the value of the consequence gravity index is not affected. For
the case of big differences other factors, such as various interpretations of the term "injury",
may play a role. Two interesting examples are the following:
a) Accident in Portugal, 12.01.79:
- SONATA & H.S.: 75 injuries;
- MHIDAS: 0 injuries / 75 persons exposed.
b) Accident in Bangladesh, 12.06.85:
- FACTS: 5 dead / 30 injured;
- MHIDAS: 5 dead / 100 injured (30 badly).

In general differences in basic data of accidents commonly recorded in more than one acci-
dent data bases are not so often as it has been observed for accident case histories avail-
able in the literature /56/ with the exception of parameters (such as number of injuries) that
can not be unambiguously defined. This should be attributed to the fact that for most of the
accidents various literature references are used and through the cross reference the quality
of the data included in accident data bases is increased.
However the differences in accident data, especially information for a certain accident
appearing in one of the accident data bases but not in others, show the difficulties in
collecting accident data without any structured accident reporting procedure. Accident data
bases use all possible sources such as accident reports, publications in scientific journals or
reports from news papers. Complete accident investigation reports (e.g. the Piper Alpha
Investigation report /61/) become very seldom available and refer to catastrophic accidents.
Scientific publications in safety related journal focus on the causes of accidents and try to
identify precautionary measures that can prevent similar accidents in the future but they
hardly contain information on the date of the accidents, while other data (place, conse-
quences) are not always adequately described. Newspaper reports focus on the spectacular
aspects of accidents which may attract public interest /84/. Date and place is normally given
with accuracy while other data (consequences, speculation on causes) are based on the first
not always verified information. Obviously extraction of high quality data from these sources
is a very difficult task.
This is also reflected in the causes of accidents recorded in accident data bases (see
Table 12). There is a significant portion of accidents for which causes are not reported. Fur-
thermore there is normally a single cause for each accidents (with few exception mainly in
FACTS and MHIDAS). However recent accident investigations show /1,61-75/ that there are
immediate and underlying causes of accidents. Identification of underlying causes is very
important for a successful accident prevention policy. Safety management aspects are the
emerging now as the most important underlying cause of accidents /1,61-76/, a fact that is
also recognized by chemical manufacturers /68,69,76/, so that new accident data bases
developed by operation companies for their own use have been "specifically designed to

14
identify causes, both immediate and underlying, not just circumstances surrounding the
accident" /77/.
Therefore the older approach to distinguish between technical failures and human errors as
accident causes is now gradually abandoned /71.76/. Improvement of design standards,
plant Inspection and technical safety could drastically reduce the frequency of accidents in
the 50's and 60's in U.K. /65/ and in the 70's in Japan /76/ and now the role of Human
Factors for accident prevention has become dominant /1,61-65,70-76/. Consequently
techniques for auditing and improving safety management systems are developed /78,79/.
Accidents reported are a small fraction of dangerous occurrences /63,65,80/. Full investiga-
tion of near misses is desirable /68,69,77-80/ for early identification of latent errors before a
severe accident occurs. A structured accident reporting system such as the MARS, which
has been established by the Commission within the framework of application of the
SEVESO-Directive / 1 / , can guarantee a high quality of data and recording of both immedi-
ate and underlying causes for the vast majority of accidents reported / 1 / . Though expansion
of this system to cover minor accident, dangerous occurrences and near misses is not prac-
ticable, application of the same accident investigation and reporting principals in a network
of accident data bases with the active participation of authorities, manufacturers and
dangerous chemicals transporters can secure adequate and complete recording of acci-
dents, incidents and dangerous occurrences in a consistent way.

5. ACCIDENT CHARACTERISTICS

The comparison of accidents recorded in various accident data bases showed that none of
these accident data collections can claim that all severe accidents have been included in it.
Data collection in a certain time period is performed using all possible accident data
sources. Consequently the reference basis is also not known (a complete accident data
collection could make reference to the global amounts of chlorine produced, transported,
etc.). Therefore use of these data for statistical purposes (e.g. to define accident frequencies
in time of for various chlorine applications) is questionable.
However a statistical analysis of this data is useful for identifying trends and priorities for
actions/improvements.

5.1 Type of Accidents Involving Chlorine

Mainly chlorine release is involved whenever chlorine is reported among the chemicals
involved; there is however a significant number of accidents involving chlorine associated
with explosions, fires or both of them.
The trivial case of a fire or explosion caused by reasons not related to chlorine, damaging in
turn installations processing, transferring or storing chlorine covers the major part of such
accidents. There are however cases where chlorine has been also involved or even pro-
voked fires and explosions. There are 11 such accidents recorded in FACTS, 8 in MHIDAS, 4

15
in SONATA, 6 ¡η Handbook Störfälle and 1 in MARS attributed to explosive reactions of chlo­
rine with:
­ H ydrogen : In electrolytic cells, especially in mercury cells in case of operation distur­
bances since the area of anode and cathode is not separated, (see also
Figure 3), or chlorine drying towers.
­ Organics : Natural gas, ethene, ethanol, gasoline, oils, seal oils from defect seals on
machinery or instruments.
­ Ammonia : Due to NCI3 production.
­ Bleach.
­ Iron.
A paper / 8 1 / from Du Pont discusses the experience of two unusual incidents occurred in
the early 70's involving the explosive reactivity of organics and liquid chlorine. Both incidents
have been considered as surprising, though the violent reactions of organics and chlorine
are known, because the explosions occurred when chlorine reacted with materials used
many years in this service. Conclusions and recommendation of the accident Investigations
are given in detail. These investigations dramatically demonstrated that the following
materials can be explosively reactive with chlorine:
a) Polypropylene filter element (used for filtering chlorine).
b) Silicone oil (used as a stable fluid in instrument diaphragms such as D/P (diaphragm
pressure) cells, integral orifice flowmetre D/P units and "Chemseal" pressure gauges).
c) Dibutylphthalate (commonly used in pressure transmitters).
d) Polychlorinated biphenyl heat transfer fluids.
e) H ydrocarbon oils (commonly used in diaphragm and other type pumps for chlorine ser­
vice).
f) Glycerin, which is used for instruments in chlorine service.
g) Drawing wax, used to slip loose liners inside steel tanks or pipe.
This is a limited incomplete list of materials used by that time by Du Pont in chlorine service.
Alternative materials for such uses are Indicated with a suggestion for testing prior to use
/81/.
Chlorine can be also evolved by other substances during an accident. There are 58 such
cases in FACTS, 24 in MHIDAS, 7 in Handbook Störfälle, 3 in MARS and 1 in SONATA.
In most of these accidents hypochlorites (sodium or calcium) have been involved. Bleach
accidental mixing with other chemicals (hydrogen chloride, sulphuric acid, iron chloride, sul­
phates and others not identified) can create chlorine emissions. Such accidents do not only
occurred in process or storage plants but also during other commercial uses of bleach
(disinfection, cleaning) even in household having consequences to man.
Chlorine has also been emitted by the decomposition of various materials (bleach, fertilizers,
etc.). Such accidents refer mainly to fire accidents in warehouses (see also /1/).
Finally chlorine has been emitted after the reaction of chemicals (trichlorocyanuric acid,
pellets of chemicals not specified, etc.) with water. Accidental contamination with water but
also humidity condensation and rainwater have contributed to such accidents.
In one case (accident on 17.06.88 in U.S.A., recorded in FACTS and MH IDAS) rain water
entering from an open window in a warehouse reacted with pellets causing fire and chlorine
release. The gas cloud reached half a mile over a town and about 30,000 persons were
evacuated.

16
Classification of accidents according to the type of activity is very useful. Typical activities
normally considered in the data bases include process, storage, transport and transfer activ-
ities. Unambiguous classification is not always possible (e.g. rail car loading/unloading
operations can be classified as rail transport accidents, transfer accidents or by the type of
installations where loading/unloading took place). Therefore no comparison is possible if the
classification made in each data base is adopted. Table 14 gives a classification of accidents
from various sources according to their origin by using common rools. It can not be claimed
that this classification is absolutely accurate since there is not always enough information
available.
Table 14 shows that accidents involving chlorine may occur in any type of application of this
chemical. Therefore due care and application of safety rules is a must whenever chlorine (or
substances that can readily release chlorine such as bleach, etc.) is handled.

5.2 Quantities Involved

As has been also earlier discussed quantity of chemicals involved in accidents is not
reported very often. Table 10 shows that the quantity of chlorine involved is known in about
35% to 40% of the accidents reported in the various accident collection (but in MARS the
portion of accidents involving chlorine is known in the 75% of the cases).
In the majority of the accidents for which chlorine quantity is known the amount of chlorine is
between 250 kg and 2.51 (D = 3, severe accident) or 2.51 and 251 (D = 4, very severe
accident) but there is also a significant number of accidents causing injuries reported where
less than 250 kg of chlorine has been involved (D=2, important accident).
EPA has set a reportable quantity (RQ) for various hazardous substances, which for chlorine
is as low as 10 pounds /57/. EPA RQs are 2 to 5 orders of magnitude lower than the art. 5
SEVESO-Directive threshold values. There were only 136 accidents for which both the
quantity of substance released was known and a reportable quantity threshold has been
assigned. In almost 50 out of the 136 of these accidents the quantity involved was not
exceeding the reportable quantity, in about 33 the quantity involvedv^asjjp to 10 times of
the RQ and in 35 cases between 10 and 100 times of the RQ.

5.3 Accident Consequences

Mainly consequences to man (fatalities and/or injuries and evacuation) are recorded in the
various accident data bases (see Table 15). Other type of consequences such as traffic clo-
sure, amount of material damage, etc. are very rarely recorded. Number of persons evacu-
ated has not been always recorded.
Environmental damages (such as plant/vegetation etching, pollution, etc.) have been
reported in very few cases (less than 10). Even in MARS there are only 5 out of the 16 acci-
dents involving chlorine with reported environmental damage. Even in this case quantifica-
tion of damages is hardly given.
The number of accidents in MARS as a whole with reported environmental damage is rather
low (about 15%) /1,82/. A similar observation was made in the EPA review /57/, though
specific emphasis on environmental issues has been given. Only 3% of the accidents col-

17
lected by EPA indicated environmental damage and in another 10% of the records no envi-
ronmental damage verified has been reported. In 87% of the records no information on
environmental damage has been reported. A more extensive review of accidents involving
dangerous chemicals in various literature sources (accident data bases, reports of the Rhine
Commission, French Environmental Ministry accident inventories / 4 / , various accident
reviews, pollution abstracts, Enviroline, chemical abstracts, NTIS, Aqualine and the indices
of the Marine Pollution Bulletin) /82,83/ showed that environmental consequences of acci-
dents were very seldom reported indicating that this issue has not yet received adequate
consideration.
Tables 17 through 21 and Figures 6 through 10 show the relation of quantity of chlorine
involved with the consequences observed (for those accidents for which adequate quantita-
tive information are available) with the help of the accident gravity indices. Table 16 gives the
definition of the accident gravity indices for accidents involving chlorine. In most of the cases
duration of evacuation is not available; 1 day has been then assumed. The complete defini-
tion of accident gravity indices is given in / 1 / .
The comparison of the two indices shows that in general there is a tendency that of conse-
quences severity increases with the amount of chlorine involved in the accident. However
there is no simple linear relation between extent of damages and amount of chlorine
involved (in such a case both indices should have always the same values). Obviously local
conditions have also an influence on the extent of the consequences. The same has been
also established in other accident review /57,82,83/.
Table 22 shows the distribution of number of accidents for which the consequences are
known versus the year of accident occurrence. Quantitative data on consequences to man
are more frequently recorded for accidents occurred before 1970 and for the majority of
accidents occurred before 1960. Accidents from the same period are also more frequently
commonly recorded in more than one data collection (see also Table 6 and Par. 4 above).
This also suggests that the best documented past accidents have been preferentially
included in the accident data bases.
On the contrary evacuation is reported more often in rather recent accidents (see Table 23).
This should be attributed to the rash urban development of industrial centres resulting in
urbanization of areas close to industrial activities as well as the increased need of chemical
transportation and their wide use.
Tables 24 through 27 and Figures 11 through 14 show that reaction by evacuation was in
general proportional to the extent of damages of the accidents. There are however few cases
suggesting of over-reaction, which in most of the cases is however justified by the potential
danger due to the high amount of chlorine involved (see Tables 28 through 31 and Fig-
ures 15 through 18).
Data on accident consequences are also very useful for checking the applicability of various
consequences models that are developed. However enough data of this type are sparingly
available in the output of the accident data bases. The amount of chlorine involved is
reported in only slightly more than one third of the accidents recorded (see Table 10).
Release rate is recorded in even fewer cases (14 in MHIDAS, 9 in FACTS, 6 in SONATA, 3 in
Handbook Störfälle). Extent of area of consequences of distance between release point and
causalities is also very rarely available. There are only 12 cases for which both amount of
chlorine released (in 5 out of these 13 duration also) and information on distances from
release point where consequences were observed (see Table 32). In one case (Case 5) only

18
release amount and duration was available in Handbook Störfälle, while details on conse-
quences were taken from other source /86/. Some of these accidents are included also in
other data bases than those indicated in Table 32 but there none of the information used in
Table 32 is given. Based on the consequences and the toxic properties of chlorine (see
Tables 3 and 4) chlorine concentration can be estimated. Making an assumption, whenever
necessary, on emission duration, chlorine concentrations have been also estimated using
various consequence estimation methods suggested for safety reports such as:
a) Overlays for estimation chlorine concentrations for neutral (Pasquill D) and inversion
(Pasquill F) conditions given in /43/. The only parameter required is the chlorine release
rate.
b) The computer programme STOER which is based on the relevant VDI Guideline /87/
and is available from VDI. It is an interactive relatively easy to use in connection with the
VDI Guidelines. Two examples of the output for cases 7 and 10 are given in Appendix 1.
Both release rate and duration are needed as an input as well as gas temperature
(whenever chlorine is released in gaseous form). Dimensions of the source (all three) can
be specified but the programme can be also used by assuming a point source. However
dimensions of the source have a significant effect on calculations. In addition to the
specified wind velocity the programme may perform calculations for various conditions
with low wind velocity (1 m/s) corresponding to worst dispersion conditions resulting to
pessimistic estimations (see Table 34).

c) The computer code HEGADAS from SHELL Research Ltd (version Aug. 1988). This pro-
gramme has been selected for fitting the results of hydrogen fluoride release tests
/88,89/. Hartwig /90/ also found that the version of DEGADIS can give a good simula-
tion of carbon dioxide field releases in complex terrains with obstacles while the
programme STOER gave rather conservative estimations. Release rate, size of release
source and gas temperature have to be specified for HEGADAS. Typical parameters cor-
responding to flat terrain and Pasquill D stability class were used (except few runs made
simulating Pasquill F stability class). Examples of batch input and output files for cases 7
and 10 are given in Appendix 2.

