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Section 1
MANUAL ON
CHEMICAL POLLUTION
PROBLEM ASSESSMENT
AND
RESPONSE ARRANGEMENTS
1999 Edition
ELECTRONIC EDITION
B INTERNATIONAL MARITIME ORGANIZATION

London, 1999
Licensed to Anglo-Eastern Group for 1 copy. © IMO

Print edition
First (ISBN:
Published
978-92-801-6096-3)
in 1987
by the INTERNATIONAL MARITIME
First Published ORGANIZATION
in 1987
by the4INTERNATIONAL
Albert Embankment,MARITIME
LondonORGANIZATION
SE1 7SR
4 Albert Embankment, London SE1 7SR
Second edition 1999
Electronic edition, 2008
Printed in the United Kingdom by MPG-Books Ltd, Bodmin
6 8 10 9 7
ISBN:
IMO978-92-801-6096-3
PUBLICATION
Sales number: EA630E
IMO PUBLICATION
Sales number: IA630E
Copyright # International Maritime Organization 1999
Copyright # International Maritime Organization 1999

All rights reserved.
No part of this publication may be reproduced,
stored in a retrieval system or transmitted in any form
or by any means without prior permission in writing
from the International Maritime Organization.
All rights reserved.

No part of this publication may be reproduced,
stored in a retrieval system or transmitted in any form
or by any means without prior permission in writing
from the International Maritime Organization.

Foreword
This publication, prepared by the Marine Environment Protection

Committee of the International Maritime Organization (IMO)
supersedes the 1986 edition of section 1 of the Manual on Chemical
Pollution. For the purpose of this Manual, hazardous materials (HNS)
include, but are not limited to: noxious liquid substances, described
under Annex II of MARPOL 73/78 and the International Bulk Chemical
Code (IBC Code); dangerous goods, described in the International
Maritime Dangerous Goods Code (IMDG Code); gases regulated under
the International Gas Carrier Code (IGC Code); and solid cargoes
covered by the Code of Safe Practice of Solid Bulk Cargoes (BC Code). It
provides guidance to Governments on ways of assessing hazards
associated with spillages of hazardous and noxious substances and of
setting up response organizations. Further, it describes safe operational
practice in response. The present section of this Manual does not deal
with the recovery of packages lost during incidents at sea, nor with
problems particular to radioactive and explosive substances. These
matters are covered in section 2 of the Manual: Search and Recovery of
Packaged Goods Lost at Sea.
Problems related to oil pollution casualties and related information are
specifically addressed in the Manual on Oil Pollution (sections I to VI).
iii

Contents
Page
Chapter 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
Chapter 2 Regulatory framework for the carriage of HNS at sea
2.1 General remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.2 Principal conventions of the International Maritime
Organization (IMO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3 HNS in bulk . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.4 HNS in package form (dangerous goods) . . . . . . . . . . . . . . . . . 8
2.5 Emergency precautions on board . . . . . . . . . . . . . . . . . . . . . . . . 10
2.6 Notification and reporting of accidents causing or
likely to cause spillage of HNS . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Annex 2-1 Example of a POLREP . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Chapter 3 Hazards and fate of released HNS
3.1 General remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.2 Cargo flows . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.3 Hazardous properties of HNS . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
3.4 Behaviour and fate of released HNS . . . . . . . . . . . . . . . . . . . . . 31
Annex 3-1 Definitions of terms used to describe hazard
characteristics. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Annex 3-2 Example of a chemical compatibility chart . . . . . . . . . . . . . . 48
Annex 3-3 A classification flow chart. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
Chapter 4 Chemical emergency preparedness
4.1 General remarks on emergency response
systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
4.2 Optimized response organization . . . . . . . . . . . . . . . . . . . . . . . . 55
4.3 Response support system (RSS) . . . . . . . . . . . . . . . . . . . . . . . . . 58
Chapter 5 Response methods and techniques
5.1 General remarks. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
5.2 Systematic approach to emergency response. . . . . . . . . . . . 62
5.3 Response on board ships . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
5.4 Response options for spills at sea . . . . . . . . . . . . . . . . . . . . . . . 71
5.5 Health and safety strategy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
Annex 5-1 Maritime safety card . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98

Annex 5-2 Levels of protection for pre-determined
levels of hazards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
Chapter 6 Case histories
6.1 General remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
6.2 Case history 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
6.3 Case history 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
6.4 Case history 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
6.5 Case history 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
6.6 Case history 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
6.7 Case history 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
6.8 Case history 7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
6.9 Case history 8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
6.10 Summary of measures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
vi .

Chapter 1
Introduction
Broadly defined, hazardous and noxious substances (HNS) are those

substances that due to their intrinsic properties may, if released,
endanger human life, the environment or property. However, for the
purpose of this Manual, this definition excludes oil, as oil-related
pollution matters are dealt with in other IMO technical manuals.
In recent years, there has been a rapid growth in the transport and
storage of HNS. If allowed to escape, these materials can present a
danger to a ship’s crew, the vessel, coastal populations and/or the
environment. Accordingly, public concern over these materials has
grown, and both Governments and industry have taken steps to
address and respond to such incidents.
Marine spills involving HNS are not as frequent as oil spills, and may
receive little publicity due to their less visible nature. However, on a
global basis, marine spills involving HNS are not rare. In fact, a world-
wide survey of marine HNS emergencies* (see table 1) showed that:
. there is a wide range of cargoes which need to be considered
as potential threats;
. most accidents involved mainly two classes of HNS:
flammable liquids and corrosive materials;
. one to two major HNS accidents can be expected each year;
. a wide variety of ship types were associated with HNS
accidents; and
. HNS accidents were almost equally divided between ‘‘bulk’’
and ‘‘packaged goods’’ shipments.
There is no doubt that if a spill involving HNS is to be handled
successfully and damage minimized, careful planning is essential.
Many of the factors which need to be taken into account when
preparing for HNS events, including the drawing up of chemical-spill
plans, are similar to those required for oil spills. A number of countries
have adapted their oil spill contingency plans to address chemical spill
incidents. In addition to using the oil spill planning framework, these
countries have also tended to rely on the same basic organizational
arrangements in order to avoid creating two separate response
structures. Given the wide range of chemicals and their diverse
hazards and properties, expertise from the chemical industry may be
required to ensure that safe and practical procedures are followed.
* Brian Mansfield, ‘‘Can Overboard’’, Technical Seminar on Chemical Spills,

1994.

Chapter 1
Table 1: Examples of accidents involving ships carrying HNS

(1917–1995)
Location (Year) Vessel HNS Quantity Accident type

name involved
Port of (1917) Mont- Explosives 2,600 tonnes Explosion (3,000 people
Halifax, Blanc killed, 9,000 injured)
Canada
Port of Texas (1947) Ammonium 2,200 tonnes Fire and explosion (468
City, USA Grandcamp nitrate killed) causing a
domino effect (fire/
explosion) on a vessel
berthed nearby (250 m)
which carried
ammonium nitrate and
sulphur
Off Italian (1974) Cavtat Tetraethyl lead 150 tonnes in Collision and sinking
coast drums
Tetramethyl lead 120 tonnes in
drums
Port of (1976) René 16 Ammonia 180 tonnes Hose rupture
Landskrna,
Sweden
North Sea (1979) Sindbad Chlorine 51 one-tonne Cylinders lost at sea
cylinders due to bad weather
Adriatic Sea (1984) Brigitta Vinyl chloride 1,300 tonnes Sinking
Montanari
Off Spanish (1987) Cason Mixed dangerous 1,000 tonnes Fire and grounding
coast cargo in package
form
Off Dutch (1988) Anna Acrylonitrile 547 tonnes Collision and sinking
coast Broere Dodecylbenzene 500 tonnes
Off Italian (1991) Acrylonitrile 550 tonnes 1,000 Sinking
coast Alessandro Primo Dichloroethane tonnes
Off one of (1994) Tus Caustic soda 4,200 tonnes Grounding
the Greek
archipelagic
islands
Bay of (1995) Chung Mu Styrene 310 tonnes Collision
Zhanijiang, No.1
China
Thus, although elements of preparedness and response for oil and HNS
are similar in the recommended organizational and administrative
structures, there are some differences from a technical standpoint in
terms of protective and safety measures and pollution response
equipment. In the latter case, these differences are due to a number of
reasons:
. oil normally floats in viscous layers; this behaviour is valid
only for a minor proportion of HNS;
. oil spills are highly visible; in many cases spills involving
HNS are not so easy to see;