Table 33 summarizes the chlorine concentration predictions with the three methods men-
tioned above and the estimations from accident data. In most of the cases the agreement is
rather good as order of magnitude. In general STOER gives more conservative estimations
than HEGADAS.
Big discrepancies exist for case 5 (but the accident report /86/ indicates that about 30% of
the chlorine has been absorbed in the river and do not actually reached far downwind).
For case 6 a cloud of such a size can be only predicted by STOER in the extreme case of
wind velocity 1 m/s and inversion at 20 m. On the other hand all predictions are too con-
servative for case 7.
This comparison shows that collection of accident data is very useful for verifying
assumptions made in the development or application of various models (models and codes
validation requires the performance of experiments simulating as much as possible the
assumptions used in model development). Information on atmospheric conditions at the
time of release is very decisive for the correct application of the models and codes. Probably

19
use of the background material collected also together with the operation of accident data
bases can provide a more complete set of data that could be used for comparing all
available heavy gas dispersion codes (it shall be clarified that in addition to the ihree
methods readily available there are various computer programmes available in the market).

5.4 Using the Experience for Accident Prevention

Causes of accidents in various accident data collection are shown in Table 12. For a signifi-
cant portion of these accidents recording of causes has not been achieved. The reverse is
valid for MARS (see Tables 35 and 36) due to the official established accident reporting pro-
cedure and the data quality control guaranteed by the interaction among plant operator,
competent authorities and the Commission.
All sources indicate (see Tables 12 and 13) that component failures, operator errors and
unexpected/undesired chemical reactions are the most frequent immediate causes. Other
factors such as events impinging on the installation, natural events, etc. may also provoke
accidents. Hazards of unexpected/undesired reactions involving chlorine have already been
discussed in Par. 5.1 above.
Piping and piping elements are involved rather often in accidents. This explains also the par-
ticular interest in reviewing accidents involving pipeworks /64,73/. Valve failures are reported
among accident causes in more than 30 of the accidents included in MHIDAS and the same
number is valid for accidents in FACTS. Corrosion danger in handling chlorine has been
long established and therefore there exist a long time guidelines on proper material selection
for the construction of the installation (see e.g. /8,33-36/ etc.). However accidents attributed
to corrosion still happen. This results in defining more frequent inspections of preventive
maintenance in chlorine installations after accidents / 1 / .
Failure of transfer hoses occurs also rather frequent in accidents during chlorine transfer
indicating the another area that requires due care. Consequently means for quick isolation
and safe diversion of chlorine are necessary. These are the main trends concerning immedi-
ate accident causes involving chlorine indicated from the accidents stored in the various
accident data collections (FACTS, MHIDAS, SONATA, Handbook Störfälle). They constitute
also the lessons learned from accidents involving chlorine notified in MARS / 1 / and can be
recognized in the case histories of accidents involving chlorine given by Lees in /85/. There
is one more lessons learned related to the need of strength impurities control, a lesson that
has been also learned from various accidents involving run away reactions / 9 1 / .
Underlying causes can not be readily identified for accidents in the various accident data
collections. Access to background material could probably facilitate this.
The importance of safety management and of safety reviews in preventing accidents is indi-
cated by the figures in Table 36. After the Lord Cullen report on the Piper Alpha disaster / 6 1 /
off-shore oil and gas exploration and production installations are becoming gradually subject
to a control regime similar to the one foreseen by the SEVESO-Directive /92/. More attention
is payed to safety management and there is a movement from prescriptive to goal-setting
regulation. Initiatives from the industry are expected for improving safety management and
enhancing safety. Systematic methods for early detection of general failure types that are
potential causes of accidents /78,93/ can actively contribute to enhancing safety. However
the authorities should not be restricted in setting safety goals and waiting for the results.

20
They have to stimulate interest of safety by inspections and auditings of safety procedures.
Human factors for safe handling of hazardous substances such as chlorine are important not
only for industrial installations but in every phase of hazardous substances handling, trans-
port and use. This is underlined by accidents involving chlorine recorded in the accident data
bases such as the following:
- Accident during toilet cleaning by bleach and detergent causing one fatality.
- Chlorine release to potable water network causing 24 injuries.
- Chlorine release from supposed empty tanks (4 such accidents reported in MHIDAS and
1 in FACTS).

Proper handling of hazardous substances is required not only during normal operations but
also during emergencies. There are at least two cases recorded in which use of fire water to
extinguish fires of chemicals caused the release of chlorine.

6. CONCLUSIONS

This review of accidents involving chlorine that can be found in various accident data bases
and collections accessible to the public shows that:
a) None of the current accident data bases can collect all accidents occurred. The more
severe the accident consequences are the higher the probability that this accident will be
included in an accident data base becomes. Therefore statistical figures obtained from
data banks (such as accident frequencies, accident frequency / consequence relations,
etc.) shall be used with great care due to this limitations.
b) Accident data bases are very useful enabling the identification of:
- Measures necessary to prevent accidents and dangerous occurrences or to mitigate
accident consequences should an accident occur.
- Trends and priorities for effective accident prevention policies.
- Verifying the assumptions of consequence models.
c) There is a need to define all terms related to accidents in an unambiguous way to avoid
misinterpretation and unproper use of data.
d) Collection of complete and accurate accident reports is very difficult without a well
defined accident reporting procedure. Operation of MARS / 1 / showed that it is possible
to collect the experience gained from accidents and make it publically and readily avail-
able for accident prevention purposes without jeopardizing industrial secrecy. Industrial
organization also disclose regularly data on accidents (see e.g. /95/).

Accident reporting to a single reference point for any level of accident and incident for any
type of activity will create an enormous bureaucratic procedure. A network of collaborating
data bases operating in the same principals can facilitate exchange of information. Close co-
operation of this network with structured accident reporting systems such as MARS or
others that are expected to operate in the future (e.g. on occupational accidents) could
assist in collecting full and accurate accident reports. The experience from dangerous

21
occurrences and near misses is also important for accident prevention purposes. The OSHA
regulation / 3 1 / already foresees that manufactures should inform their personnel on the
causes of accidents. There are also examples of companies of industrial organizations that
collect accident data systematically /68,69,76,95/. Consequently cooperation of this
accident data base network with industry may permit a wider accident data collections
eliminating difficulties in data acquisition. For this reason guidelines for accident
investigation and reporting have to be developed that will be commonly applied by industry,
authorities and all other interested organizations. In addition to the circumstances of the
accident complete data on accident consequences (to man and the environment) and on
immediate and underlying causes of accidents should be also collected.

22
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28
TABLES
 Table 1 - Properties of chlorine. Sources /7-13/.

Greenish yellow gas, pungent odour (orange-yellow as liquid)

CAS Registry No. 7782-50-5

EEC No. 017-001-00-7
Atomic weight 35.45
Molecular weight 70.90
Chemical formula Cl
2
Melting point -100.98°C
Normal boiling point (atmospheric pressure) -34.05°C
Vapour pressure (at 20°C) 6.32 bar
Critical temperature 1144°C
Critical pressure 77.1 bar
Critical density 0.573 kg/I
Specific heat 0.498 kJ/kg.K(0°C)
0.501 kJ/kg.K(100°C)
0.505 kJ/kg.K(200°C)
Density (liquid) 1.468 kg/I (0°C, 3.67 bar)
(saturated gas) 12.07 g/l(0°C, 3.67 bar)
(dry gas) 3.21 g/l (0°C, atm. press.)
(gas) 2.49 (relative to air)
Viscosity (liquid) 340 μΡα-S (20°C)
(gas) 14.0 μΡ3.ε (20°C)
Latent heat of vaporization 287.4 kJ/kg (68.7 kcal/kg)

31
 Table 2 - Physico-chemical propesties of chlorine. Sources /7-13/.

Solubility in water 1.46 g /100 g water (0°C)

0.6g/100gwater(25°C)
0.57g/100gwater(30°C)
Very soluble in alkaline solutions

Non-flammable gas

Forming explosive mixtures

with organic gases

Lower Explosion Limit 3.1-8.1 % hydrogen in chlorine

Wet chlorine reacts with metals.

Ignition temperatures of dry chlorine gas 170°C (iron)
200°C (copper)
>200°C (steel but can be as low as
50°C in présense of impurities)
>500°C (Nickel)

Violent reaction with alcohols,

substances containing nitrogen
(ammonia, amines)

Can react to cause fires or explosions

upon contact with turpentine, illuminating
gas, polypropylene, rubber and many
organic substances, phosphines and
some salts.

Table 3 - Chlorine toxicity data. Sources /7.10-14/.

LCL (Inhalation-human) 2530 mg/m /30 min

LC (Inhalation-rat) 293 ppm/1 h

LC (Inhalation-mouse) 137 ppm/1 h

LCL (Inhalation-dog) 800 ppm/30 min

LCL (Inhalation-cat) 660 ppm/4 h

LCL (Inhalation-rabit) 660 ppm/4 h

LCL (Inhalation-guinea pig) 330 ppm/7 h

LCL (Inhalation-mammal) 500 ppm/5 min

1 ppm = 3 mg/m

32
 Table 4 - Effects to man by chlorine in air. Sources 77,10-14/.

Odour detection 0.02-1 ppm (or up to 3.5 ppm)

Irritation 1-2 ppm

Eye irritation 1-3 ppm

Long term exposure with effects limited to minor 0.01-1.4 ppm

changes In pulmonary function

Intolerance level 3-5 ppm

Sensation of stringing and burning of eyes 3-6 ppm (or 5-8 ppm)
to some individuals, with associated blepharospasm,
redness and watering

Immediate irritation of nose, throat and eyes 15 ppm

with cough and lachrymation

Immediate cough with a choking sensation 30 ppm

retrosternal chest pain and a sense of
constriction in the chest. Wheezing due
to development of brancho constriction
many occur. Possibility of nausea and vomiting

Development of a chemical tracheo-bronchitis 40-60 ppm

and pulmonary oedema. The latter many develop
after a latent period of several hours with
marked respiratory distress, restlessness,
possibly cyanosis and frothy sputum.
If secondary infection occurs, bronchopneumonia
many develop after a few days.

Fatal levels: 50 ppm acute danger

400 ppm/30 min
1000 ppm/5 min

Guidelines for exposure: 3

To protect general population from sensory <0.1 mg/m (0.034 ppm)
irritation and significant reduction in
ventilatory capacity
3
MIK (maximum immission concentration) for protection 0.3 mg/m (0.1 ppm)
of the area around plants using chlorine (in FRG)

TLV and MAK 0.5 ppm (forsorne countries 1 ppm)

STEL and peak-MAK for maximum 1 ppm (for some countries 3 ppm)
5 min

Guidelines for respiratory protection:

Chemical cartridge respirator; gas mask with <25 ppm
canister. Supplied-air respirator or self-contained
breathing apparatus with full face piece, helmet

Self-contained breathing apparatus with full face >25 ppm or unknown

piece operated in positive pressure mode
Combination supplied-air respirator and auxiliary
self-contained breathing apparatus operated in
positive pressure mode

Fire fighting:
Self-contained breathing apparatus with full
face piece operated in positive pressure mode.

33
 Table 5 ­Commonly registered accident involving chlorine.

SOURCE No. OF ACCIDENTS

FACTS (FA) 342

MHIDAS (MH) 232
SONATA (SON) 167
HANDBUCH STÖRFÄLLE (HS) 120

(%) O
FA/ΜΗ 112 33%­48%
FA/SON 83 24%­50%
FA/HS 58 17%­48%
M H/SON 83 36%­50%
MH/HS 75 32%­63%
SON/HS 76 46%­63%
Common in at least 2 sources 195
FA/MH/SON 57 17%­25%­34%
FA/MH/HS 46 13%­20%­38%
FA/SON/HS 42 12%­25%­35%
MH/SON/HS 55 24%­33%­46%
Common ¡η at least 3 sources 92
Common in all 4 sources 36 11%­16%­22%­30%

(*) Share of commonly registered accidents overthetotal numberofaccident involving chlorine registered
in each source '

34
 Table 6 - Accidents involving chlorine vs. year fo occurrence (values in parenthesis gire
the share over the smallest accident population).

NUMBER OF ACCIDENTS
\sOURCE FA
FA FA FA MH MH
FA FA FA MH MH SON MH MH SON SON SON
YEAR ^ v FA MH SON HS MH SON HS SON HS HS SON HS HS HS HS

Not known 4 1

up to 1940 39 15 16 6 15 14 6 10 6 6 10 6 6 6 6
(100%) (88%) (100%) (63%) (100%) (100%) (63%) (100%) (100%) (100%) (100%)

1941-1950 19 8 8 2 8 4 1 4 1 2 4 1 1 1 1
(100%) (50%) (50%) (50%) (50%) (100%) (50%) (50%) (50%) (50%) (50%)

1951-1960 21 11 14 7 11 4 3 2 2 5 2 2 2 1 1
(100%) (29%) (43%) (29%) (29%) (71%) (14%) (29%) (29%) (14%) (14%)

1961-1970 48 39 37 37 22 20 20 21 26 26 13 16 15 20 13
(56%) (54%) (54%) (57%) (70%) (70%) (35%) (43%) (41%) (54%) (35%)

1971-1980 104 86 52 68 37 28 28 32 40 37 20 17 22 27 15
(43%) (54%) (41%) (62%) (59%) (54%) (38%) (25%) (32%) (40%) (22%)

1981-1989 107 72 40 - 19 13 - 14 - - 8 - - - -
(26%) (33%) (35%) (20%)

TOTAL 342 232 167 120 112 83 58 83 75 76 57 42 46 55 36

(48%) (50%) (48%) (50%) (63%) (63%) (34%) (35%) (38%) (46%) (30%)

35
 Table 7 - Distribution of number of accidents involving chlorine vs. country of occurrence.

NUMBER OF ACCIDENTS
\S0URCE FA
FA FA FA ΜΗ ΜΗ
N. FA FA FA ΜΗ ΜΗ SON ΜΗ ΜΗ SON SON SON
YEAR ^v FA ΜΗ SON HS ΜΗ SON HS SON HS HS SON HS HS HS HS

USA 135 114 56 48 64/65 39 29 40 32 33 32/33 23 24 26 20

NL 82 3 1 1 2 1 1 - 1 - - 1 - - -
UK 10 28 9 6 4 6 1 4 2 2 3 1 1 1 1
FRG 22 13 6 24 6 3 8 4 11 5 3 5 2 3 2
CAN 13 11 7 4 8 4 3 3 2 3 2 2 2 1 1
S 6 9 19 13 4 8 6 8 9 11/13 4 4 6 8 4
J 7 5 2 2 4 1 1 2 2 2 1 1 1 2 1
F 6 4 2 2 3 1 2 2 2 1 1 2 1 1 1
Ν 5 6 9 5 3 2 2 3 3 5/4 2 2 2 3 2
DK 2 2 4 3 1 1 1 2 2 3/2 1 1 1 2 1
IND 5 6 3 - 2 3 - 2 - - 2 - - '- -
I 1 2 13 1 1 1 - 2 1 1 1 - - 1 -
BRA - 1 11
AUS 1 8 2 2 - - - 2 2 2 - - - 2 -
Β 2
SP 2 2 2 1 1 2 1 1 1 1 1 1 1 1 1
ΜΕΧ 1 2 2 - 1 ί - 1 - - 1 - - - -
SF 1 1 3 3 1 1 1 1 1 3 1 1 1 1 1
PRC 2 1 1 - 1/- 1 - 1 - - 1/- - - - -
RUM 1 2 2 1 1 1 1 2 1 1 1 1 1 1 1
BGD 1 - - - 1 - - - - - - - - -
BUL - 1 - - - - 1 - - - - - - -
CH 1
CHI - 1
DDR - - 1 - - - - - 1 - - - - -
ET 1
ISR - 1 1 - - - 1 1 1 - - - 1 -
Ρ - 1 1 - - - 1 1 1 - - - 1 -
PHI - 1
POL - - - - - - - - - - - - - -
SU 1 - - - 1 - - - - - - - - -
SRILANKA - 1
TR
YU 1 1 - 1 1 - 1 - 1 - - 1 - - -
ZA 1
SEA 5 - 4

NOT KNOWN 26 5 1

TOTAL 342 232 167 120 112 82 58 83 75 76 57 46 42 55 36

36
 Table 8 - Accidents involving chlorine in USA that caused fatalities/injuries (1981-1985).

NUMBER OF ACCIDENTS

^"^^-^^^ YEAR
1981 1982 1983 1984 1985 TOTAL

FA 7 8 3 - - 18

MH 5 2 2 - 1 10

SON 3 1 1 - 1 6

EPA 2 19 20 4 46

EPA/FA 2 2 - - 5

EPA/MH 1 - - 3

EPA/SON 1 - - 3

EPA/FA/MH 1 - - 3

EPA/FA/SON 1 - - 3

EPA/MH/SON - - - 2

All 4 - - - 2

37
 Table 9 - Consequence gravity incides of accidents involving chlorine.

NUMBER OF ACCIDENTS
COMMON IN
^ v . SOURCE
AT LEAST ALL 4
FA MH SON HS MARS
GRAVITY^^. 2 3
INDEX VALUE ^ v ^ SOURCES SOURCES

Not known 28 37 38 22-48 13-24 3-11 4

142
None (-) J 51 34 4 0-26 0-13 0-5 3

Worth of note (1) - - - - - - - -

Important (2) 77 50 32 31 14-35 8-19 1-6 6

Severe (3) 82 65 36 25 22-45 12-25 8-12 2

Very severe (4) 28 30 20 18 16-25 14-18 10-11 -

Catastrophic (5) 13 8 8 4 6-10 6-8 3 1

TOTAL 342 232 167 120 195 92 36 16

Table 10 - Actual/Potential Danger Index (D) for accidents involving chlorine.

NUMBER OF ACCIDENTS

^ \ . SOURCE
FA MH SON HS MARS
D ^ ^ ^ ^

Not known 224 134 110 75 4

Negligible(-) 25 10 3 - -

Worth of note (1) 7 5 - - 2

Important (2) 24 13 11 3 4

Severe (3) 26 31 15 19 5

Very severe (4) 28 24 15 12 1

Catastrophic (5) 8 15 13 11 -

Total D known 118(35%) 98(42%) 57(34%) 45(37.5%) 12(75%)

TOTAL 342 232 167 120 16

38
Table 11 - Differences in basic accident data for accidents recorded in more than one accident
data collections.

NUMBER OF ACCIDENTS IN

AT LEAST
ALL 4
2 sources 2 sources

Total 195 92 36

Differences 129 78 35

No differences 66 14 1

Differences in:
- Country 12 5 3
(in 1 source missing) 5 2 2
- Date 50 31 13
1 day 10 6 3
few days 6 5 3
weeks 2 2 1
months 1 1 1
1 year 1
in 1 source missing 30 17 5

- Fatalities/injuries 69 48 27
Fatalities 8 4 2
Injuries 57 44 27

- Consequence Gravity Index 34 26 14

by1 15 12 6
at least 2 19 14 8

- Minor differences or 49 25 5
in 1 source information
missing/not known

39
Table 12 - Causes of accidents involving chlorine as they have been recorded in various
accident data collections.

NUMBER O F ACCIDENTS INVO LVING CHLO RINE

^^SOURCE FA MH SON HS
CAUSES ^"---—_

Technical failure 70 97 20 26

Corrosion 2 13 4 7

Reaction 27 4 3

Human 92 63 10 13

Natural events 2 1 1 1

External fire 1 14 3 4

Power supply failure 1 7

Impact 3 17 2 1

Transport accident 4 26 15 20

Sabotage 3 2 1'

Not known/not reported 174 34 109 36

TOTAL 342 232 167 120

Table 13 - Type of accidents involving chlorine (R: Release, E: Explosion, F: Fire)

NUMBER OF ACCIDENTS
""^^^SOURCE
FA MH SON HS MARS
TYPE ^ " " ~ " - ^

R 245 182 86 93 12

R&E 31 21 8 8 3

R&F 20 15 10 8 1

R, E & F 15 4 3 10

None 0 31 10 4 1

Not known 56Π

TOTAL 342 232 167 120 16

(*) Potential chlorine release

(**) I nformation of these accidents available in condensed form only, type of accident could not be
identified.

40
 Table 14 - Origin of accidents involving chlorine.

NUMBER OF ACCIDENTS

" ■ OS URCE FA MH SON HS

ORIGIN _______^

- Chlorine in processing 95 64 39 38

- Chlorine storage 27 26 30 8

- Chlorine transfer 51 25 8 13

- Pipelines 8 8 16 13

PROCESS PLANTS 181 123 93 72

- Chlorine in cylinders 42 36 6 2

- Warehouses 12 11 1 3

- Water treament/swimming pools 22 6 6 3

- Other uses (cleaning, disinfection) 4 2

- Storage in power plants 2 3 1

CHLORINE USES 82 55 16 9

- Rail transport 51 41 33 30

- Road transport 17 9 7 5

- Water ways/sea transport 11 2 17 2

TRANSPORT 79 52 57 37

UNKNOWN 2 1 2

TOTAL 342 232 167 120

41
 Table 15 - Chlorine accidents causing fatalities and injuries and/or public evacuation.

NUMBER OF ACCIDENTS

^^-^SOURCE
FA MH SON HS MARS
CONSEQUENCES-"*"-^

Fatalities 43 33 26 18

Injuries 175 140 86 71 8

Evacuation 65 69 19 25 3

Total causing 218 177 101 83 10

consequences

TOTAL 342 232 167 120 16

Table 16 - Definition of gravity indices used for accidents involving chlorine.

Amount of Consequence Number of

Actual / Potential chlorine Gravity Intervention Evacuation
Danger Index(D) involved Index Index (M) man-days
Fatalities Injuries
(t) (C)

Negligible(-) None Negligible(-) - - Negligible(-) -

Worthy of note (1) -0.025 Worthy of note (1) - - Worthy of note (1 ) 1-10

Important (2) 0.025<x<0.25 Important (2) - 1-10 Important (2) 11-100

Severe (3) 0.25<x<2.5 Severe (3) 1-5 11-50 Severe (3) 101-5000

Very Severe (4) 2.5<x-25 Very Severe (4) 6-20 51-200 Very Severe (4) 5001-50000

Catastrophic (5) >25 Catastrophic (5) >20 >200 Catastrophic (5) >50000

42
Table 17 - Consequences vs. Actual/Potential Danger Indices for accidents in FACTS.

"\^ c - 1 2 3 4 5 TOTAL
D ^ < ^

1 1 1 2

2 11 4 1 16

3 1 3 8 3 15

4 1 3 6 3 6 19

5 1 1 1 1 2 2 8

TOTAL 3 1 19 20 9 8 60

Table 18 - Consequences vs. Actual/Potential Danger Indices for accidents in MHIDAS.

^ s . D - 1 2 3 4 5 TOTAL
C ^ \

- 8 8

1 2 2

2 3 4 4 1 12

3 6 6 10 6 1 29

4 6 2 5 3 5 21

5 1 2 3 5 1 12

TOTAL 24 16 22 15 7 84

43
 Table 19 - Consequences vs. Actual/Potential Danger Indices for accidents in SONATA.

^ ^ c - 1 2 3 4 5 TOTAL
D ^ > ^

- 3 3

2 3 1 6 1 11

3 7 2 4 1 1 15

4 5 2 3 3 1 14

5 2 3 2 4 2 13

TOTAL 20 8 15 8 5 56

Table 20 - Consequences vs. Actual/Potential Danger Indices for accidents in Handbook

Störfälle.

\ ^ c - 1 2 3 4 5 TOTAL
D \ ^

2 2 2

3 4 5 1 1 11

4 4 1 1 6

5 1 1 4 2 8

TOTAL 1 8 9 6 3 27

44
Table 21 - Consequences vs. Actual/Potential Danger Indices for accidents involving chlorine
in MARS.

^\. c - 1 2 3 4 5 TOTAL
D ^ \

1 1 1 2

2 2 1 3

3 3 1 4

4 1 1

TOTAL 3 4 2 1 10

45
Table 22 - Number of accidents with consequences recorded vs. year of accident occurrence.

NUMBER OF ACCIDENTS (·)

^ " ~ - - - - — - ^ _ SOURCE FA MH SON HS
DATE — ^ ^ - ^

up to 1960 52 (66%) 29 (85%) 33 (87%) 14 (93%)

1961-1970 33 (67%) 38 (97%) 32 (86%) 24 (65%)

1971-1980 47 (48%) 73 (89%) 42(81%) 44 (65%)

1981-1989 67 (60%) 63 (83%) 23 (58%)

NOT KNOWN 1 (25%) 1 (100%)

TOTAL 200 (58%) 204 (88%) 130 (78%) 82 (68%)

Table 23 - Number of accidents with public evacuation recorded vs. year of accident occurrence.

NUMBER OF ACCIDENTS (*)

SOURCE FA MH SON HS
DATE ^ ^ _

up to 1960 3 (4%) 1 (3%) -(0%) -(0%)

1961-1970 10(20%) 15 (38%) 6(16%) 6(16%)

1971-1980 24 (24%) 22 (27%) 13 (25%) 19 (28%)

1981-1989 28 (25%) 31 (41%) - (0%)

NOT KNOWN - (0%) -(0%)

TOTAL 65 (19%) 69 (30%) 19(11%) 25 (20%)

(*) (Values in parenthesis indicate percentage of the total number of accidents recorded in the same period
and source).

46
 Table 24 - Intervention index vs. consequences index (FACTS).

^ ^ M - 1 2 3 4 5 TOTAL
C ^ v ^

- 1 1 2

2 1 2 3 6

3 4 11 15

4 5 1 6

5 2 2 4

TOTAL 5 21 7 33

Table 25 -Intervention index vs. consequences index (MHIDAS).

^ ^ M - 1 2 3 4 5 TOTAL
C ^ \

- 3 5 4 2 14

2 2 10 2 14

3 1 6 6 13

4 2 2 7 2 13

5 1 2 3

TOTAL 8 9 30 8 2 57

47
 Table 26 - Intervention index vs. consequences index (SONATA).

^ ^ M - 1 2 3 4 5 TOTAL
C ^ ^

1 1 2

2 2 2 4

3 2 2

4 6 6

TOTAL 9 4 1 14

Table 27 - Intervention index vs. consequences index (Handbook Störfälle).

^ ^ M - 1 2 3 4 5 TOTAL
C ^ \

1 1 2
1

2 3 3
3 2 2
4 1 1
5

TOTAL 6 1 1 8

48
 Table 28 - Intervention index vs. actual/potential danger index (FACTS).

^ ^ M - 1 2 3 4 5 TOTAL
D ^v^

2 1 1
3 2 1 3
4 2 1 3
5 3 1 4

TOTAL 2 7 2 11

Table 29 - Intervention index vs. actual/potential danger index (MHIDAS).

^ ^ M - 1 2 3 4 5 TOTAL
D ^ \

2 1 1 2

3 2 5 1 8
4 1 2 1 4

5 8 1 1 10

TOTAL 1 2 16 3 2 24

49
 Table 30 - Intervention index vs. actual/potential danger index (SONATA).

^ ^ M - 1 2 3 4 5 TOTAL
D ^ \

1
2
3
4
5 3 1 1 5

TOTAL 3 1 1 5

Table 31 - Intervention index vs. actual/potential danger index (Handbook Störfälle).

^ ^ M - 1 2 3 4 5 TOTAL
D ^ ^

1
2
3 1 1
4
5 1 1 2

TOTAL 1 1 1 3

50
Table 32 ­ Accidents for which amount of chlorine released and distance of consequences are
known.

No. Year/ Data Concentration Assumptions

Emission Consequences
Country Source (s) Estimation for calculations

CASE1 1961/USA MH, SON, 301 rel. 15 km evac. 10­15 ppm (2.2 km) rei. time: 30 min­
HS, LEES [85] (r­2.2 km) 2 ppm (10 km) 60 min
Cloud 6 miles long Pool: 3x6 m

CASE 2 1972/F MH 101 rel. Vegetation damages 10­15 ppm (2.5 km) rel. time: 10­20 min
in 2.5x0.6 km Pool: 3x6 m

CASE 3 1973/USA SON 551 ¡η 5.5 h Damagewithin 10­15 ppm (900 m) Pool: 2x4 m
2.59 km (r ζ 900 m)

CASE 4 1973/CAN MH 15.51 rel. Chlorine detected ­ 1 ppm (2.4 km) rel. time: 30 min
1.5 miles ~ 2.4 km Pool: 3x6 m

CASE 5 1976/NL HS, [86] 51 in 15 min Public disturbance 8.5­40 ppm (400 m) Pool: 3x5 m
Vegetation damage 2.4­15 ppm (1 km)
0.8­5 ppm (1.8 km)
from [86]

CASE 6 1977/USA MH 0.2 t Cloud 3 miles long 2 ppm (4.8 km) rel. time: 5 min
1 mile wide, 2000 ft Pool: 1x1 m
high Gas temp.: 15°C

CASE 7 1978/NL MH 5t Cloud 400 m 2 ppm (400 m) Pool: 3x5 m

13.9 kg/s

CASE 8 1979/USA MH 4701 Cloud 28 miles 2 ppm (45 km) rel. time: 30­60 min
Pool: 14x20 m

CASE 9 1981/USA MH Urei. 5 km evac. 10­15 ppm (1.25 km) rel. time: 10­30 min
Pool: 3x6 m
Gas temp.: 50°C
2
CASE 10 1982/USA FA 0.44 m in Cloud 2.59 km 2 ppm (900 m) Pool: 2x4 m
10 min (r~900m)
CASE 11 1986/USA MH 0.24 t Cloud 1/2 sq. mile 2 ppm (625 m) rel. time: 5 min
disp. after 4 h Pool: 1x1