Introduction
. oil spill response technology is well developed; this is not the

case for HNS;
. skimming of oil from the water surface can be carried out
with reasonable success; this is often not always feasible for
HNS.
This Manual is designed to assist national and local response
organizations in developing effective spill response procedures under
the unique conditions imposed by the marine environment and, more
specifically, to be used by the following groups:
. decision-makers from governmental agencies or private
industry;
. local response managers lacking a maritime background,
but who are involved with emergency personnel and are
familiar with response procedures for HNS;
. ship personnel, who will need to co-ordinate with shore-
based response teams in case of emergencies; and
. port authorities or terminal managers, who need guidance
in integrating shore-based response with shipboard re-
sponse.
Two other references supported by IMO are recommended: Awareness
and Preparedness for Emergencies at Local Level (APELL) for Port Areas*
and Guidance Concerning Chemical Safety in Port Areas{. The first was
jointly produced with the United Nations Environment Programme
(UNEP) and the second with the Organization for Economic Co-
operation and Development (OECD).
* To obtain a copy, write to: Industry and Environment Office, UNEP, Tour
Mirabeau, 39 – 43 Quai André Citroën, 75739 Paris Cedex 15, France.
{
This document is catalogued as OECD Environment Monograph No. 118. For
information on how to obtain a copy, write to: OECD Paris Centre, 22 rue André
Pascal, 75775 Paris Cedex 16, France.

Chapter 2
Regulatory framework for the carriage
of HNS at sea
2.1 General remarks
HNS cargoes may be carried at sea either in bulk or in package form.

There are many ship types which carry HNS. These include:
. dry bulk carriers, which carry solid bulk cargoes such as
grain, fishmeal, ores and semi-manufactured products;
. oil/bulk/ore carriers or combination carriers, which are
multi-purpose carriers of bulk cargoes, either in liquid or
solid form, and are designed to avoid having to make the
return voyage in ballast;
. containerships, which are specialized carriers that transport
packaged goods in containers and are mainly designed for
general dry cargo (box-type), although specialized contain-
ers can take solids (e.g., powder) or liquid chemicals in
portable (ISO) tanks;
. general cargo ships, which usually carry cargo in relatively
small consignments (e.g., crates, boxes, drums or sacks), all
placed in close proximity in several large holds;
. ro–ro vessels, which are designed with facilities for quick
loading and discharging, with cargoes being moved on and
off using road trailers or rail tank cars;
. chemical carriers, which are a specialized class of tankers
designed to carry liquid chemicals and are referred to as
‘‘chemical carriers’’, ‘‘product tankers’’, or ‘‘parcel tankers’’;
and
. gas carriers, which carry liquefied gas cargoes under
pressure, under reduced temperature conditions, or both.
These liquefied cargoes will evaporate rapidly when exposed
to ambient pressure and temperature.
2.2 Principal conventions of

the International Maritime Organization (IMO)
The two most important international conventions covering the sea

transport of HNS in bulk and in package form are:
. the International Convention for the Safety of Life at Sea
(SOLAS), 1974, as amended (see SOLAS, chapter VII);

Chapter 2
. the International Convention for the Prevention of Pollution

from Ships, 1973, as modified by the Protocol of 1978
relating thereto (MARPOL 73/78), as amended (see MARPOL,
Annexes II and III).
2.3 HNS in bulk

Bulk HNS cargoes are those loaded without packaging directly into cargo
tanks or holds of ships.
2.3.1 Bulk liquid HNS

Chemical tankers vary in size from about 400 m 3 to 40,000 m3 capacity,
with tank sizes ranging from about 70 m3 up to 3,000 m3 for specialized
cargoes. Some of these ships are dedicated to particular products or
routes, but most of them carry a wide range of chemicals having
differing properties and hazards.
Figure 2.1: Cargo tank layout of a chemical (parcel) carrier (Source: IMO)
Provisions for the construction and equipment for ships carrying liquid
chemicals in bulk are set out in IMO’s Code for the Construction and
Equipment of Ships Carrying Dangerous Chemicals in Bulk (BCH Code)
and the International Code for the Construction and Equipment of Ships
Carrying Dangerous Chemicals in Bulk (IBC Code). Operational safety
procedures are set out in the Tanker Safety Guide (Chemicals) of the
International Chamber of Shipping (ICS).
Gas carriers vary in size up to 135,000 m3 capacity. These ships carry
gas cargoes in liquefied form through the application of reduced
temperatures, increased pressures, or a combination of both. The
largest ships are used for the liquefied natural gas (LNG) trades, while
the other main products include propane, butane, ammonia and vinyl
chloride, which are carried in LPG carriers.
Figure 2.2: A typical fully refrigerated LPG carrier

(Source: Roger C. Ffooks (editor), Gas Carrier, Fairplay Ltd, London, 1984

Regulatory framework for the carriage of HNS at sea
Ships designed to carry liquefied gases in bulk are regulated by IMO’s

International Code for the Construction and Equipment of Ships
Carrying Liquefied Gases in Bulk (IGC Code), which contains
provisions for the construction and equipment of gas carriers built
after mid-1986. The Tanker Safety Guide (Liquefied Gas) published by
the ICS contains operational safety procedures and complements the
requirements set out in the IGC Code.
For gas carriers built before 1986, there are two other gas codes: IMO’s
Code for the Construction and Equipment of Ships Carrying Liquefied
Gases in Bulk (Gas Carrier Code) covers ships built between 1976 and
1986; the Code for Existing Ships Carrying Liquefied Gases in Bulk
covers ships built before 1976.
Whereas the Codes dealing with gas carriers and chemical tankers are
mandatory under SOLAS and MARPOL for ships built after 1986, older
ships should comply with earlier codes.
2.3.2 Bulk solid HNS
The hazards associated with shipment of solid bulk products include:

. structural damage due to improper distribution of the cargo;
. loss or reduction of stability during the voyage, either due to
a shift of cargo, or to the cargo liquefying under combined
factors of vibration and motion of the ship; and
. chemical reactions such as the emission of toxic or
explosive gases.
IMO’s Code of Safe Practice for Solid Bulk Cargoes (BC Code) highlights
the dangers associated with the shipment of certain types of bulk
cargoes, lists typical products which are shipped and gives advice on
their properties.
Figure 2.3: Schematic diagram of a bulk carrier

Chapter 2
The various IMO codes for the carriage of bulk HNS can be used to
respond effectively to incidents. Sections of the codes contain details
on chemical hazards, pollution category, etc. These are vital for an
effective response, since a hazard evaluation of the product in question
can be obtained by consulting the relevant sections.
a b c d e f g h i j k l m n o
Electrical
equipment
yrogetac noitulloP
dna yrotaripseR
i' i'' i''' Special requirements
noitcetorp eye
lortnoc latnem
Product name
-norivne knaT
(see chapter 15)
noitcurtsnoc
rebmun NU
fo slairetaM
stnev knaT
noitcetorp
tniophsalF
epyt knaT
noitceted
epyt pihS
gniguaG
sdrazaH
ruopaV
puorG
C806>
ssalC
eriF
15.11.2 to 15.11.4,
Acetic acid D S 3 2G Cont. No T1 IIA No R F A Y1,Z E 15.11.6 to 15.11.8,
15.19.6
15.11.2 to 15.11.4,
Acetic anhydride 1715 D S 2 2G Cont. No T2 IIA No R F-T A Y1 E 15.11.6 to 15.11.8,
15.19.6
Acetochlor A P 2 2G Open No Yes O No A No 15.19.6
Acetone cyanohydrin 1541 A S/P 2 2G Cont. No T1 IIA Yes C T A Y1 E 15.1, 15,12, 15.17 to
15.19, 16.6.1 to 16.6.3
Acetonitrile 1648 III S 2 2G Cont. No T2 IIA No R F-T A No 15.12, 15.19.6
Acrylamide solution 2074 D S 2 2G Open No NF C No No No 15.12.3, 15.13, 15.16.1,
(50% or less) 15.19.6, 16.6.1
Figure 2.4: Extract from chapter 17 of the IBC Code (Source: IMO)
2.4 HNS in package form (dangerous goods)