CASE 12 1989/USA MH 0.51 in 10 min 1 sq. mile evac. 2­5 ppm (900 m) Pool: 1x1

51
Table 33 - Comparison of estimated chlorine concentrations with gas dispersion calculations.

Estimation CHART STOER HEGADAS

No. [4 m/s, Pasq. D]
(see Table 32) [43] [871
CASE1 5-10 ppm (2.2 km) 15 ppm (2.2 km) 2.2 km: 12-25 ppm 2.2 km: 3-5 ppm
2 ppm (10 km) 2 ppm (4.5 km) 10km:~ 1 ppm 10 km: 0.05-0.1 ppm

CASE 2 10-15 ppm (2.5 km) 15 ppm 4-18 ppm 2-3.5 ppm

CASE 3 10-15 ppm (900 m) 15ppm(Pasq. D) 8 ppm - 22 ppm 10 ppm

CASE 4 1 ppm (2.4 km) 2 ppm (Pasq. D) 8-10 ppm 4 ppm

15 ppm (Pasq. F)

CASE 5 8.5-40 ppm (400 m) 15ppm(D)-150ppm(F) 550 ppm 101 ppm

2.4-15 ppm (1 km) 15 ppm 30 ppm 13 ppm
0.8-5 ppm (1.8 km) 2ppm(D)-15ppm(F) 4-10 ppm 4 ppm

CASE 6 2 ppm (4.8 km) « 2 ppm 0.005-0.15 ppm 0.07 ppm

CASE 7 2 ppm (400 m) 400 ppm 1000-2000 ppm 200 ppm

CASE 8 2 ppm (45 km) - 2-8 ppm 0.035 ppm

CASE 9 10-15 ppm (1.25 km) 2 ppm (Pasq. D) 4-20 ppm (2 m/s neutral) 1-3 ppm
15 ppm (Pasq. F) (126 ppm Pasq. F)

CASE 10 2 ppm (900 m) 2ppm (Pasq. D) 2-3.5 ppm 5 ppm

15 ppm (Pasq. F)

CASE 11 2 ppm (625 m) 2ppm (Pasq. D) 0.4-1.2 ppm 1-6 ppm

15 ppm (Pasq. F)

CASE 12 2-5 ppm (900 m) 2ppm (Pasq. D) 0.5 ppm (4 m/s neutral) 1.7 ppm
15 ppm (Pasq. F) 0.5-2 ppm (2 m/s neutral) (72 ppm Pasq. F)

52
 Table 34 - Summary of results of calculations using STOER.

\PARAMETRO
CHLORINE CONCENTRATION (ppm)
RELEASE
DISTANCE NEUTRAL
RATE WIND 1m/s
Km
(t/h)
Wind Wind
CASE \ STABLE NEUTRAL UNSTABLE
2m/s 4m/ss

1 60 2.2 25 4580 2280 1133

10 1 883 35-147 5-31
30 2.2 12 2300 1162 605
10 0.7 555 30-120 5-30

2 120 2.5 8-27 4-18 960-3275 250-1140 70-457

60 2.5 4-10 780-2000 205-835 61-375

3 10 0.9 22 8 654 385 245

4 31 2.4 13-29 8-10 1300-2113 308-1011 4

5 20 0.4 680-936 551 5510-5630

1.0 39-84 30 1580-2507
1.8 4-9 557-1423 152-661 50-306

6 2.4 4.8 0.004-0.017 0.002-0.01 0.8-2.6 0.15-0.6 0.03-0.15

7 50 0.4 1580-2667 1280-2040 6667-8340 (6 m/s)

950-1523

8 940 45 5-18 2-8.5 6200-16920 279-937 27-115

470 45 5-18 2-7.5 5567-16100 269-919 26-115

9 6 1.25 4-19 2.3-6.3 245-673 67-321 25-165

2 1.25 5-6 2.1 233 68-131 20-77.5

10 4 0.9 2.3-9 1.7-3.4 117-264 32-144 13-81.5

11 3 0.625 0.6-3.1 0.4-1.2 18-62 6-32 2.7-18.5

12 3 0.9 0.5-1.7 0.3-0.6 22-50 6-27 2.5-15

53
 Table 35 - Immediate causes of accidents stored in MARS.

NUMBER OF ACCIDENTS
IMMEDIATE CAUSES
ACCIDENTS INVOLVING ALL ACCIDENTS
CHLORINE

1.1 Operator erros 5 28

1.1.1 Operation related 3 21
1.1.2 Maintenance related 2 7

1.2 Component failure 5 54

1.2.1 Piping and piping elements 3 25
I.2.6 Instrumentation 1 9
I.2.5 Machninery - 6
I.2.3 Valves - 6
I.2.2 Weldings 1 5

1.3 Corrosion 1 11

1.4 Chemical reactions 1 21

1.5 Electrostatic loads - 7

1.6 On-site events not connected _ 3

with the installation

1.7 Off-site events impinging on . 8

the installation

1.8 Natural events - 5

Under investigation 4 14

Not known 1 4

None - 2

TOTAL 16 121

54
 Table 36 - Underlying causes of accidents stored in MARS.

NUMBER OF ACCIDENTS
IMMEDIATE CAUSES
ACCIDENTS INVOLVING
ALL ACCIDENTS
CHLORINE

11.1 Managerial/organisational 12 88
omissions
11.1.4 Insufficient/unclear 8 62
procedures
11.1.9 Design inadequacies 8 54
11.1.1 Lack of safety culture 14
11.1.7 Insufficient training 2 11
11.1.5 Insufficient supervision 1 5

11.2 Design inadequacies 9 65

11.2.2 Inadequate safety analysis 8 47
II.2.5 Codes provided for limited 3 30
protection
1 15
11.2.3 Design error
2 14
11.3 Short-cuts
4 14
Under investigation
4
Unknown

TOTAL 16 121

55
FIGURES
 Saltor
brine

Brine Treating
• treatment chemicals
Purified
brine
Brine
1
resaturation

Brine
feed
1
Hydrogen
Electrolysis Chlorine (cell gas)
*
1
Cell liqilor Hydrogen
' cooling
Salt Caustic evap. Clj cooling H2S04
and salt recovery Weak and drying
* H2
'H 2 SO 4
•
■

50% Na OH Hydrogen
1 compression
Caustic cooling Chlorine
and filtering compression
1 Hydrog en
, 5 0 ? &NaOH Droduct
pro duct ■■

■
Chlorine
Caustic purification
concentrator
»■
CI, gas
2

739 \ MoOH pre duct

Chlorine
pro auct liquefaction
'
Caustic fusion
and flaking Liq uid CI,
'
i product
An!lydrous
m N-if )H
pro ducts

r
Cl 2 F ree v« , Chlorine
;nt * recovery

I *

Figure 1 ­ Flow diagram of diaphragm­cell operation in a chlorine­caustic plants. Source / 8 / .

59
 Salt

Brine
resaturation

Treating
Brine
purification chemicals

Hg Brine
feed

Electrolysis Chlorine (cell gas)

Hydrogen
/■v.
HjO Hg­Na
amalgam Cl 2
/ ■ \ ­
T3
Φ Decomposer Cone
Clj cooling Hydrogen
α and drying Η,εο, cooling
X
Q O
ce
Brine
öS dechlorination
o Chlorine Hydrogen
m compression
compression
­e
Weak _ CI, gas .Hydrogen
Caustic H2S04 "product ι *■
filtering product
Chlorine
50%NaOH liquefaction
"product
Vent
Caustic Chlorine _Liquid Clj
concentrator recovery product

,73%NaOH
product

Caustic fusion
a n d flaking

Anhydrous
•NaOH
products

Figure 2­ Flow diagram of mercury­cathode­cell operation in a chlorine­caustic plants.

Source / 8 / .

60
 Ό ra

ra O
i- v>
+->
c o
O) 'ZÎ
O v>
I C D
O to
Ί ' Ι ' ­S"\>
o °
<—
■a ­tWWWWII'

Sodium ¡on
>■

►
Χ

(Na+)
z> ?·
o sc \ S E
S.E
12 o o

1%.
I
ί­
α)

4-
^ ■ « β « +*JJ
■ Ι ιΊ
Γ

XJ Q.

<··5

I
"D QJ
■°1 α>
Q>
C

t; XI
t­ o.
ν
'u. 0<Γ
Ά

Figure 3 - Chlorine electrolysis cells: (a) mercury cell; (b) ordinary diaphragm cell; (c) new
membrane cell (7). Source / 8 / .

61
 amyl chloride high pressure lubricants
ethylene dichloride fireproofing agent for
chlorofluoro hydrocarbons textiles (with anti­
carbon tetrachloride chlorinated paraffins—* mony oxide)
1,1,1'trichloroe thane plasticizer for
1,1,2­trichloroethane p o l y v i n y l chloride)
trichloroethylene detergents
perchloroethylene
methyl chloride moisture­, flame­, acid­,
production of organic phosgene and insect­proofing of
chemicals by oxy­ methylene chloride chlorinated waxes­· » wood, fabrics, wire,
chlorination proc­ chloroform chlorinated and cable
esses (often inter­ ethyl chloride naphthalenes solvent
changeable with allyl chloride chloroacetic acid
oxyhydrochlori­ chlorosulfonic acid 2,4­dichlorophenoxyacetic
nation processes) chloroprene acid(2,4­D)
­herbicides
chloroanthraquinone 2,4,5­trichlorophenoxy­
chloro anilines acetic acid (2,4,5­T)
dichloropropane chloroacetyl chloride—«­tear gas (chloroaceto­
chlorobenzene phenone)
dichloropropenes — ­soil dichlorobenzenes
fumi­ trichlorobenzene
m e th allyl chloride gan ts tetrachlorobenzene
benzene hexachloride
polychlorinated
biphenyls
chlorotoluenes
hexachlorothane
chlorophenols
chloral
hexachlorocyclo­
pentadiene ^_
Chlorine- perchloromethyl organic synthesis
electrolysis of mercaptan ­ dye intermediate
brine pulp and paper tetrachlorophthalic fumigant
electrolysis of bleach­
textiles anhydride «­flame retardant for
fused salt plastics
electrolysis of
magnesium sodium chlorate bleach textiles
chloride water purification wood pulp
electrolysis of antiseptic
hydrochloric epichlorohydrin
acid hypochlorous acid calcium hypochlorite
catalytic oxida­ sodium hypochlorite
tion of hydro­ lithium hypochlorite
chloric acid chlorinated trisodium
chemical reaction phosphate ■cleaner and disinfectant
of potassium
chloride and sanitizers (eg, for swimming pools)
nitric acid household and commercial bleaches
chlorinated isocyanurates detergents for automatic dishwashers
(potassium dichloroisocyanurate, scouring powders
production of in­ sodium dichloroisocyanurate, chlorinated cleaners and sanitizers
organic chemicals­ trichloroisocyanuric acid)
hydrochloric acid
phosphorus trichloride
sanitizing and disin­ phosphorus pentachloride
fecting agent(eg,for phosphorus oxychloride
municipal water sup­ titanium trichloride
plies, swimming titanium tetrachloride
pools) ferric chloride (by­product of
titanium tetrachloride production)
waste and sewage aluminum chloride, anhydrous
treatment sulfur monochloride
sulfur dichloride
slimicide sul fu ryl chloride
mercurous chloride
mercuric chloride
silicon tetrachloride
zinc chloride from zinc metal
antimony pentachloride
antimony trichloride
stannous chloride
arsenic trichloride
bismuth trichloride
chlorine trifluoride
molybdenum pentachloride
iodine monochloride ­pharmaceutical (antiseptic)
iodine trichloride ­pharmaceuticals

Figure 4 ­ Chlorine derivatires. Source / 8 / .

62
 steel pickling­ ­ferric chloride
(by­product)

production of
chlorinated hydro­
carbons via
oxyhydrochlorination
processes (often vinyl chloride from ace­
interchangeable with tylene
oxychlorination ethyl chloride
processes) other chlorinated hydro­
carbons

modifier in ore bene­ methyl chloride

ficiation (flotation) ethyl chloride
processes production of alkyl 1,4­dichlorobutane (tetra­
refining of tin and chlorides via methylene adiponitrile
tantalum substitution reactions­ d ¡chloride) o t h e r organic
higher alkyl chlorides synthesis products
Grignard reagents:
organometallics
alkylchlorosilanes ­ silicone resins and
elastomers
chemical milling baths
(metal working) calcium chloride (waste
by­product)
gaseous flux for babbit­
ting operation aluminum chloride, anhy­
drous
barium chloride
cadmium chloride
Hydrochloric acid—- cobaltous chloride
by­product cupric chloride
from salt and magnesium chloride from
sulfuric acid brines
from chlorine and nickel chloride
hydrogen chemical reagent stannic chloride
and intermediate ■ titanium tetrachloride
oil well acidizing chlorosulfonic acid
food processing (eg, in production of metallic
sugar refining, chlorides and other zinc chloride
brewing industry, inorganic chemicals — antimony trichloride
and for manufac­ arsenic trioxide arsenic trichloride
ture of mono­ bismuth trichloride
sodium glutamate lithium chloride
and gelatin) zirconium tetrachloride

catalyst for production

of aniline by nitro­
benzene reduction
latex coagulating
agent
deliming agent for
hides

refractories
alloys
desulfurization agent zirconium ­ photoflash bulbs
for petroleum water repellent agent
pyrotechnics
pH control pigments
scale removal
veterinary medicine chlorine
silica gel
silica, hydrated
other inorganic chemicals

aniline hydrochloride

rubber accelerator
I dipheny lamine­ plastics stabilizer
dyes rocket propellants
production of pesticides
hydrochlorides­
amine hydrochlorides ­ pharmaceuticals

hydrazine dihydrochloride­ ­chlorine scavenger

for hydrogen
other hydrochlorides chloride gas
streams

Figure 5 ­ Hydrochloric acid derivatives. Source / 8 / .

63
 Figure 6 - Differences of Consequences Index - Actual/Potential Danger Index (FACTS).

Figure 7 - Differences of Consequences Index - Actual/Potential Danger Index (MHIDAS).

64
 Figure 8 - Differences of Consequences Index - Actual/Potential Danger Index (SONATA).

10

Figure 9 - Differences of Consequences Index - Actual/Potential Danger Index (Handbook

Störfälle).

65
Figúrelo- Differences of Consequences Index - Actual/Potential Danger Index (MARS
accidents involving chlorine).

Figure 11 - Difference of Intervention Index-Consequence Index (FACTS).

66
 -5 -4 -3 -2

Figure 12 - Difference of Intervention Index-Consequence Index (MHIDAS).

Figure 13 - Difference of Intervention Index-Consequence Index (SONATA).

67
 Figure 14 - Difference of Intervention Index-Consequence Index (Handbook Störfälle).

Figure 15 - Difference of Intervention Index - Actual/Potential Danger Index (FACTS).

68
Figure 16 - Difference of Intervention Index - Actual/Potential Danger Index (MHIDAS).

Figure 17 - Difference of Intervention Index - Actual/Potential Danger Index (SONATA).

69
Figure18-Difference of Intervention Index - Actual/Potential Danger Index (Handbook
Störfälle).

70
 APPENDIX 1
Samples of STOER Output Files
== STOER V2.00 == 02.02.1992 =======================================
CASE 7
**********************
* Eingabeparameter *
**********************

Gasart: Chlor
Freisetzungsform: unter Druck verflüssigt
Standortparameter:
Ausbreitungsgebiet: ebenes Gelände ohne Hindernisse
Rauhigkeitsklasse 3 Z0 = .50 m
mittlere Bebauungshöhe .0 m
Quellparameter der Punktquelle:
Quellabmessungen XQ = .0 m
YQ = .0 m
ZQ = .0 m
Quellhöhe .5 πι
Emissionsdauer 360. s
o. Lachenanteil: .139E+05 g
*************************************
* Ergebnis der Schwergasausbreitung *
*************************************

Freigesetzt wurden insgesamt .5004E+07 g Chlor

Berechnete Freisetzungsart: kontinuierlich
Char. Länge Lcc= 1.0 m
Char. Geschwindigkeit Uc = 4.5 m/s
Gaskonzentration am Kopplungspunkt: .300E+05 mg/m**3
Diese 1% der Anfangsvolumenkonzentration werden erreicht bei der
- mittleren Ausbreitungssituation:
in einer Quellentfernung von 243.7 m
- ungünstigsten Ausbreitungssituation:
in einer Quellentfernung von 300.6 m
Mindestwert für 1. Aufpunkt in Blatt 1
XA= 1218.7m (mittlere Ausbreitungssituation)
XA = 1503.1 m (ungünst. Ausbreitungssituation)
**************************************
* Berechnung aller Immissionsdaten *
**************************************

Aufpunktkoordinaten : XA= 400. m ; YA= o. m ; ZA= 0. m

Für diesen Aufpunkt müssen die Konzentrationen interpoliert werden.
vorgegebene Ausbreitungssituation
Ausbreitungsklasse 2 Schichtung: indifferent
keine Inversion
Windgeschwindigkeit in Anemometerhöhe 2.0 m/s
Transportgeschwindigkeit 1.6 m/s

73
 Zeit (s) Kon:Konzentration(mg/m**3)
123.4 .206E+04
149.3 .379E+04
175.3 .431E+04
201.3 .371E+04
227.2 .257E+04
253.2 .167E+04

höchste Konzentration 4307. mg/m**3

nach 175. s
Dosis .2934E+07 mg*s/m**3

== STOER V2.00 == 02.02.1992

CASE 7
**********************
* Eingabeparameter *
**********************

Gasart: Chlor
Freisetzungsform: unter Druck verflüssigt
Standortparameter:
Ausbreitungsgebiet: ebenes Gelände ohne Hindernisse
Rauhigkeitsklasse 3 Z0 = .50 m
mittlere Bebauungshöhe .0 m

Quellparameter der Flächenquelle:

Quellabmessungen XQ = 3.0 m
YQ = 2.5 m
ZQ = .0 m
Quellhöhe .5 m
Emissionsdauer 360. s
Freigesetzte Masse o. Lachenanteil : .139E+05 g
*************************************
* Ergebnis der Schwergasausbreitung *
*************************************

Freigesetzt wurden insgesamt .5004E+07 g Chlor

Berechnete Freisetzungsart: kontinuierlich
Char. Länge Lcc= 1.0 m
Char. Geschwindigkeit Uc = 4.5 m/s
Gaskonzentration am Kopplungspunkt: .300E+05 mg/m**3
Diese 1% der Anfangsvolumenkonzentration werden erreicht bei der
- mittleren Ausbreitungssituation:
in einer Quellentfernung von 243.7 m
- ungünstigsten Ausbreitungssituation:
in einer Quellentfernung von 300.6 m

74
 Mindestwert für 1. Aufpunkt in Blatt 1
XA = 1218.7 m (mittlere Ausbreitungssituation)
XA = 1503.1 m (ungünst. Ausbreitungssituation)
**************************************
* Berechnung aller Immissionsdaten *
**************************************

Aufpunktkoordinaten: XA= 400. m ; YA= 0. m ; ZA= 0. m

Für diesen Aufpunkt müssen die Konzentrationen interpoliert werden.
vorgegebene Ausbreitungssituation
Ausbreitungsklasse 2 Schichtung: indifferent
keine Inversion
Windgeschwindigkeit in Anemometerhöhe 2.0 m/s
Transportgeschwindigkeit 1.6 m/s
Zeit (s) Konzentration (mg/m**3)
123.4 .381E+04
149.5 .704E+04
175.6 .800E+04
201.7 .686E+04
227.9 .474E+04
254.0 .308E+04
höchste Konzentration 7999. mg/m**3
nach 176. s
Dosis .5466E+07 mg*s/m**3

== STOER V2.00 == 02.02.1992 ========================================

CASE 7
**********************
* Eingabeparameter *
**********************

Gasart: Chlor
Freisetzungsform: unter Druck verflüssigt
Standortparameter:
Ausbreitungsgebiet: ebenes Gelände ohne Hindernisse
Rauhigkeitsklasse 3 Z0 = .50 m
mittlere Bebauungshöhe .0 m
Quellparameter der Flächenquelle:
Quellabmessungen XQ = 3.0 m
YQ = 2.5 m
ZQ = .0 m
Quellhöhe .5 m
Emissionsdauer 360. s
Freigesetzte Masse o. Lachenanteil: .139E+05 g

75
*************************************
* Ergebnis der Schwergasausbreitung *
*************************************

Freigesetzt wurden insgesamt .5004E+07 g Chlor

Berechnete Freisetzungsart: kontinuierlich
Char. Länge Lcc= 1.0 m
Char. Geschwindigkeit Uc = 4.5 m/s
Gaskonzentration am Kopplungspunkt: .300E+05 mg/m**3
Diese 1% der Anfangsvolumenkonzentration werden erreicht bei der
- mittleren Ausbreitungssituation:
in einer Quellentfernung von 243.7 m
- ungünstigsten Ausbreitungssituation:
in einer Quellentfernung von 300.6 m
Mindestwert für 1. Aufpunkt in Blatt 1
XA = 1218.7 m (mittlere Ausbreitungssituation)
XA = 1503.1 m (ungünst. Ausbreitungssituation)
**************************************
* Berechnung aller Immissionsdaten *
**************************************

Aufpunktkoordinaten : XA= 400. m ; YA= 0. m ; ZA= 0. m

Für diesen Aufpunkt müssen die Konzentrationen interpoliert werden.
vorgegebene Ausbreitungssituation
Ausbreitungsklasse 2 Schichtung: indifferent
keine Inversion
Windgeschwindigkeit in Anemometerhöhe 4.0 m/s
Transportgeschwindigkeit 3.1 m/s
Zeit (s) Konzentration (mg/m**3)
86.0 .295E+04
105.9 .563E+04
125.8 .608E+04
145.6 .585E+04
165.5 .384E+04
185.4 .220E+04
höchste Konzentration 6119. mg/m**3
nach 136. s
Dosis .3292E+07 mg*s/m**3

== STOER V2.00 == 02.02.1992

CASE 7
**********************
* Eingabeparameter *

76
**********************

Gasart: Chlor
Freisetzungsform: unter Druck verflüssigt
Standortparameter:
Ausbreitungsgebiet: ebenes Gelände ohne Hindernisse
Rauhigkeitsklasse 3 ZO = .50 m
mittlere Bebauungshöhe .0 m
Quellparameter der Flächenquelle:
Quella'bmessungen XQ = 3.0 m
YQ = 2.5 m
ZQ = .0 m
Quellhöhe .5 m
Emissionsdauer 360. s
Freigesetzte Masse o. Lachenanteil:: .139E+05
.139E+05 g
*************************************
* Ergebnis der Schwergasausbreitung *
*************************************

Freigesetzt wurden insgesamt .5004E+07 g Chlor

Berechnete Freisetzungsart: kontinuierlich
Char. Länge Lcc= 1.0 m
Char. Geschwindigkeit Uc = 4.5 m/s
Gaskonzentration am Kopplungspunkt: .300E+05 mg/m**3
Diese 1% der Anfangsvolumenkonzentration werden erreicht bei der
- mittleren Ausbreitungssituation:
in einer Quellentfernung von 243.7 m
- ungünstigsten Ausbreitungssituation:
in einer Quellentfernung von 300.6 m
Mindestwert für 1. Aufpunkt in Blatt 1
XA = 1218.7 m (mittlere Ausbreitungssituation)
XA = 1503.1 m (ungünst. Ausbreitungssituation)
**************************************
* Berechnung aller Immissionsdaten *
**************************************

Aufpunktkoordinaten : XA= 400. m ; YA= 0. m ; ZA= 0. m

Für diesen Aufpunkt müssen die Konzentrationen interpoliert werden.
mittlere Ausbreitungssituation
Ausbreitungsklasse 2 Schichtung: indifferent
keine Inversion
Windgeschwindigkeit in Anemometerhöhe 4.0 m/s
Transportgeschwindigkeit 3.1 m/s
Zeit (s) Konzentration (mg/m**3)
86.0 .295E+04
105.9 .563E+04
125.8 .608E+04
145.6 .585E+04

77
 165.5 .384E+04
185.4 .220E+04

höchste Konzentration 6119. mg/m**3

nach 136. s

Dosis .3292E+07 mg*s/m**3

Ausbreitungsklasse 1 Schichtung: stabil

mit Inversion in einer Höhe von 20.0 m
Transportgeschwindigke:it 1.0 m/s

Zeit (s) Konzentration (mg/m**3;)

151.2 .147E+05
165.6 .220E+05
180.0 .249E+05
194.3 .239E+05
208.7 .199E+05
223.1 .151E+05

höchste Konzentration .2503E+05 mg/m**3

nach 184. s

Dosis .2098E+08 mg*s/m**3

ungünstigste Ausbreitungssituation
Ausbreitungsklasse 1 Schichtung: stabil
mit Inversion in einer Höhe von 20.0 m
Transportgeschwindigkeit 1.0 m/s
Maximaldosis .2098E+08 mg*s/m**3

ungünstigste Ausbreitungssituation
Ausbreitungsklasse 1 Schichtung: stabil
mit Inversion in einer Höhe von 20.0 m
Transportgeschwindigkeit 1.0 m/s
Maximalkonzentration .2503E+05 mg/m**3
nach 184. s

78
== STOER V2.00 == 02.02.1992 ========================================
CASE 7b
**********************
* Eingabeparameter *
**********************

Gasart: Chlor
Freisetzungsform: unter Druck verflüssigt
Standortparameter:
Ausbreitungsgebiet: ebenes Gelände ohne Hindernisse
Rauhigkeitsklasse 3 Z0 = .50 m
mittlere Bebauungshöhe .0 m

lellparameter der Punktquelle:

Quellabmessungen XQ = .0 m
YQ = .0 m
ZQ = .0 m
Quellhöhe .5 m
Emissionsdauer 360. s
Freigesetzte Masse o. Lachenanteil: .139E+05 g
*************************************
* Ergebnis der Schwergasausbreitung *
*************************************

Freigesetzt wurden insgesamt .5004E+07 g Chlor

Berechnete Freisetzungsart: kontinuierlich
Char. Länge Lcc= 1.0 m
Char. Geschwindigkeit Uc = 4.5 m/s
Gaskonzentration am Kopplungspunkt: .300E+05 mg/m**3
Diese 1% der Anfangsvolumenkonzentration werden erreicht bei der
- mittleren Ausbreitungssituation:
in einer Quellentfernung von 243.7 m
- ungünstigsten Ausbreitungssituation:
in einer Quellentfernung von 300.6 m
Mindestwert für 1. Aufpunkt in Blatt 1
XA = 1218.7 m (mittlere Ausbreitungssituation)
XA = 1503.1 m (ungünst. Ausbreitungssituation)
**************************************
* Berechnung aller Immissionsdaten *
**************************************

Aufpunktkoordinaten : XA= 400. m ; YA= 0. m ; ZA= 0. m

Für diesen Aufpunkt müssen die Konzentrationen interpoliert werden.
vorgegebene Ausbreitungssituation
Ausbreitungsklasse 2 Schichtung: indifferent
keine Inversion
Windgeschwindigkeit in Anemometerhöhe 6.0 m/s
Transportgeschwindigkeit 4.7 m/s

79
 Zeit (s) Konzentration (mg/m**3)
72.1 .117E+04
90.5 .232E+04
108.9 .245E+04
127.4 .244E+04
145.8 .157E+04
164.2 875.
höchste Konzentration 2460. mg/m**3
nach 123. s
Dosis .1245E+07 mg*s/m**3

== STOER V2.00 == 02.02.1992 ========================================

CASE 7b
**********************
* Eingabeparameter *
**********************

Gasart: Chlor
Freisetzungsform: unter Druck verflüssigt
Standortparameter:
Ausbreitungsgebiet: ebenes Gelände ohne Hindernisse
Rauhigkeitsklasse 3 Z0 = .50 m
mittlere Bebauungshöhe .0 m
Quellparameter der Flächenquelle:
Quellabmessungen XQ = 3.0 m
YQ = 2.5 m
ZQ = .0 m
Quellhöhe .5 m
Emissionsdauer 360. s
Freigesetzte Masse o. Lachenanteil: .139E+05 g
*************************************
* Ergebnis der Schwergasausbreitung *
*************************************

Freigesetzt wurden insgesamt .5004E+07 g Chlor

Berechnete Freisetzungsart: kontinuierlich
Char. Länge Lcc= 1.0 m
Char. Geschwindigkeit Uc = 4.5 m/s
Gaskonzentration am Kopplungspunkt: .300E+05 mg/m**3
Diese 1% der Anfangsvolumenkonzentration werden erreicht bei der
- mittleren Ausbreitungssituation:
in einer Quellentfernung von 243.7 m
- ungünstigsten Ausbreitungssituation:
in einer Quellentfernung von 300.6 m

80
 Mindestwert für 1. Aufpunkt in Blatt 1
XA = 1218.7 m (mittlere Ausbreitungssituation)
XA = 1503.1 m (ungünst. Ausbreitungssituation)
**************************************
* Berechnung aller Imraissionsdaten *
**************************************

Aufpunktkoordinaten: XA= 400. m ; YA= 0. m ; ZA= 0. m

Für diesen Aufpunkt müssen die Konzentrationen interpoliert werden.
vorgegebene Ausbreitungssituation
Ausbreitungsklasse 2 Schichtung: indifferent
keine Inversion
Windgeschwindigkeit in Anemometerhöhe 6.0 m/s
Transportgeschwindigkeit 4.7 m/s
Zeit (s) Konzentration (mg/m**3)
72.1 .217E+04
90.7 .431E+04
109.3 .454E+04
127.9 .452E+04
146.4 .286E+04
165.0 .159E+04
höchste Konzentration 4568. mg/m**3
nach 122. s
Dosis .2320E+07 mg*s/m**3