HNS packaged in small quantities are usually known as ‘‘dangerous
goods’’. These substances can be transported by ships in drums or
boxes, either individually or in freight containers. The contents of
portable tanks, intermediate bulk containers, road vehicles, and rail
wagons fall within the general category of ‘‘dangerous goods’’.
Figure 2.5: Examples of some packages (not drawn to scale) used for
transporting dangerous goods (Sources: IMO, Hazardous Cargo Bulletin)

The International Maritime Dangerous Goods Code (IMDG Code) is used

for the carriage of dangerous goods. It describes:
. design and testing for packaging;
. marking, labeling, and placarding;
. documentation to accompany the dangerous goods; and
. stowage and segregation requirements.
This Code applies to all ships carrying dangerous goods in package form.
The IMDG Code places dangerous goods into nine main classes (see
table 2).
Table 2: Classes and types of substances according to the IMDG Code
Class
number Description Examples
1 Explosives Trinitrotoluene
2 Gases Acetylene
3 Flammable liquids Ethyl alcohol
4 Flammable solids (including self-reactive solids Calcium carbide

and liquids); substances liable to spontaneous
combustion and those which, in contact with
water, emit flammable gases
5 Oxidizing substances and organic peroxides Sodium chlorate
6 Toxic and infectious substances Sodium cyanide
7 Radioactive substances Radium
8 Corrosives Sodium hydroxide (caustic

soda)
9 Miscellaneous dangerous substances and Polychlorinated biphenyls

articles
All substances, materials, and articles which appear in the IMDG Code
are listed in its General Index. This gives the product’s UN number, its
Emergency Schedule number (EmS No.), its Medical First Aid Guide table
number (MFAG Table No.), and the IMDG Code page number of the
individual schedule for the product concerned. Substances recognized
as marine pollutants are also indicated as such in this index.
Although written primarily with the mariner in mind, the provisions of
this Code can provide guidance to all those involved in the storage,
transport and handling of the substances referenced in this document.
Individuals can include port authorities and all those involved in the
transport chain from the manufacturer to the receiver. Furthermore, in
emergencies, specific information can be obtained from the individual
schedules, as well as from the General Index of the Code. However, it does

Chapter 2
not contain detailed occupational health and safety information or data

on the substances and materials listed in the Code and responders
should ensure they have access to complementary information from
other sources.
2.5 Emergency precautions on board
In operational environments, no matter how closely regulations are

followed, accidents can always happen. On vessels carrying HNS in
bulk, spillages may occur on board which require response by the
ship’s crew or by shore personnel. Packaged dangerous goods may
become damaged and leak. This would require response action by the
ship’s crew or shore personnel.
IMO has developed response procedures for incidents involving

dangerous goods. The IMO publication Emergency Procedures for Ships
Carrying Dangerous Goods (EmS) provides basic information on:
. special emergency equipment to be carried by ships;
. emergency procedures to be followed; and
. emergency action in case of spillage or fire.
The IMO publication Medical First Aid Guide for Use in Accidents
Involving Dangerous Goods (MFAG) gives information and specifies the
actions to be taken should a ship’s crew member be exposed to the
substances carried, and where treatment is limited to the facilities
available on board. The MFAG should be used in conjunction with the
information provided in the IMDG Code and EmS. However, it should be
specially noted that the guidance given in the MFAG not only refers to the
dangerous goods as covered by the IMDG Code, but also to other
substances covered by the codes mentioned in section 2.3.1
60089
a60089
60089
Figure 2.6: Examples of an EmS and of a MFAG table (Source: IMO)
10

The information contained in both the EmS and the MFAG is primarily
for shipboard use, where the master and the ship’s crew have to respond
to an accident without external assistance. This information, although
generic and non-specific in nature, may be of use to shore-based
personnel when responding to an accident. However, the responders
should also consult complementary information sources from national
agencies.
2.6 Notification and report of accidents causing

or likely to cause spillage of a HNS
A casualty or an accidental discharge from a ship or terminal may give
rise to pollution or a threat of pollution of the marine environment. Such
incidents must be reported without delay to the national authorities.
This should maximize the time available in which to raise an effective
response.
Article 8 of the MARPOL Convention contains the mandatory reporting
requirements by ships for incidents involving HNS. This article requires
that incidents causing, or likely to cause, the discharge of a HNS be
reported by the vessel by the fastest means available. This should be
carried out with the highest priority, by supplying all details and
circumstances to the nearest coastal State. Governments must ensure
that installations for the operation of all ship reporting systems are
instructed to re-transmit without delay, to the officer or organizations
designated to deal with these reports. In turn, these organizations
should then transmit data without delay to other coastal States which
might be affected by the accident.
The recommended reporting procedure is given in IMO Assembly
resolution A.648(16), General principles for ship reporting systems and
ship reporting requirements, including guidelines for reporting
incidents involving dangerous goods, harmful substances and/or
marine pollutants, with the aim of harmonizing the different reporting
systems.
Should an accident occur, the nearest coastal State would therefore
expect to receive details from the shipmaster such as:
. the identity of the ship (including type and size);
. the course, speed and condition of the ship;
. the name of the shipowner or his representative;
. the time and date of the occurrence of the incident;
. the geographical position;
. a description of the accident (including damage and injuries
sustained);
. the wind and sea conditions;
. the type and quantity of cargo on board;
11

Chapter 2
. description of packages including identification marks;

. the name(s) of the manufacturer(s) of the substance(s),
consignee(s) and consignor(s);
. an estimate of the quantity of cargo lost; and
. the action already taken (for example, transfer of cargo/
ballast/fuel).
Within the framework of regional agreements for co-operation in cases of
an emergency situation arising from maritime related accidents,
pollution reporting systems for the exchange of information (POLREP)
are in use between contracting parties to these agreements, when poll-
ution of the sea has occurred, or when there is a threat of such pollution.
Annex 2-1 provides an example of a report. Details on pollution reporting
systems may be found in section II of the IMO Manual on Oil Pollution:
Contingency Planning.
12

Annex 2-1
Example of a POLREP
1 This annex contains an example of a POLREP system for use

between contracting parties to the Protocol on Co-operation in
Combating Pollution of the Mediterranean Sea by Oil and Other
Harmful Substances in Cases of Emergency of the Barcelona
Convention, and between the contracting parties and the IMO/UNEP
Regional Marine Pollution Emergency Response Centre for the
Mediterranean Sea (REMPEC). It is used for exchanging information
when pollution of the sea has occurred or when there is such a threat.
Further details on systems for pollution reporting are found in appendix
5 of of the IMO Manual on Oil Pollution, section II: Contingency Planning.
A summarized list of POLREP is given below:
Introduction Address from....... to.......

Identification
Serial number to.......
Part 1: 1 Date and time

Pollution 2 Position
warning 3 Incident
(POLWARN) 4 Outflow
5 Acknowledge
40 Date and time

41 Position
42 Characteristics of pollution
43 Source and cause of pollution
44 Wind direction and speed
45 Current or tide
Part II: 46 Sea state and visibility
Pollution 47 Drift of pollution
information 48 Forecast
(POLINF) 49 Identity of observer and ships on scene
50 Action taken
51 Photographs or samples
52 Names of other States informed
53–59 Spare
60 Acknowledge
13

Chapter 2
Part III: 80 Date and time

Pollution 81 Request for assistance
facilities 82 Cost
(POLFAC) 83 Pre-arrangements for the delivery
84 Assistance to where and how
85 Other States requested
86 Change of command
87 Exchange of information
88–89 Spare
99 Acknowledge
2 The division into three parts is only for identification purposes.

For this reason, consecutive numbers are not used. This enables the
recipient to recognize, merely by looking at the numbers, whether part
I (1–5), part II (40–60) or part III (80–99) is being referred to. Parts I, II and
III can be transmitted all together in one report or separately. Single
numbers from each part can be transmitted separately or combined
with numbers from the two other parts in one report.
EXAMPLE: POLREP REPORT FORMAT (mixed report of parts I and II)

Address From: ITA
To: MLT and REMPEC
Date time group 181100z June
Identification POLREP BARCELONA CONVENTION
Serial number ITA/POLLUX/1
1 Date and Time 1 181100z
2 Position 2 368 20’N 148 55’E
3 Incident 3 Chemical tanker collision
4 Outflow 4 Not yet; Aniline
43 Source and cause of 43 Italian chemical tanker, POLLUX, of

pollution Genoa, 10000 GRT, call sign xxx in
collision with French bulk carrier
CASTOR of Marseilles, 25000 GRT,
call sign yyy. Two tanks possibly
damaged in POLLUX. No damage in
CASTOR
44 Wind direction and speed 44 90 - 7 m/s
45 Current direction and 45 180 - 0.3 knots
speed and/or tide
46 Sea state and visibility 46 Wave height 2 m. 10 nautical miles
14

49 Identity of observer/ 49 CASTOR, figure 43 refers

reporter - Identity of ships
on scene
50 Action taken 50 Restricting access to/use of area and
warning given to vessels navigating in
10 mile radius. Aerial surveillance of
area being carried out.
53 Names of other States 53 REMPEC
and organizations
informed
15

Chapter 3
Hazards and fate of released HNS
3.1 General remarks

A major maritime accident can be defined as a low-probability event but
of potentially high consequence involving a vessel or a maritime-related
activity. The vessel may be plying the open seas, navigating through
coastal waters, berthed, or anchored in a port or its approaches. Most
maritime accidents fall into one of the following categories:
. collision: the striking together of two vessels while under
way;
. ramming: the striking of a moored vessel by a moving vessel,
also referred to as a collision;
. contact: a vessel that strikes an external object other than
another vessel or sea bottom (e.g., a jetty or dock wall);
. grounding: a vessel that touches the sea bottom and remains
aground for an appreciable amount of time, also referred to
as stranding;
. fire/explosion: a fire and/or an explosion is started by the
cargo, and is the first step in the chain of events leading to
the casualty;
. cargo transfer failure: a cargo spill or release takes place at
the point of loading/unloading;
. sinking: a vessel sinks because of water leakage caused by
metal fatigue or adverse load distribution;
. loss of container integrity: power failure to the container
storing the hazardous cargoes;
. container loss: packages containing HNS which are lost at
sea, are damaged and start to leak their contents in
ecologically vulnerable areas or on shore if washed ashore;
and
. domino effect: an accident aboard a vessel causes an
accident on a nearby vessel, or at a fixed installation ashore.
3.2 Cargo outflows

In the planning stages for dealing with an accident, in addition to the
inherent properties of the chemical and its fates, the probable quantities
of outflow of the hazardous cargo need to be assessed in order to
determine the overall impact of the spilled chemical.
Proper estimates of outflows would require historical data based on type
of accident, type, number and size of the tanks, type and extent of
damage, the vessel’s loading condition and the properties of the cargo.
17

Chapter 3
For some administrations, these could present difficulties since either

the resources or the data or both might not always be available. These
estimates involve a certain amount of modelling work. However, in the
absence of such data, approximations based on detailed studies carried
out elsewhere can be used as general guidance for planning purposes.
Studies have been undertaken on the outflow fractions from collisions
and grounding from chemical carriers carrying liquid bulk cargoes.
Estimates for cargo outflows from chemical carriers involving fires are
exceedingly complex and difficult to evaluate.
The following is a general summary of one such study* which can
provide useful information for planning purposes on the size of
accidental outflows in the absence of specific data.
Chemical tankers are broadly divided into three classes, based on their
structural integrity, ships of types 1, 2 and 3. Type 3 ships are single-skin
tankers with a certain survivability standard (higher than for oil
tankers), type 2 ships are double-skin tankers and type 1 ships are
double-skin tankers with higher cargo tank integrity requirements
than type 2 ships (see figure 3.1).
Figure 3.1: Tank configurations for each ship type

(Source: Swedish Coast Guard)
In the case of groundings involving a single-skinned tanker, the tanks

will be ruptured in the bottom and some cargo will escape as the cargo of
a loaded tanker is generally exerting a hydrostatic overpressure on the
tank bottom relative to the outside area water pressure. This
overpressure is, as a rough average, equivalent to a liquid column of
about 18 of the tank depth in a tanker that is fully loaded with a soluble
* Baltic Marine Environment Protection Commission – Helsinki Commission,

Study of the risk for accidents and the related environmental hazards from the
transportation of chemicals by tankers in the Baltic Sea area, Baltic Sea
Environmental Proceedings No. 34, 1990
18

cargo and lighter than water. The fraction of the tank content will
therefore escape before equilibrium is reached. The fraction may be
increased to double that value to take into account part-loaded ships
with increased freeboard and the pumping effect of waves and swells
around the grounded vessel. A total of 14 of the content in each cargo
tank having been ruptured in the bottom should therefore be regarded
as being lost. In the case of a double-bottom ship, the cargo is located
somewhat higher up relative to the outside sea level and a total of 38 of the
content of a leaking tank should be regarded as lost in the rare case of
damage to the tank inner bottom.
In the case of cargoes heavier than water or highly soluble, the entire
content of a leaking tanker will flow out following a grounding in a single-
or double-bottom tanker if the inner tank is damaged.
Figure 3.2: Outflows from groundings

(Source: Baltic Sea Environment Protection Commission, 1990)
In the case of collision, the damage often occurs above the waterline but
may extend further down. In some cases a bulbous bow may complicate
the rupture. If the damage is limited to the side above the waterline, only
the cargo located above the lower edge of the damage will escape. In the
case of damage below the waterline, water will fill the tank and lift all
lighter-than-water cargo. In the case of a heavier-than-water cargo, only
the portion located above the lower edge of the damage will escape.
Soluble cargoes will show complex behaviour and will eventually be lost.
3.3 Hazardous properties of HNS

A maritime accident involving a vessel transporting HNS may result in
an uncontrolled release of a product potentially damaging to life, the
environment or property. The effects of the spill will depend on the
characteristics of the substance, the quantities involved and the time-
factor of the spillage. The vulnerability of the surrounding area and the
effectiveness of the emergency measures taken to minimize the accident
can affect the outcome. HNS may present one or any combination of the
following hazards:
19

Chapter 3
. flammability;
. explosivity;
. toxicity;
. infection;
. reactivity;
. corrosivity; and
. radioactivity.
A description of these hazards can be found in annex 3-1.
3.3.1 Fire hazards
A fire is a chemical process involving oxygen which gives off energy,
mainly in the form of heat. This chemical process is also known as
‘‘combustion’’. The speed at which a fire develops varies greatly,
depending on the material’s combustibility, energy content, physical
form (e.g., wood shavings versus timber blocks) and the availability of
oxygen. In addition to heat or thermal radiation, fires involving HNS may
generate smoke and toxic gases. These are important risk factors to be
taken into account while responding to a fire.
3.3.1.1 Hazards from the products of combustion

Three products produced in varying degree by fires are:
. heat, causing burns of different damage;
– first-degree burns affect the outer layer of the skin;
– second-degree burns cause blistering and penetrate fur-
ther into the skin; and
– third-degree burns penetrate even further and damage
nerve endings;
Table 3a: Effects of thermal radiation on unprotected skin (Source: ILO)
Radiation level Number of seconds before