81
== STOER V2.00 == 02.02.1992 ========================================
CASE 10
**********************
* Eingabeparameter *
**********************

Gasart: Chlor
Freisetzungsform: unter Druck verflüssigt
Standortparameter :
Ausbreitungsgebiet: ebenes Gelände ohne Hindernisse
Rauhigkeitsklasse 3 Z0 = .50 m
mittlere Bebauungshöhe .0 m
Quellparameter der Punktquelle:
Quellabmessungen XQ = .0 m
YQ = .0 m
ZQ = .0 m
Quellhöhe .5 m
Emissionsdauer 600. s
Freigesetzte Masse o. Lachenanteil: .110E+04 g
*************************************
* Ergebnis der Schwergasausbreitung *
*************************************

Freigesetzt wurden insgesamt .6600E+06 g Chlor

Berechnete Freisetzungsart: kontinuierlich
Char. Länge Lcc= .4 m
Char. Geschwindigkeit Uc = 2.7 m/s
Gaskonzentration am Kopplungspunkt: .300E+05 mg/m**3
Diese 1% der Anfangsvolumenkonzentration werden erreicht bei der
- mittleren Ausbreitungssituation:
in einer Quellentfernung von 88.4 m
- ungünstigsten Ausbreitungssituation:
in einer Quellentfernung von 109.0 m
Mindestwert für 1. Aufpunkt in Blatt 1
XA = 441.8 m (mittlere Ausbreitungssituation)
XA = 544.9 m (ungünst. Ausbreitungssituation)
**************************************
* Berechnung aller Immissionsdaten *
**************************************

Aufpunktkoordinaten: XA= 900. m ; YA= 0. m ; ZA= 2. m

vorgegebene Ausbreitungssituation
Ausbreitungsklasse 2 Schichtung: indifferent
keine Inversion
Windgeschwindigkeit in Anemometerhöhe 2.0 m/s
Transportgeschwindigkeit 1.6 m/s

83
 Zeit (s) Konzentration (mg/m**3)
403.9 .437
605.9 5.07
807.9 6.70
1009.9 6.40
1211.9 1.79
1413.9 .247
höchste Konzentration 6.869 mg/m**3
nach 927. s
Dosis 4169. mg*s/m**3

== STOER V2.00 == 02.02.1992 ========================================

CASE 10
**********************
* Eingabeparameter *
**********************

Gasart: Chlor
Freisetzungsform: unter Druck verflüssigt
Standortparameter :
Ausbreitungsgebiet: ebenes Gelände ohne Hindernisse
Rauhigkeitsklasse 3 Z0 = .50 m
mittlere Bebauungshöhe .0 m
Quellparameter der Flächenquelle:
Quellabmessungen XQ = 2.0 m
YQ = 2.0 m
ZQ = .0 m
Quellhöhe .5 m
Emissionsdauer 600. s
Freigesetzte Masse o. Lachenanteil: .110E+04 g
*************************************
* Ergebnis der Schwergasausbreitung *
*************************************

Freigesetzt wurden insgesamt .6600E+06 g Chlor

Berechnete Freisetzungsart: kontinuierlich
Char. Länge Lcc= .4 m
Char. Geschwindigkeit Uc = 2.7 m/s
Gaskonzentration am Kopplungspunkt: .300E+05 mg/m**3
Diese 1% der Anfangsvolumenkonzentration werden erreicht bei der
- mittleren Ausbreitungssituation:
in einer Quellentfernung von 88.4 m
- ungünstigsten Ausbreitungssituation:
in einer Quellentfernung von 109.0 m

84
 Mindestwert für 1. Aufpunkt in Blatt 1
XA = 441.8 m (mittlere Ausbreitungssituation)
XA = 544.9 m (Ungunst. Ausbreitungssituation)
**************************************
* Berechnung aller Immissionsdaten *
**************************************

Aufpunktkoordinaten: XA= 900. m ; YA= 0. m ; ZA= 2. m

vorgegebene Ausbreitungssituation
Ausbreitungsklasse 2 Schichtung: indifferent
keine Inversion
Windgeschwindigkeit in Anemometerhöhe 2.0 m/s
Transportgeschwindigkeit 1.6 m/s

Zeit (s) Konzentration (mg/m**3)

403.9 1.72
605.9 20.2
807.9 26.7
1009.9 25.6
1211.9 7.17
1413.9 .994

höchste Konzentration 27.42 mg/m**3

nach 927, s
Dosis 1664E+05 mg*s/m**3

== STOER V2.00 == 02.02.1992 ======

CASE 10
**********************
* Eingabeparameter *
**********************

Gasart: Chlor
Freisetzungsform: unter Druck verflüssigt
Standortparameter :
Ausbreitungsgebiet: ebenes Gelände ohne Hindernisse
Rauhigkeitsklasse 3 Z0 = .50 m
mittlere Bebauungshöhe .0 m

Quellparameter der Flächenquelle:

Quellabmessungen XQ = 2.0 m
YQ = 2.0 m
ZQ = .0 m
Quellhöhe .5 m
Emissionsdauer 600. s
Freigesetzte Masse o. Lachenanteil : .110E+04 g

*************************************
* Ergebnis der Schwergasausbreitung *

85
*************************************

Freigesetzt wurden insgesamt .6600E+06 g Chlor

Berechnete Freisetzungsart: kontinuierlich
Char. Länge Lcc= .4 m
Char. Geschwindigkeit Uc = 2.7 m/s
Gaskonzentration am Kopplungspunkt : .300E+05 mg/m**3
Diese 1% der Anfangsvolumenkonzentration werden erreicht bei der
- mittleren Ausbreitungssituation:
in einer Quellentfernung von 88.4 m
- ungünstigsten Ausbreitungssituation:
in einer Quellentfernung von 109.0 m
Mindestwert für 1. Aufpunkt in Blatt 1
XA = 441.8 m (mittlere Ausbreitungssituation)
XA = 544.9 m (ungünst. Ausbreitungssituation)
**************************************
* Berechnung a l l e r Immissionsdaten *
**************************************

Aufpunktkoordinaten : XA= 900. m ; YA= 0. m ; ZA= 2. m

vorgegebene Ausbreitungssituation —
Ausbreitungsklasse 2 Schichtung: indifferent
keine Inversion
Windgeschwindigkeit in Anemometerhöhe 4.0 m/s
Transportgeschwindigkeit 3.1 m/s
Zeit (s) Konzentration (mg/m**3)
218.9 .909
383.9 9.23
548.9 10.1
713.9 10.2
878.9 5.25
1043.9 .357
höchste Konzentration 10.20 mg/m**3
nach 745. s
Dosis 5953. mg*s/m**3

== STOER V2.00 == 02.02.1992

CASE 10
**********************
* Eingabeparameter *
**********************
Gasart: Chlor

86
Freisetzungsform: unter Druck verflüssigt
Standortparameter:
Ausbreitungsgebiet : ebenes Gelände ohne Hindernisse
Rauhigkeitsklasse 3 ZO = .50 m
mittlere Bebauungshöhe .0 m
Quellparameter der Flächenquelle:
Quellabmessungen XQ = 2.0 m
YQ = 2.0 m
ZQ = .0 m
Quellhöhe .5 m
Emissionsdauer 600. s
Freigesetzte Masse o. Lachenanteil:: .110E+04 g
*************************************
* Ergebnis der Schwergasausbreitung *
*************************************

Freigesetzt wurden insgesamt .6600E+06 g Chlor

Berechnete Freisetzungsart: kontinuierlich
Char. Länge Lcc= .4 m
Char. Geschwindigkeit Uc = 2.7 m/s
Gaskonzentration am Kopplungspunkt: .300E+05 mg/m**3
Diese 1% der Anfangsvolumenkonzentration werden erreicht bei der
- mittleren Ausbreitungssituation:
in einer Quellentfernung von 88.4 m
- ungünstigsten Ausbreitungssituation:
in einer Quellentfernung von 109.0 m
Mindestwert für 1. Aufpunkt in Blatt 1
XA = 441.8 m (mittlere Ausbreitungssituation)
XA = 544.9 m (Ungunst. Ausbreitungssituation)
**************************************
* Berechnung a l l e r Immissionsdaten *
**************************************

Aufpunktkoordinaten: XA= 900. m ; YA= 0. m ; ZA= 2. m

mittlere Ausbreitungssituation
Ausbreitungsklasse 2 Schichtung: indifferent
keine Inversion
Windgeschwindigkeit in Anemometerhöhe 4.0 m/s
Transportgeschwindigkeit 3.1 m/s
Zeit (s) Konzentration (mg/m**3)
218. .909
383. 9.23
548. 10.1
713. 10.2
878. 5.25
1043.9 .357
höchste Konzentration 10.20 mg/m**3

87
 nach 745. s

Dosis 5953. mg*s/m**3

Ausbreitungsklasse 1 Schichtung: stabil

mit Inversion in einer Höhe von 20.0 m
Transportgeschwindigkeit 1.0 m/s

Zeit (s) Konzentration (mg/m**3)

697.7 45.2
887.7 529.
1077.7 770.
1267.7 779.
1457.7 350.
1647.7 43.7

höchste Konzentration 793.1 mg/m**3

nach 1213. s

Dosis .4781E+06 mg*s/m**3

Ausbreitungsklasse 2 Schichtung: indifferent

mit Inversion in einer Höhe von 20.0 m
Transportgeschwindigkeit 1.0 m/s

Zeit (s) Konzentration (mg/m**3)

629.7 27.2
871.7 272.
1113.7 422.
1355.7 318.
1597.7 97.0
1839.7 21.7

höchste Konzentration 431.5 mg/m**3

nach 1180. s

Dosis .2802E+06 mg*s/m**3

Ausbreitungsklasse 3 Schichtung: labil

mit Inversion in einer Höhe von 20.0 m
Transportgeschwindigkeit 1.0 m/s

Zeit (s) Konzentration (mg/m**3)

563.7 16.5
858.7 169.
1153.7 244.
1448.7 123.
1743.7 39.5
2038.7 13.1

höchste Konzentration 244.5 mg/m**3

nach 1154. s

Dosis .1787E+06 mg*s/m**3

88
 ungünstigste Ausbreitungssituation
Ausbreitungsklasse 1 Schichtung: stabil
mit Inversion in einer Höhe von 20.0 m
Transportgeschwindigkeit 1.0 m/s
Maximaldosis .4781E+06 mg*s/m**3

'■ ungünstigste Ausbreitungssituation

Ausbreitungsklasse 1 Schichtung: stabil
mit Inversion in einer Höhe von 20.0 m
Transportgeschwindigkeit 1.0 m/s
Maximalkonzentration 793.1 mg/m**3
nach 1213. s

89
 APPENDIX 2
Samples of HEGADAS Input and Output Files
 TITLE HEGADAS-S CASE 7
ICNT = 0 CONTOURS OR CONTENTS CODE
ISORF = 2 SURFACE TRANSFER CODE
*
POOL DATA

PLL 3.00 *H SOURCE LENGTH

PLHW = 2.50 *M SOURCE HALF-WIDTH
*
AMBIENT CONDITIONS

zo 10. kH REFERENCE HEIGHT

ÜO 4.0 k K/S WIND VELOCITY AT HEIGHT ZO
AIRTEMP = 15.0 k DEG.CELSIOS AIR TEKP. AT GROUND LEVEL
RH 0.6 RELATIVE HOHIDITY
TGROÜND = 15.0 ► DEG.CELSIOS EARTH-S SURFACE TEMPERATURE

DISP

ROUGH = 0.3E-01 i* M SURFACE ROUGHNESS PARAMETER

MONIN = -20.000 '* K MONIN - OBOKHOV LENGTH
CROSSW = 0.064 ik H**(1-BETA) CROSSWIND (DELTA)
0.905 ' (BETA)
*
CLOUD
4
XSTEP = 10.0 t OUTPUT STEP LENGTH
XMAX = 500. * X AT WHICH CALC. IS STOPPED
CAMIH = 0.0000001 * KG/H3 CA AT WHICH CALC. IS STOPPED
CO 0.035 * KG/H3 OPPER CONCENTRATION LIMIT
CL 0.017 * KG/M3 LOWER CONCENTRATION LIMIT
if

SOURCE
4
FLUX 0.927 * KG/H2/S GAS EMISSION FLUX
TEMPGAS = 15. * DEG.CELSIOS TEMPERATORE OF EMITTED GAS
CPGAS = 29.16 * J/HOLE/'DEG.C SPECIFIC HEAT OF EHITTED GAS
HWGAS = 71.00 * KG/KMOLE MOL. WEIGHT OF EMITTED GAS
WATGAS = 0. * MOLAR FRACTION PICKED-UP WATE
*

93
ÏHSHAIN HEGADAS-S PROGRAM ( VERSION AÜG88 PAGE 0
DATE 03/02/92 TIME 04:57

«« HEGADAS-S CASE 7 »»

CALCULATION CODE ICNT = 0

SURFACE BEAT TRANSFER MODEL ISURF = 2
THERMODYNAMIC MODEL THERMOD = NORMAL
SOURCE LENGTH PLL = 3.0000 M
SOURCE HALF-WIDTH PLW = 2.5000 M
WIND VELOCITY AT HEIGHT ZO UO = 4.0000 M/S
REFERENCE HEIGHT ZO = 10.000 M
SURFACE ROUGHNESS PARAMETER ZR = 0.30000E-01 M
AIR TEMP. AT GROUND LEVEL TAP = 15.000 DEG.CELSIUS
HONIN - OBUKHOV LENGTH OBUKL = -20.000 H
DELTA = 0.64000E-01 M**(1-BETA)
BETA = 0.90500
SPREADING CONSTANT CE = 1.1500
OUTPUT STEP LENGTH DXO = 10.000
X AT WHICH CALC. IS STOPPED XMAX = 500.00
CA AT WHICH CALC. IS STOPPED CAMIN = 0.10000E-06 KG/H3
UPPER CONCENTRATION LIMIT CU = 0.35000E-01 KG/M3
LOWER CONCENTRATION LIMIT CL = 0.17000E-01 KG/M3
EVAPORATION FLUX Q = 0.92700 KG/M2/S = 13.905 KG/S
RELATIVE HUMIDITY R = 0.60000
TEMPERATURE OF EMITTED GAS TGE = 15.000 DEG.CELSIUS
SPECIFIC HEAT OF EMITTED GAS CPG = 29.160 J/HOLE/DEG.CELSIUS
MOL. WEIGHT OF EMITTED GAS FMG = 71.000 KG/KHOLE
EARTH-S SURFACE TEMPERATURE TW2P = 15.000 DEG.CELSIUS
MOLAR FRACTION PICKED-UP WATER W2P = O.OOOOOE+00
HEAT GROUP IN HEAT FLUX QH HEATGR = 24.000