(kW/m2)* Pain is felt Blistering starts
22 2 3
18 2.5 4.3
11 5 8.5
8 8 13.5
5 16 25
2.5 40 65
Below 2.5 Prolonged exposure tolerated
*Note: 5 kW/m2 is the radiation of a candlelight at a distance of 10 cm.
20

. solid particles (e.g., soot and ashes) can cause severe health
damage which can result in permanent injuries and death;
. toxic cases generated by the fire.
Examples of products resulting from fires are listed in table 3b.
Table 3b: Combustion by-products for some typical burning materials

(Source: OECD and UNEP/IE)
Combustion by-product Material burning
Carbon monoxide Most materials

Hydrogen cyanide Wool, cotton, silk, polyurethanes,
acrylonitrile polymers, urea-containing
resins
Nitrogen oxides Nitrocellulose, polyamides
Hydrogen chloride Polyester resins (some)
Polyvinyl chloride (PVC)
Chlorinated hydrocarbons
Sulphur dioxide Sulphur compounds, coal, mineral oil
Isocyanates Polyurethanes
Phosgene Polyvinyl chloride, pesticides (some)
Ammonia Polyamides, wool, silk, phenol resins
Hydrogen fluoride Teflon (polytetrafluoroethylene) and
other fluorine-containing compounds
Hydrogen bromide Bromine-containing compounds
Generally, most deaths in fires are caused by asphyxiation and not by

direct contact with the flame or exposure to heat.
3.3.1.2 Types of fires

Some types of fires associated with HNS releases are:
. flame jets: formed when a gas escapes to the atmosphere,
from a hole in a high-pressure line, and encounters an
ignition source;
. fireballs: formed in fires burning at sufficient rapidity for the
burning mass to rise into the air as a cloud or ball;
. vapour cloud fires: formed when a cloud or plume of
flammable gas (or vapour) encounters an ignition source.
In some cases, the fire will flash back to the spill source,
engulfing all in its path; and
. liquid pool fires: formed when a quantity of flammable liquid
is spilled on a surface (e.g., ship’s deck, jetty, land or water).
21

Chapter 3
3.3.1.3 Evaluation of flammability

Some common measures that can assist responders in evaluating the
flammability of a substance are:
. the flashpoint;
. the auto-ignition temperature; and
. the explosive (flammability) range or limits.
Further details on these properties are found in annex 3-1.
3.3.2 Explosive hazards

Explosions are characterized by a sudden release of energy generating a
shock or a strong pressure wave. These shock waves are referred to as
blast waves and are responsible for the associated loud bang. An
explosion may involve either a rapid chemical reaction (e.g.,
combustion) or the sudden release of contained thermal or mechanical
energy (e.g., the bursting of a pressure vessel).
Many substances may undergo various processes leading to an
explosion. Flammable gases, vapours and solids can create explosive
mixtures in air; some metals can react with corrosive liquids to
generate hydrogen, which can form explosive hydrogen–air mixtures;
other substances may react with water and generate poisonous and
pyrophoric gases, etc.
3.3.2.1 Explosions from compressed liquefied gases

In the case of compressed liquefied gases, the energy of the explosion is
stored in the difference of pressure between the inside of the container
and the atmospheric pressure. When a compressed liquefied gas reaches
a temperature above its normal boiling point, a sudden release of
pressure triggers the boiling, or flashing, of the liquid, creating a very
large increase in the material volume (for example, the expansion ratio of
propane is 270:1 and for LNG 635:1). This boiling/flashing condition
may be explosive, as in the case of a boiling liquid expanding vapour
explosion (BLEVE).
3.3.2.2 Explosive mixtures

There are two types of combustion that can lead to a shock wave: a
deflagration and a detonation. The main difference between the two
resides in the speed at which the reaction is taking place. A
deflagration is a combustion process propagating at subsonic speed,
while the more powerful detonation occurs at supersonic speed. The
faster the speed of propagation, the stronger the blast effect.
When a flammable gas, or a flammable vapour, is released and mixed
with air in an appropriate ratio, the mixture becomes explosive. Dust
emanating from certain cargoes may also constitute an explosive
hazard, especially while loading, unloading and cleaning tanks. The
22

explosion will occur as soon as energy input is provided. Shocks, friction,

heat, sparks, static electricity, fire or polymerization can trigger the
process.
A common measure used by first responders to evaluate the explosive

potential of a substance is the explosive limits or range (abbreviated LEL,
for lower explosive limit, and UEL, for upper explosive limit – see annex
3-1). The broader the explosive range of a substance, the greater the
probability of encountering a potentially explosive condition.
Table 3c: Examples of explosive (flammable) limits for some HNS

(Source: R.J. Lewis, Jr., Sax’s Dangerous Properties of Some Materials,
9th edition)
Substance LEL (%) UEL (%) Range (%)
Ammonia 16 25 9
n-Butylamine 1.7 9.8 8.1
Ethylene oxide 3 100 97
Vinyl chloride 4 22 18
3.3.2.3 Vapour cloud explosion (VCE)
A large atmospheric release of a gaseous or vapourized flammable

substance is the preliminary step leading to a potential vapour cloud
explosion (VCE). For a blast to take place, a substance has to be
released and mixed in open air in a quantity that will allow the
mixture to form a cloud. As soon as a fraction of this cloud lies within
the explosive range and encounters an ignition source, a flash fire, a
deflagration or, sometimes, even a detonation may occur with
devastating consequences.
3.3.2.4 Boiling liquid expanding vapour explosion (BLEVE)
The sudden and catastrophic vaporization of a contained liquid results

in a boiling liquid expanding vapour explosion or BLEVE (pronounced
‘‘blevey’’). A BLEVE is a physical process. Pressurized tanks containing
liquefied gas may partially fail and vent off their content, or may fail
suddenly and catastrophically lead to a BLEVE.
To cause a BLEVE, a liquefied substance does not need to be flammable.

However, if flammable, the likelihood of a fire resulting from the BLEVE
is high. If there is no ignition source the resulting cloud will drift off. If a
sufficiently large flammable cloud develops, a flash fire, a fireball or a
vapour cloud explosion is possible. A corrosive or toxic cloud drifting off
will jeopardize living organisms found in its path.
23

Chapter 3
Although flame/heat impingement on a tank is a well-known cause of

BLEVEs, it is not the only one. Pressurized tanks have been known to
lose structural integrity and BLEVE from corrosion, mechanical damage
or from undergoing internal chemical reactions (e.g., polymerization).
There is no warning sign before a BLEVE takes place. BLEVEs have been
known to occur when pressure safety relief valves were operating.
Accounts of higher-pitch sound from product venting off through the
safety valve as a sign of imminent danger have been proven to be
inaccurate. Extreme caution is required when a potential BLEVE
situation exists. Although a BLEVE is unlikely to involve a ship’s
tanks, the possibility of a BLEVE exists for portable tanks and every
effort must be made to prevent flame impingement or flame pools in
the proximity of these containers where these are carried on board.
3.3.2.5 Hazards from explosions

Explosions can result in several hazards including blast, projectiles, fire
and thermal radiation and toxicity. The shock wave can destroy
buildings and blow away anything in its path with considerable force.
The projectiles, either from a ruptured tank or from the objects
surrounding the explosion, will represent a significant hazard. In
many cases, the production of projectiles or fragments by the
explosion is the one threat which extends the furthest (some pressure
vessels have travelled over 1.5 km).
When a flammable gas or liquid is involved, fire and thermal radiation
from the fire are obviously of concern. Secondary fires can sometimes
create more significant threats. Similarly, when toxic or corrosive
substances are released, a hazardous cloud will disperse and is likely
to impact everything downwind.
The risks associated with the hazards progressively diminish when
moving away from the site of the explosion. Distance therefore remains
a valuable means of protection.
3.3.3 Static electricity hazards

Under certain circumstances the build-up of static electricity can pose
serious explosion or fire hazards, specifically when certain operations
give rise to the accumulation of electric charge which may be released
suddenly in electrostatic discharges with enough energy to ignite a
flammable environment. Importantly, it is the level of potentially
explosive or flammable vapours, gases or fine powders in the
atmosphere that gives rise to this hazard.
The build-up of static electricity may occur in a number of ways, such as:
. the rubbing of the skin against a personal protective
garment which has not been treated with an anti-static
finish;
24

. the act of filling or discharging powdered, granular or flaked

products in flexible intermediate bulk containers con-
structed from certain fabrics;
. splashing or turbulence during the initial pumping of
certain liquids into an empty tank; and
. the spraying of liquid from a nozzle during tank washing.
It is generally found that a liquid with an electric conductivity lower than
104 picoSiemens per metre is capable of retaining a significant
electrostatic charge and hence with the potential for static electricity
build-up.
Some guidelines for dealing with the hazards from static electricity can
be followed during response operations:
. when substances are being transferred, electrical grounding
should be the first and last step of the operation; hoses
should remain earthed until they are clear of the dangerous
atmosphere;
. splashing in the tanks should be avoided;
. inert gas conditions in tanks should be ensured;
. response personnel working near the transfer operation
must also be grounded and must wear specially-treated
clothing and footwear; and
. if specially-treated clothing is not worn, certain combina-
tions of fabrics must be avoided (e.g., nylon or cotton in
combination with PVC materials).
3.3.4 Toxic hazards

HNS can cause both short-term and long-term toxicological damage to
the marine environment. The most immediate concern however, should
be the protection of human health. This section focuses on the toxic
hazards posed to human life and health by HNS spills. Much of its
content can also be applied to the contamination affecting biological
systems in the marine environment.
3.3.4.1 Routes of exposure

Life-forms can be subjected to toxic effects when exposed to HNS. There
are four primary routes into the human body:
. inhalation is the major route of entry for gases and
particulate matter;
. ingestion is not a major concern for responders when proper
protective clothing is used and adequate hygiene and
decontamination procedures are followed. Ingestion of
contaminated food may represent a risk for local popula-
tions during HNS incidents;
25

Chapter 3
. skin and eye contacts are a problem in response, since some

substances can pass directly through the skin into the
bloodstream, while others cause immediate surface damage
due to their corrosive nature; and
. injection is a route of entry, where the skin is punctured or
injured.
3.3.4.2 Effects of HNS

The toxic effects of HNS may appear during exposure or immediately
after termination of the exposure or may be delayed for some time after
exposure.
A distinction is usually made between acute and chronic effects:
. acute effects are those that occur within a relatively short
period of time (minutes, hours, or days) following a short-
term exposure to a HNS, with the most extreme effect being
death;
. chronic effects are those that persist over a long period of
time whether or not they occur immediately on exposure or
their occurrence is delayed. Chronic effects may be:
– lethal, i.e., causing death of the organism;
– sublethal, i.e., detrimental to health, but not causing
death.
Some toxic effects are reversible, while others are irreversible.
A distinction is also made on whether the site of action of the HNS is local
or systemic:
. local effects occur at the primary site of contact, e.g., a skin
reaction following exposure to an organic solvent;
. systemic effects occur once the HNS has been absorbed and
circulated throughout the body, to a site distant from the
original contact or point of entry, e.g., liver damage following
inhalation of hydrocarbon vapours. In this respect, some
organs are known to be particularly sensitive to damage by
specific substances.
Terms frequently used to describe common toxic effects are found in
annex 3-1.
3.3.4.3 Determination of exposure limits for airborne HNS releases

A sudden release of a toxic gas or vapour into the atmosphere generally
poses a greater hazard to response personnel and the local population
than one involving a non-volatile material. Thus, one of the key tasks in
preparing for and responding to a gaseous HNS release is to determine
26

the concentration that can be tolerated by exposed populations. It is this

established ‘‘target’’ concentration that will determine the extent of the
exclusion zone.
Detailed exposure limits for airborne gases and vapours are published
by various government agencies. These limits are used as guidelines for
the operational handling of chemicals, and are known as the threshold
limit values (TLV) or maximum accepted concentrations (MAC).
Another useful airborne exposure limit is the immediately dangerous to

life or health (IDLH) concentration. This is the maximum airborne
concentration to which a human can tolerate a 30-minute exposure
without suffering any irreversible health effects.
Since exposure limits are continually being updated, the latest revisions
should be consulted. These values were developed for occupational
hazards in the workplace, where the exposed person is defined as a
‘‘healthy worker’’. This should be kept in mind when used for
situations involving elderly persons, young children or any individuals
with pre-existing health problems, all of whom may be at greater risk
than a ‘‘healthy worker’’.
Exposure limits are time-weighted averages and are set for single-
substance exposures. TLVs and IDLHs can only provide guidelines for
assessing exposure limits during emergencies. They should not be
regarded as definitive lines between safe and dangerous
concentrations. The application of any exposure limit value to an
emergency requires specialist interpretation. Such advice should be
sought during a formal review of the toxicity of the substance.
3.3.4.4 Factors affecting the toxic potential
The release of many HNS cargoes can pose toxicological threats. The
immediate concern should be the protection of human life and health.
The toxic hazard posed by a released material will depend on a number of
factors, such as:
. the amount spilled;
. the presence of more than one HNS released;
. the time frame over which spillage occurs, i.e., instanta-
neous or continuous;
. the physico-chemical properties of the substance;
. the route of exposure into the body;
. the concentration and duration of exposure;
. the stage of development of the individual;
. the physiological condition of the individual; and
. the prevailing meteorological conditions.
27

Chapter 3
3.3.5 Reactivity and corrosivity hazards

Some substances may react spontaneously under the effect of an energy
source (e.g., heat or friction) or when in contact with another substance.
Damage can occur when the reaction runs uncontrolled, and releases
energy in quantities and at rates too high to be dissipated readily by the
environment. Adverse consequences can include the generation of toxic
gases, excessive heat, rupture of the containment system, fire and
explosion. Some of the more common dangerous reactions are:
. Reactions with air, water or moist air
Some substances will:
– generate heat when mixed with water (e.g., concentrated
inorganic acids);
– become spontaneously flammable (e.g., white phosphorus
or phosphine); or
– give off flammable or toxic gases (e.g., calcium carbide or
aluminium phosphide).
Strong acids and bases may generate large amounts of
corrosive fumes when they come in contact with water.
Knowledge of the reactivity of a substance with water is
essential in a marine spill response, since the application of
water and water-based foams in the presence of a water-
reactive HNS can lead to a worsening of the situation.
. Reactions between incompatible HNS
Strong oxidizing or reducing agents (e.g., peroxides or
hydrazines) can react violently with organic and inorganic
materials. These reactions can generate heat and flammable
or toxic gases.
The inadvertent combination of various HNS cargoes may
generate a new substance, which may present hazards more
severe than those associated with the original materials. For
example, a slightly acidic alum solution will generate toxic
chlorine gas when mixed with calcium hypochlorite pellets.
. Polymerization reactions
Some HNS molecules are capable of reacting with them-
selves in a process called polymerization. They may do so
even under ambient conditions. Polymerization can be
triggered by heat or common substances such as water or
rust. When polymerization does take place, the heat given
off, or the expansion in volume caused by the reaction, can
lead to the rupture of the containment system and to the
spreading of residual material. A polymerization reaction,
once begun, is difficult to stop. Control of conditions
conducive to polymerization during transport are para-
mount to prevent accidents. The use of an inhibitor and
28

strict temperature controls are imperative to prevent the

polymerization of acrylic acid during transport. Contact
between the cargo and acids or various salts must be
avoided.
. Decomposition reactions
Some HNS spontaneously decompose at room temperature
from exposure to light or from the effect of heat, friction, or
pressure. For example, some organic peroxides must be kept
under controlled temperatures to prevent their sponta-
neous, and sometimes violent, decomposition.
Corrosivity is a special type of chemical reactivity. Corrosive
substances have three different types of properties, which
are of concern to responders of HNS incidents:
. they can cause chemical burns, causing destruction or
irreversible alteration of the human skin tissue at the
point of contact;
. they can corrode the materials used in the construction of
response equipment. For example, steel pumps will be
severely damaged on contact with chlorosulphonic acid;
or
. they can produce flammable vapours when in contact
with some materials, such as metals or fibrous products.
For example, iron and aluminium may react with some
strong acids or bases to release hydrogen, which in air
forms explosive hydrogen–air mixtures.
A chemical compatibility chart and general information on
the inadvertent mixing of substances from different chemi-
cal families can be found in annex 3-2.
3.3.6 Nuclear radiation hazards