WIND PROFILE EXPONENT ALPHA = 0.18340

USTAR = 0.33622E+00 M/S

LENGTH GAS BLANKET L = 0.75848E+01 H

WIDTH GAS BLANKET Β = 0.63207E+01 M
1HSMAIN HEGADAS-S PROGRAM ( VERS PAGE 1
DATE 03/02/92 TIME 04:57

«« HEGADAS-S CASE 7 »»

DISTANCE CA SZ SY IH DP YCU ZCU YCL ZCL I

R B TMP CONC
(H) (KG/M3) (Η) ( Η ) " (H) (H) (M) (H) (H) (DEG.C) (I VOL.)
**********************************************************************************

-.379E+01 0.300E+01 0.00 0.00 6.32 6.32 0.00 6.32 0.00

0.379E+O1 0.300E+01 0.22 0.00 6.32 6.32 0.77 6.32 0.88 26.023 15.0 0.100E+03

TAKE-UP FLUX = 0.1451 KG/M2/S = 13.9117 KG/S

0.721E+02 0.543E-01 1.51 12.67 24.13 32.53 0.76 37.79 1.72 1.767 15.0 0.181E+01
0.148E+03 0.830E-02 5.42 21.88 31.78 0.00 0.00 0.00 0.00 -4.767 15.0 0.276E+00
0.224E+03 0.262E-02 12.30 29.62 35.26 0.00 0.00 0.00 0.00 -14.743 15.0 0.872E-01
0.30OE+O3 0.123E-02 20.98 36.51 37.16 0.00 0.00 0.00 0.00 -27.268 15.0 0.410E-01

94
 0.375E+03 0.706E-03 31.08 42.82 38.26 0.00 0.00 0.00 0.00 -41.892 15.0 0.235E-01
0.451E+03 0.454E-03 42.42 48.71 38.87 0.00 0.00 0.00 0.00 -58.365 15.0 0.151E-01
0.527E+03 0.315E-03 54.83 54.27 39.16 0.00 0.00 0.00 0.00 -76.475 15.0 0.105E-01
0.603E+03 0.231E-03 68.21 59.56 39.23 0.00 0.00 0.00 0.00 -96.043 15.0 0.767E-02
0.679E+03 0.176E-03 82.49 64.63 39.12 0.00 0.00 0.00 0.00 -116.970 15.0 0.585E-02
0.755E+03 0.138E-03 97.64 69.51 38.87 0.00 0.00 0.00 0.00 -139.227 15.0 0.460E-02
0.831E+03 0.111E-03 113.57 74.23 38.52 0.00 0.00 0.00 0.00 -162.648 15.0 0.370E-02
0.906E+03 0.914E-04 130.25 78.80 38.08 0.00 0.00 0.00 0.00 -187.204 15.0 0.304E-02
0.982E+03 0.764E-04 147.62 83.25 37.57 0.00 0.00 0.00 0.00 -212.827 15.0 0.254E-O2
0.106E+04 0.648E-04 165.68 87.59 36.99 0.00 0.00 0.00 0.00 -239.478 15.0 0.216E-02
0.113E+04 0.555E-04 184.38 91.82 36.37 0.00 0.00 0.00 0.00 -267.112 15.0 0.185E-02
0.121E+04 0.481E-04 203.70 95.96 35.70 0.00 0.00 0.00 0.00 -295.684 15.0 0.160E-02
0.129E+04 0.421E-04 223.62 100.01 35.00 0.00 0.00 0.00 0.00 -325.157 15.0 0.140E-02
0.136E+04 0.371E-04 244.12 103.99 34.26 0.00 0.00 0.00 0.00 -355.516 15.0 0.124E-02
0.144E+04 0.329E-04 265.23 107.89 33.49 0.00 0.00 0.00 0.00 -386.781 15.0 0.110E-02
0.151E+04 0.294E-04 286.87 111.72 32.70 0.00 0.00 0.00 0.00 -418.878 15.0 0.979E-03
0.159E+04 0.264E-04 309.04 115.49 31.88 0.00 0.00 0.00 0.00 -451.765 15.0 0.880E-03
0.166E+04 0.239E-04 331.73 119.21 31.04 0.00 0.00 0.00 0.00 -485.431 15.0 0.795E-03
0.174E+04 0.217E-04 354.93 122.86 30.18 0.00 0.00 0.00 0.00 -519.870 15.0 0.721E-O3
0.182E+04 0.197E-O4 378.62 126.47 29.30 0.00 0.00 0.00 0.00 -555.053 15.0 0.657E-03
0.189E+04 0.181E-04 402.77 130.02 28.42 0.00 0.00 0.00 0.00 -590.964 15.0 0.601E-03
0.197E+04 0.166E-04 427.37 133.53 27.52 0.00 0.00 0.00 0.00 -627.535 15.0 0.552E-03
0.204E+04 0.153E-04 452.45 136.99 26.61 0.00 0.00 0.00 0.00 -664.807 15.0 0.508E-O3
0.212E+04 0.141E-04 477.96 140.41 25.69 0.00 0.00 0.00 0.00 -702.767 15.0 0.470E-03
0.220E+04 0.131E-04 503.92 143.79 24.76 0.00 0.00 0.00 0.00 -741.377 15.0 0.435E-03
0.227E+04 0.121E-04 530.30 147.14 23.82 0.00 0.00 0.00 0.00 -780.648 15.0 0.404E-03
0.235E+04 0.113E-04 557.10 150.44 22.88 0.00 0.00 0.00 0.00 -820.534 15.0 0.377E-03
0.242E+04 0.106E-04 584.33 153.71 21.92 0.00 0.00 0.00 0.00 -861.078 15.0 0.351E-03
0.250E+04 0.988E-05 611.98 156.95 20.95 0.00 0.00 0.00 0.00 -902.249 15.0 0.329E-03
0.258E+04 0.926E-05 640.01 160.16 19.98 0.00 0.00 0.00 0.00 -944.000 15.0 0.308E-03
0.265E+04 0.870E-05 668.45 163.33 19.00 0.00 0.00 0.00 0.00 -986.318 15.0 0.290E-O3
0.273E+04 0.818E-05 697.30 166.48 18.01 0.00 0.00 0.00 o.oo ******** 15.0 0.272E-03
0.280E+04 0.771E-05 726.53 169.59 17.02 0.00 0.00 0.00 o.oo ******** 15.0 0.257E-03
0.288E+04 0.728E-05 756.10 172.68 16.03 0.00 0.00 0.00 o.oo ******** 15.0 0.242E-03
0.295E+04 0.689E-05 786.03 175.74 15.04 0.00 0.00 0.00 o.oo ******** 15.0 0.229E-03
0.303E+04 0.652E-05 816.31 178.78 14.04 0.00 0.00 0.00 o.oo ******** 15.0 0.217E-03
0.311E+04 0.618E-05 846.96 181.79 13.05 0.00 0.00 0.00 o.oo ******** 15.0 0.206E-03
0.318E+04 0.587E-05 877.98 184.78 12.04 0.00 0.00 0.00 o.oo ******** 15.0 0.195E-03
0.326E+O4 0.558E-05 909.33 187.74 11.04 0.00 0.00 0.00 o.oo ******** 15.0 0.186E-03
0.333E+04 0.531E-05 940.99 190.68 10.04 0.00 0.00 0.00 o.oo ******** 15.0 0.177E-03
LHSHAIN HEGADAS-S PROGKAK ( VERSION AÜG88 ) PAGE 2
DATE 03/02/92 TIME 04:57

«« HEGADAS-S CASE 7 »»

DISTANCE CA SZ SY HIDP YCU ZCU YCL ZCL III· TKP CONC

(H) (KG/H3) (H) (H) (H) (H) (H) (H) m (DEG.C) (t VOL.)
**************************************************************************************************************

0.341E+04 0.506E-05 972.99 193.60 9.04 0.00 0.00 0.00 O.oo ******** 15.0 0.168E-03
0.349E+04 0.482E-05 1005.32 196.50 8.04 0.00 0.00 0.00 o.oo ******** 15.0 0.161E-03
0.356E+04 0.461E-05 1037.99 199.38 7.04 0.00 0.00 0.00 o.oo ******** 15.0 0.153E-03
0.364E+04 0.440E-05 1071.03 202.24 6.02 0.00 0.00 0.00 o.oo ******** 15.0 0.146E-03
0.371E+04 0.421E-05 1104.42 205.08 5.00 0.00 0.00 0.00 o.oo ******** 15.0 0.140E-03
0.379E+04 0.403E-05 1138.20 207.90 3.96 0.00 0.00 0.00 o.oo ******** 15.0 0.134E-03

95
TITLE HEGADÀS-S CASE 10
ICHT = 0 CONTOURS OR CONTENTS CODE
ISURF = 2 SURFACE TRANSFER CODE

POOL' DATA

PLL = 2.00 *k M SOURCE LENGTH

PLHW =: 2.00 *k H SOURCE HALF-WIDTH

AMBIENT CONDITIONS <

zo = 10. <k K REFERENCE HEIGHT

Ü0 = 4.0 ''M/S WIND VELOCITY AT HEIGHT ZO
AIRTEMP = 15.0 *k DEG.CELSIÜS AIR TEMP. AT GROUND LEVEL
RH = 0.6 < RELATIVE HUMI DI TY
TGROUND ~ 15.0 ik DEG.CELSIÜS EARTH-S SURFACE TEMPERATURE
*
HTCD
UlOr
*
ROUGH . 0.3E-01 <k Ν SURFACE ROUGHNESS PARAMETER
HONIN = -20.000 ik M MONIN - OBÜKHOV LENGTH
CROSSW = 0.064 <k K**(1-BETA) CROSSWIND (DELTA)
0.905 ' (BETA)
*
CLOUD

XSTEP = 10.0 * OUTPUT STEP LENGTH

XHAX = 1000. < X AT WHICH CALC. IS STOPPED
CAMIN = 0.0000001 *k KG/M3 CA AT WHICH CALC. IS STOPPED
CÜ = 0.035 *k KG/H3 UPPER CONCENTRATION LI MI T
CL = 0.017 *k KG/H3 LOWER CONCENTRATION LI MI T

SOURCE
4
FLUX = 0.1375 *k KG/M2/S GAS EMISSION FLUX
TEHPGAS = 15. ik DEG.CELSIÜS TEMPERATÜRE OF EMITTED GAS
CPGAS = 29.16 ik J/HOLE/'DEG.C SPECIFIC HEAT OF EMITTED GAS
HWGAS = 71.00 'k KG/KMOLE HOL. WEIGHT OF EMITTED GAS
WATGAS = 0. ' MOLAR FRACTION PICKED-OP WATE
*

97
1HSMAIN HEGADAS-S PROGRAM ( VERSION AÜG88 PAGE O
DATE 03/02/92 TIME 05:30

«« HEGADAS-S CASE 10 >>>>

CALCULATION CODE ICNT = 0

SURFACE HEAT TRANSFER MODEL ISURF = 2
THERMODYNAMIC MODEL THERMOD = NORMAL
SOURCE LENGTH PLL = 2.0000 M
SOURCE HALF-WIDTH PLW = 2.0000 H
WIND VELOCITY AT HEIGHT ZO UO = 4.0000 M/S
REFERENCE HEIGHT ZO = 10.000 H
SURFACE ROUGHNESS PARAMETER ZR = 0.30000E-01 H
AIR TEMP. AT GROUND LEVEL TAP = 15.000 DEG.CELSIOS
MONIN - OBÜKHOV LENGTH OBUKL = -20.000 H
DELTA = 0.64000E-01 H**(1-BETA)
BETA = 0.90500
SPREADING CONSTANT CE = 1.1500
OUTPUT STEP LENGTH DXO = 10.000
X AT WHICH CALC. IS STOPPED XMAX = 1000.0
CA AT WHICH CALC. IS STOPPED) CAHIN = 0.10000E-06 KG/H3
UPPER CONCENTRATION LIMIT CO = 0.35000E-01 . KG/M3
LOWER CONCENTRATION LIMIT CL = 0.17000E-01 KG/M3
EVAPORATION FLUX Q = 0.13750 KG/M2/S = 1.1000 KG/S
RELATIVE HUMIDITY R = 0.60000
TEMPERATURE OF EMITTED GAS! TGE = 15.000 DEG.CELSIOS
SPECIFIC HEAT OF EMITTED GASi CPG = 29.160 J/MOLE/DEG.CELSIUS
MOL. WEIGHT OF EMITTED GAS FMG = 71.000 KG/KMOLE
EARTH-S SURFACE TEMPERATURE TW2P = 15.000 DEG.CELSIOS
MOLAR FRACTION PICKED-UP WATER
:ER W2P = O.O0000E+OC1
HEAT GROUP IN HEAT FLUX QH HEATGR = 24.000

WIND PROFILE EXPONENT ALPHA = 0.18340

OSTAR = 0.33622E+00 M/S

1HSMAIN HEGADAS-S PROGRAM ( VERSION AÖG88 ) PAGE 1
DATE 03/02/92 TIME 05:30

«« HEGADAS-S CASE 10 »»

DISTANCE CA SZ SY HIDP YCO ZCO YCL ZCL RIB TMP CONC

(H) (KG/M3) (M) (K) (I) (H) (M) (I) (M) (DEG.C) (I VOL.