Although radioactive materials can share other hazardous properties (e.
g., corrosivity) with non-radioactive substances, the primary concern is
their ionizing radiation characteristics. Uranium hexafluoride is an
exception to this as its corrosivity is generally the primary hazard.
Ionizing radiation is created when nuclei give off excess energy. This
radiation will lose its energy when passing through matter, including
living tissues. The resulting absorbed energy will break down some
molecules into ionized fragments.
There are four types of ionizing radiation which may be encountered
from packages being transported: alpha, beta radiation and neutron
radiation, which are extremely small particles moving at high velocity,
and gamma radiation, which has similar properties to X-rays.
29

Chapter 3
. Alpha radiation
Alpha particles are completely absorbed by a few centi-
metres of air. Outside the body, alpha radiation energy will
dissipate while penetrating clothing or the dead cells of the
epidermis. If ingested or inhaled, alpha emitters will strongly
ionize internal tissues.
. Beta radiation
Beta particles can travel more than a metre through air and
can penetrate several millimetres of aluminium and of
plastic. Beta emitters represent both external and internal
hazards. This type of emission can damage skin and internal
organs.
. Neutron radiation
Neutrons interact with atoms and molecules in complex
ways. Collisions between the neutron and the smallest atom,
hydrogen, result in the greatest transfer of energy from the
neutron to the absorbing medium. Neutrons have a range of
many metres in air and many centimetres in tissue.
Moderated, that is, slowed down, neutrons will eventually
be absorbed by or pass through a human body.
. Gamma radiation
Gamma rays are the most penetrating of all radiations. They
will pass through human tissues in a manner similar to
X-rays. Gamma rays can cause skin burns and can damage
internal organs.
Protection from ionizing radiation has two important aspects:
. External sources of radiation
Exposure from an external source (such as an intact
package of radioactive material or one which has damaged
shielding) can be reduced by increasing your distance from
the sources, reducing your time in the vicinity of the source
and providing intervening shielding between you and the
source.
. Internal and external contamination
Protective clothing and respiratory protection will minimize
the potential for intake and skin contamination from loose
material (such as from a damaged and leaking package).
3.3.7 Other hazards

An additional hazard of certain cargoes relates to their mode of carriage,
rather than to the inherent properties of the cargo itself. An example of
such a cargo is that of liquefied gas carried at cryogenic temperatures. If
this cargo is allowed to escape and come into contact with the ship
structure, brittle fracture of the steel can occur leading to substantial
damage with the increased possibility of a release.
30

The low temperature of such cargoes is a danger to personnel. Skin

contact with the cargo can cause cold burns or frostbite. The injury is
caused by heat being taken from the human body as the cold liquid
evaporates, giving rise to cold burns.
3.4 Behaviour and fate of released HNS

3.4.1 Short-term behaviour
3.4.1.1 General remarks
Certain actions should always be taken when HNS accidents occur.
These are often the same for most types of accidents, regardless of the
circumstances and the HNS involved (see chapter 5).
When responding to a HNS spill in water, it is important that the
measures are adjusted to allow for the HNSs physical behaviour. The
patterns of spill behaviour in water of various HNS groups are
discussed in this section.
Figure 3.3: Principal behaviours of a HNS when spilled into water

Figure 3.3 illustrates the principal behaviours of a HNS when spilled into
water. However, it should be stressed that this diagram is simplified. A
HNS spill may exhibit more than one of these behaviours at the same
time. For example, the chemical may float on the water surface and at the
same time evaporate and/or dissolve. The chemical may also react with
water. Furthermore, in figure 3.3 it is being assumed that the only form
of HNS in the water column is the dissolved component. However, under
certain conditions, tiny droplets of HNS do form which have a different
behaviour from the dissolved component.
31

Chapter 3
Figure 3.4: A graphical representation of HNS behaviours according to the

behaviour groups in the behaviour classification system
3.4.1.2 Behaviour classification system: classification flow chart

A graphical illustration of the behaviour classification system for HNS
spills in water is shown in figure 3.4. The system is based on HNS
physical behaviour in water (solubility, density, and vapour pressure)
and it comprises 12 behaviour groups (G, GD, E, ED, etc.) for releases
of HNS, as well as three groups for packages (where PF = package/floater,
PI = package/immersed and PS = package/sinker). A detailed flow chart
of the system is presented in annex 3-3.
It should be noted that the behaviour classification system is applicable
only for the initial behaviour of HNS spills in water, and does not
describe its long-term fate.
3.4.1.3 Behaviour groups of the classification system

The following physical properties determine a chemical’s behaviour
when it is spilled into water:
. solubility: the ability of a substance (a gas, a liquid or a solid)
to form, with a solvent, a homogeneous mixture in which no
settling occurs. It describes the maximum concentration, in
percentage, of the substance in the solution, at a given
temperature. Water is a very common solvent. Solubility of a
substance in water is the maximum concentration by weight
of the substance in a solution of water.
32

. density: the mass, in grams, of one millilitre of substance.

Substances with very different densities and which are
immiscible will tend to separate from each other (e.g., oil and
water).
. vapour pressure: the ability of a liquid or a solid to give off
vapours. The higher the vapour pressure, the faster a liquid
will tend to evaporate, and the higher the concentration of
vapours in the air. The vapour pressure is measured in
atmospheric pressure units (e.g., kPa, mm Hg, bar, atm).
These three properties are very sensitive to temperature changes.
Consequently, when solubility, density or vapour pressure values are
given, the temperature at which they were measured must also be
given. In order to group substances using this classification system, a
specific temperature may be chosen which is representative of local
climatic conditions, e.g., 10oC, 20oC.
The behaviour classification system flow chart (shown in annex 3-3),
defines the physical parameters of each of the 12 property groups of
released substances and the three groups for packages. Table 3d
shows examples of chemicals and their physical properties. By
referring to this table and to the flow chart, the chemicals can be
referred to the appropriate property groups.
Table 3d: Some chemicals and their physical properties at 20oC
Vapour
Solubility Density pressure Behaviour
Product (%)(w/w) (g/ml) (kPa) group Substance will
Benzene 0.07 0.88 10.1 E float, evaporate

rapidly
Diisodecyl 0.001 0.97 0.0001 F float

phthalate
Tall oil 0.003 0.92 0.2 F float
Sulphuric acid 100 1.85 0.001 D dissolve rapidly
Tetraethyl lead 0.0001 1.66 0.01 S sink
Trichloroethylene 0.1 1.46 7.7 S sink
Table 3e shows an overview of the 12 behaviour groups of the

classification system, along with the designations for the various
groups, and the definitions of the designations. Information is also
given on various properties that are characteristic to the groups, as
well as examples of chemicals belonging to each group. The difference
between a substance classified as ED or DE is that in the former case
evaporation takes place in a few hours and is quicker than dissolution
33