-.100E+01 0.168E+01 0.00 0.00 2.00 2.00 0.00 2.00 0.00

0.100E+01 0.168E+01 0.11 0.00 2.00 2.00 0.35 2.00 0.40 7.361 15.0 0.560E+02

TAKE-UP FLUX = 0.1376 KG/M2/S = 1.1005 KG/S

0.190E+02 0.546E-01 0.65 3.33 4.62 6.84 0.33 8.22 0.74 0.883 15.0 0.182E+01
0.390E+02 0.136E-01 1.54 5.67 5.91 0.00 0.00 0.00 0.00 -0.703 15.0 0.454E+00
0.590E+02 0.576E-02 2.69 7.67 6.56 0.00 0.00 0.00 0.00 -2.353 15.0 0.192E+00
0.790E+02 0.312E-02 4.03 9.47 6.93 0.00 0.00 0.00 0.00 -4.199 15.0 0.104E+00
0.990E+O2 0.194E-02 5.51 11.13 7.13 0.00 0.00 0.00 0.00 -6.25« 15.0 0.645E-01
0.119E+03 0.131E-02 7.14 12.70 7.23 0.00 0.00 0.00 0.00 -8.519 15.0 0.436E-01
0.139E+03 0.943E-03 8.90 14.18 7.25 0.00 0.00 0.00 0.00 -10.968 15.0 0.314E-01

98
 0.159E+03 0.708E-03 10.77 15.60 7.21 0.00 0.00 0.00 0.00 -13.598 15.0 0.236E-01
0.179E+03 0.550E-03 12.77 16.97 7.13 0.00 0.00 0.00 0.00 -16.407 15.0 0.183E-01
0.199E+03 0.438E-03 14.87 18.28 7.02 0.00 0.00 0.00 0.00 -19.376 15.0 0.146E-01
0.219E+03 0.357E-03 17.07 19.56 6.88 0.00 0.00 0.00 0.00 -22.501 15.0 0.119E-01
0.239E+03 0.296E-03 19.37 20.80 6.72 0.00 0.00 0.00 0.00 -25.774 15.0 0.985E-02
0.259E+03 0.249E-03 21.76 22.01 6.54 0.00 0.00 0.00 0.00 -29.191 15.0 0.829E-02
0.279E+03 0.212E-03 24.24 23.19 6.34 0.00 0.00 0.00 0.00 -32.744 15.0 0.707E-02
0.299E+03 0.183E-03 26.81 24.34 6.13 0.00 0.00 0.00 0.00 -36.432 15.0 0.609E-02
0.319E+03 0.159E-03 29.46 25.47 5.91 0.00 0.00 0.00 0.00 -40.247 15.0 0.530E-02
0.339E+03 0.140E-03 32.19 26.57 5.68 0.00 0.00 0.00 0.00 -44.186 15.0 0.465E-02
0.359E+03 0.123E-Ö3 35.01 27.66 5.45 0.00 0.00 0.00 0.00 -48.254 15.0 0.410E-02
0.379E+03 O.llOE-03 37.91 28.73 5.20 0.00 0.00 0.00 0.00 -52.440 15.0 0.365E-02
0.399E+O3 0.982E-04 40.88 29.78 4.95 0.00 0.00 0.00 0.00 -56.741 15.0 0.327E-02
0.419E+03 0.883E-04 43.92 30.81 4.69 0.00 0.00 0.00 0.00 -61.152 15.0 0.294E-02
0.439E+03 0.799E-04 47.03 31.83 4.42 0.00 0.00 0.00 0.00 -65.672 15.0 0.266E-02
0.459E+03 0.725E-04 50.22 32.83 4.15 0.00 0.00 0.00 0.00 -70.297 15.0 0.241E-02
0.479E+03 0.661E-04 53.47 33.82 3.88 0.00 0.00 0.00 0.00 -75.025 15.0 0.220E-02
0.499E+03 0.605E-04 56.78 34.79 3.60 0.00 0.00 0.00 0.00 -79.855 15.0 0.201E-02
0.519E+03 0.556E-04 60.16 35.75 3.33 0.00 0.00 0.00 0.00 -84.783 15.0 0.185E-02
0.539E+03 0.512E-04 63.61 36.71 3.04 0.00 0.00 0.00 0.00 -89.809 15.0 0.171E-02
0.559E+03 0.474E-04 67.12 37.65 2.76 0.00 0.00 0.00 0.00 -94.930 15.0 0.158E-02
0.579E+03 0.439E-04 70.69 38.57 2.47 0.00 0.00 0.00 0.00 -100.145 15.0 0.146E-02
0.599E+03 0.408E-04 74.32 39.49 2.18 0.00 0.00 0.00 0.00 -105.450 15.0 0.136E-02
0.619E+03 0.380E-04 78.00 40.40 1.89 0.00 0.00 0.00 0.00 -110.848 15.0 0.126E-02
0.639E+03 0.355E-04 81.75 41.30 1.59 0.00 0.00 0.00 0.00 -116.332 15.0 0.118E-02
0.659E+03 0.332E-04 85.55 42.19 1.30 0.00 0.00 0.00 0.00 -121.903 15.0 0.110E-02
0.679E+03 0.311E-04 89.41 43.08 1.00 0.00 0.00 0.00 0.00 -127.561 15.0 0.103E-02
0.699E+03 0.292E-04 93.33 43.95 0.70 0.00 0.00 0.00 0.00 -133.302 15.0 0.972E-03
0.719E+03 0.275E-04 97.30 44.82 0.40 0.00 0.00 0.00 0.00 -139.126 15.0 0.914E-03
0.739E+03 0.259E-04 101.32 45.68 0.10 0.00 0.00 0.00 0.00 -145.031 15.0 0.862E-03
0.746E+03 0.254E-04 102.70 45.97 0.00 0.00 0.00 0.00 0.00 -147.043 15.0 0.845E-03
0.759E+03 0.241E-04 106.03 46.53 0.00 0.00 0.00 0.00 0.00 -151.955 15.0 0.804E-03
0.779E+03 0.224E-04 111.16 47.38 0.00 0.00 0.00 0.00 0.00 -159.486 15.0 0.746E-O3
0.799E+03 0.209E-04 116.36 48.23 0.00 0.00 0.00 0.00 0.00 -167.134 15.0 0.695E-03
0.819E+03 0.195E-04 121.64 49.07 0.00 0.00 0.00 0.00 0.00 -174.898 15.0 0.648E-03
0.839E+03 0.182E-04 126.99 49.92 0.00 0.00 0.00 0.00 0.00 -182.776 15.0 0.605E-03
0.859E+03 0.170E-04 132.41 50.76 0.00 0.00 0.00 0.00 0.00 -190.766 15.0 0.566E-03
ÏHSHAIN HEGADAS-S PROGRAM ( VERSION A0G88 ) PAGE 2
DATE 03/02/92 TIME 05:30

«« HEGADAS-S CASE 10 »»

DISTANCE CA SZ SY HIDP YCÜ ZCÜ YCL ZCL RIB TMP CONC

(H) (KG/H3) (H) (H) (H) (M) (H) (H) (H) (DEG.C) (i VOL.)

0.879E+03 0.160E-04 137.91 51.60 0.00 0.00 0.00 0.00 0.00 -198.866 15.0 0.531E-03
0.899E+03 0.150E-04 143.48 52.44 0.00 0.00 0.00 0.00 0.00 -207.076 15.0 0.498E-03
0.919E+O3 0.141E-04 149.12 53.28 0.00 0.00 0.00 0.00 0.00 -215.393 15.0 0.469E-03
0.939E+03 0.133E-04 154.84 54.12 0.00 0.00 0.00 0.00 0.00 -223.816 15.0 0.441E-03
0.959E+03 0.125E-04 160.62 54.96 0.00 0.00 0.00 0.00 0.00 -232.343 15.0 0.416E-03
0.979E+03 0.118E-04 166.46 55.79 0.00 0.00 0.00 0.00 0.00 -240.973 15.0 0.393E-03
0.999E+03 0.112E-04 172.38 56.63 0.00 0.00 0.00 0.00 0.00 -249.704 15.0 0.372E-03
0.102E+04 0.106E-04 178.36 57.46 0.00 0.00 0.00 0.00 0.00 -258.537 15.0 0.352E-03
0.104E+04 0.100E-04 184.40 58.29 0.00 0.00 0.00 0.00 0.00 -267.469 15.0 0.333E-03
0.106E+04 0.950E-05 190.51 59.12 0.00 0.00 0.00 0.00 0.00 -276.498 15.0 0.316E-03
0.108E+04 0.902E-05 196.69 59.95 0.00 0.00 0.00 0.00 0.00 -285.624 15.0 0.300E-03
0.110E+04 0.857E-05 202.93 60.78 0.00 0.00 0.00 0.00 0.00 -294.847 15.0 0.285E-03

99
0.112E+04 0.816E-05 209.23 61.61 0.00 0.00 0.00 0.00 0.00 -304.164 15.0 0.272E-03
0.114E+04 0.777E-05 215.59 62.43 0.00 0.00 0.00 0.00 0.00 -313.573 15.0 0.259E-03
0.116E+04 0.741E-05 222.01 63.26 0.00 0.00 0.00 0.00 0.00 -323.077 15.0 0.247E-03
0.118E+04 0.707E-05 228.49 64.08 0.00 0.00 0.00 0.00 0.00 -332.671 15.0 0.235E-03
0.120E+04 0.675E-05 235.04 64.90 0.00 0.00 0.00 0.00 0.00 -342.357 15.0 0.225E-03
0.122E+04 0.645E-05 241.64 65.72 0.00 0.00 0.00 0.00 0.00 -352.132 15.0 0.215E-03
0.124E+04 0.617E-05 248.30 66.54 0.00 0.00 0.00 0.00 0.00 -361.995 15.0 0.205E-03
0.126E+04 0.590E-05 255.02 67.36 0.00 0.00 0.00 0.00 0.00 -371.946 15.0 0.196E-03
0.128E+04 O.565E-05 261.79 68.18 0.00 0.00 0.00 0.00 0.00 -381.984 15.0 0.188E-03
O.130E+04 0.542E-05 268.62 68.99 0.00 0.00 0.00 0.00 0.00 -392.109 15.0 0.180E-03
0.132E+O4 0.520E-05 275.51 69.81 0.00 0.00 0.00 0.00 0.00 -402.320 15.0 0.173E-03
0.134E+04 0.499E-05 282.46 70.63 0.00 0.00 0.00 0.00 0.00 -412.615 15.0 0.166E-03
0.136E+04 0.479E-05 289.46 71.44 0.00 0.00 0.00 0.00 0.00 -422.921 15.0 0.160E-03
0.138E+04 0.461E-05 296.51 72.25 0.00 0.00 0.00 0.00 0.00 -433.384 15.0 0.153E-03
0.140E+04 0.443E-05 303.62 73.06 0.00 0.00 0.00 0.00 0.00 -443.930 15.0 0.147E-03
0.142E+04 0.426E-05 310.79 73.87 0.00 0.00 0.00 0.00 0.00 -454.557 15.0 0.142E-03
0.144E+04 0.410E-05 318.00 74.68 0.00 0.00 0.00 0.00 0.00 -465.262 15.0 0.137E-03
0.146E+04 0.395E-05 325.27 75.49 0.00 0.00 0.00 0.00 0.00 -476.051 15.0 0.131E-03
0.148E+04 0.381E-05 332.60 76.30 0.00 0.00 0.00 0.00 0.00 -486.917 15.0 0.127E-03
0.150E+04 0.367E-05 339.97 77.11 0.00 0.00 0.00 0.00 0.00 -497.865 15.0 0.122E-03
0.152E+O4 0.354E-05 347.40 77.92 0.00 0.00 0.00 0.00 0.00 -508.891 15.0 0.118E-03
0.154E+04 0.342E-05 354.87 78.72 0.00 0.00 0.00 0.00 0.00 -519.992 15.0 0.114E-03
0.156E+04 0.330E-05 362.40 79.53 0.00 0.00 0.00 0.00 0.00 -531.173 15.0 0.110E-03
0.158E+04 0.319E-05 369.98 80.33 0.00 0.00 0.00 0.00 0.00 -542.428 15.0 0.106E-03
0.160E+04 0.308E-05 377.61 81.13 0.00 0.00 0.00 0.00 0.00 -553.759 15.0 0.103E-03
0.162E+04 0.298E-05 385.29 81.93 0.00 0.00 0.00 0.00 0.00 -565.168 15.0 0.991E-04
0.164E+04 0.288E-05 393.02 82.74 0.00 0.00 0.00 0.00 0.00 -576.649 15.0 0.959E-04
0.166E+04 0.279E-05 400.80 83.54 0.00 0.00 0.00 0.00 0.00 -588.209 15.0 0.928E-04
0.168E+04 0.270E-05 408.63 84.34 0.00 0.00 0.00 0.00 0.00 -599.838 15.0 0.898E-04
0.170E+04 0.261E-05 416.50 85.13 0.00 0.00 0.00 0.00 0.00 -611.540 15.0 0.870E-04
0.172E+04 0.253E-05 424.42 85.93 0.00 0.00 0.00 0.00 0.00 -623.320 15.0 0.843E-04
0.174E+04 0.246E-05 432.39 86.73 0.00 0.00 0.00 0.00 0.00 -635.167 15.0 0.817E-04
0.176E+04 0.238E-05 440.41 87.53 0.00 0.00 0.00 0.00 0.00 -647.087 15.0 0.792E-04
0.178E+04 0.231E-05 448.48 88.32 0.00 0.00 0.00 0.00 0.00 -659.082 15.0 0.768E-04
0.180E+04 0.224E-05 456.59 89.12 0.00 0.00 0.00 0.00 0.00 -671.143 15.0 0.746E-04
0.182E+O4 0.217E-05 464.75 89.91 0.00 0.00 0.00 0.00 0.00 -683.275 15.0 0.724E-04
0.184E+04 0.211E-05 472.95 90.70 0.00 0.00 0.00 0.00 0.00 -695.477 15.0 0.703E-04
lHSNAIN HEGADÀS-S PROGRAM ( VERSION ÀÜG88 ) PAGE 3
DATE 03/02/92 TIME 05:30

«« HEGADAS-S CASE 10 »»

DISTANCE CA SZ SY HIDP YCÜ ZCÜ YCL ZCL RIB TMP CONC

(M) (KG/M3) (M) (M) (H) (H) (M) (M) (H) (DEG.C) (I VOL.)
***************************************************************************************************

0.186E+04 0.205E-05 481.20 91.50 0.00 0.00 0.00 0.00 0.00 -707.753 15.0 0.682E-04
0.188E+O4 0.199E-05 489.50 92.29 0.00 0.00 0.00 0.00 0.00 -720.094 15.0 0.663E-04
0.190E+04 0.194E-05 497.84 93.08 0.00 0.00 0.00 0.00 0.00 -732.503 15.0 0.644E-04
0.192E+04 0.188E-O5 506.23 93.87 0.00 0.00 0.00 0.00 0.00 -744.980 15.0 0.626E-04
0.194E+04 0.183E-05 514.66 94.66 0.00 0.00 0.00 0.00 0.00 -757.530 15.0 0.609E-04
0.196»K)4 0.178E-05 523.14 95.45 0.00 0.00 0.00 0.00 0.00 -770.142 15.0 0.593E-04
0.198E+04 0.173E-05 531.66 96.24 0.00 0.00 0.00 0.00 0.00 -782,822 15.0 0.577E-04
0.200E+04 0.169E-05 540.22 97.03 0.00 0.00 0.00 0.00 0.00 -795.568 15.0 0.561E-04

100
European Communities — Commission

EUR 14444 — Review of accidents involving chlorine

G. Drogaris

Luxembourg: Office for Official Publications of the European Communities

1992 — 100 pp., 36 tab., 18 fig. — 21.0 χ 29.7 cm

Environment and quality of life series

ISBN 92­826­4403­0

Price (excluding VAT) in Luxembourg: ECU 10.50

This study comprises a review of accidents involving chlorine that can be found In various
accident data collections. Basic material has been obtained by Interrogating, FACTS,
MHIDAS and SONATA databases and reviewing the "Störfälle Handbuch". Other sources
such as CDCIR bulletins, the EPA acute hazardous events database, the accident in­
ventory of the French Ministry of Environment, and journals and text books on safety­
related issues have also been utilized.
This comparison shows that none of the existing publicly accessible accident data col­
lections may include all accidents. The probability of an accident being recorded in an
accident data collection increases with the severity of its consequences but even
major accidents can escape recording. In the absence of a structured accident repor­
ting system there are many difficulties in collecting complete and accurate accident
reports.
Therefore there are many limitations that must be seriously considered in using data
from these sources for statistical purposes. On the other hand accident databanks are
extremely useful for identifying priorities and diffusing the knowledge for effective acci­
dent prevention policies.
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