Chapter 3
whilst in the latter case dissolution is quicker than evaporation (see

annex 3-3 for an exact physical distinction). The rightmost column
shows the preferred environment (air, water surface, water body, or
bottom) into which the HNS will tend to spread.
Table 3e: An overview of the 12 behaviour groups of the behaviour

classification system (Source: Swedish Coast Guard)
Group SPREAD
designation A = air
WS = water
Meaning of Properties Examples surface
designation WB = water
body
B = bottom
G evaporate propane, butane vinyl A
Evaporate gas immediately chloride
immediately
(gases) GD evaporate ammonia A
gas/dissolver immediately WB
E float, evaporate benzene, hexane, A

evaporator rapidly cyclohexane
Evaporate
rapidly ED evaporate rapidly, methyl-t-butyl ether vinyl A
evaporator/ dissolve acetate WB
dissolver
FE float, evaporate heptane, turpentine A

floater/ toluene xylene WS
evaporator
FED float, evaporate, butyl acetate isobutanol A

floater/ dissolve ethyl acrylate WS
Float evaporator/ WB
dissolver
F float phthalates, vegetable WS

floater oils, animal oils,
dipentene, isodecanol
FD float, dissolve butanol, butyl acrylate WS
floater/dissolver WB
DE dissolve rapidly, acetone, monoethyl A

dissolver/ evaporate amine, propylene oxide WB
evaporator
Dissolve D dissolve rapidly some acids and bases WB

dissolver some alcohols, glycols
some amines
methyl ethyl ketone
SD sink, dissolve dichloromethane WB
sinker/dissolver 1,2-dichloroethane B
Sink
S sink butyl benzyl phthalate B
sinker chlorobenzene creosote,
coal tar
tetra ethyl lead
tetra methyl lead
34

3.4.1.4 Examples of behaviour
Spills of liquefied ammonia

Several extensive trials have been performed regarding the behaviour of
ammonia (behaviour group GD) in water. Liquefied ammonia shows
instant and intense boiling when in contact with water, but also
dissolves readily in water. Gaseous and liquefied ammonia, as well as
its water solution, are corrosive and hazardous to human health and
marine life respectively. The gaseous ammonia rises in air and moves
in the wind direction as a dense white cloud.
The amount of ammonia dissolved in water depends on:
– the amount of ammonia released;
– the environmental conditions; and
– how the discharge occurs – instantaneously or continu-
ously, above or below the water surface.
Approximately 60% dissolves when released above the water surface and
more than 90% when released below the water surface. A major portion of
the dissolved ammonia forms a solution of ammonium hydroxide in the
surface water layer before mixing slowly into the water body. It has been
shown that the minor non-ionized fraction of ammonia is responsible for
the toxic effects on aquatic organisms (see figure 3.5).
Figure 3.5: The dissolution of ammonia in water

Low- or high-density substances spilled in still water

(e.g., methyl alcohol and sulphuric acid)
The rate at which a freely soluble liquid mixes with water is dependent
on several factors:
– whether the liquids are lighter or heavier than water; and
– whether the water is cold, still or both.
Figures 3.6 to 3.8 show different behaviours for methyl alcohol and
sulphuric acid in still water.
35

Chapter 3
Figure 3.6: Behaviour of a continuous spill of methyl alcohol in still water

Figure 3.7: Behaviour of a continuous spill of sulphuric acid in stagnant

water (Source: Swedish Coast Guard)
36

Figure 3.8: Behaviour of an instantaneous spill of sulphuric acid

in still water (Source: Swedish Coast Guard)
Spills of sparingly soluble heavy liquids in water streams

(e.g., carbon tetrachloride, carbon disulphide,
ethylene dichloride, tetraethyl lead)
The spread of HNS spills in water streams is dependent upon the HNS
physical properties (density, solubility, vapour pressure, state of
aggregation, etc.), as well as the current velocity and shape of the
flowing water. The behaviour of heavy, sparingly soluble liquids in
flowing water has been examined. The sunken liquid was distributed
in the current’s direction, according to pool and drop size (see figure
3.9). Small fractions were formed from such spills and were distributed
as tiny droplets in all directions of the water body.
Figure 3.9: Sinking of sparingly soluble liquids in the current’s directional

flow and their dispersion into zones of different pool sizes
37

Chapter 3
3.4.1.5 Behaviour variation

Effect of cold temperature on evaporators and dissolvers
Some liquid HNS solidify in cold water and form sheets, or chunks,
which are more resistant to dissolution, or evaporation, than their
corresponding liquids. The process of solidification in cold water
depends on the water temperature, the freezing point (=melting point),
the solubility, and the evaporation rate of the substance (see tables 3d to
3e). Low temperatures decrease both the evaporation and dissolution
rates. Therefore, when a freezing point above the water temperature
coincides with a low or moderate solubility (or evaporation rate),
solidification will result upon contact with water. This type of HNS will
become a normal floater or sinker, and will be easier to pick up by
standard recovery techniques.
The first four HNS listed in table 3f have very low values of solubility and
vapour pressure. Their behaviour will not change significantly when
they change from the liquid to the solid state upon contact with water.
Benzene and cyclohexane, as liquids, are difficult to recover from the
water surface because of their rapid evaporation rate. At temperatures
below their freezing points, they solidify and their evaporation rates are
greatly reduced, making recovery easier.
Phthalic anhydride solidifies upon release into water. The solidification
process retards its dissolution and makes it easier to recover than
normally expected from its solubility value.
Table 3f: HNS solidifying in cold water
(Source: HELCOM Combating Manual, vol. III)
Property Water temperature Freezing Vapour

Substances group range{ Solubility* pressure*
o
0 C o
10 C (oC) (%) (kPa)
Tall oil, crude F (X) (X) -10 to +30 0.001 0.1

Tallow F X X +30 to +50 0.0001 0.0001
Tallow fatty F X X +35 0.01 0.001
acid F (X) (X) -20 to +50 0.01 0.001
Vegetable oils
Benzene E X +6 0.05 6
Cyclohexane E X +7 0.005 6
Creosote, coal S (X) (X) -6 to +41 0.01 0.1

tar
Phthalic S X X +131 0.3 0.0001
anhydride
X = HNS solidifies when released into water;

(X) = some grades will solidify
{ The values in the freezing range column indicate limits for various grades of
HNS
* At 10oC
38

Table 3g shows HNS with freezing points above 0oC which dissolve
rapidly, even in cold water, due to their high solubility. This results in
the formation of a growing plume of concentrated solution of the
substance moving with the flowing stream.
Table 3g: Melting points of some soluble HNS

Property Melting point Solubility

Substances group (oC) (%) (w/w)
Acetic acid D +15 100

Diethanolamine D +28 100
Ethylenediamine D +11 100
Formic acid D +8 100
Phosphoric acid (85%) D +15 to +28 100
Sodium hydroxide, solution (50%) D +8 100
Sodium hydroxide, spent solution (50%) D +8 100
Sulphuric acid (98%) D +3 100
Phenol (melting point: 41oC; solubility: 8.4%; vapour pressure: 0.1 kPa) is
an interesting intermediate example. It is often transported and handled
as a hot molten cargo. Its D group designation suggests that it dissolves
in water at ambient temperature. Nevertheless, in one incident, 400
tonnes of molten phenol leaked from a cistern and sank. It was easily
picked up by mechanical dredging. This unexpected behaviour was
explained by the sudden spillage of a large volume of phenol, rapidly
saturating the shallow harbour waters.
Figure 3.10: Sunken solidified phenol in a harbour accident

HNS that react with water

Only a few of the commonly transported HNS react rapidly with cold
water. These substances could, in theory, be classified in a behaviour
group based on their solubility, density and vapour pressure. However,
their actual behaviour does not coincide with what would be expected
39

Chapter 3
from the standard behaviour classification, since they react with water.
Some commonly transported water-reactive HNS are briefly described
below:
. acetyl chloride is a fuming liquid that, upon contact with
water, reacts violently and decomposes to hydrochloric acid
and acetic acid;
. calcium carbide is a solid (i.e., powder or lumps) which sinks,
violently reacting with water and forming acetylene, a highly
flammable and explosive gas;
. sodium and potassium are very reactive metals which float
and react violently with water, forming flammable hydrogen
gas mixtures with air. The heat of the reaction often causes
the hydrogen to ignite and explode;
. sulphonyl chloride is a fuming liquid which reacts violently
with water, and decomposes to sulphuric acid and hydro-
chloric acid;
. toluene diisocyanate is a sinking liquid which reacts slowly
with cold water to form carbon dioxide and a plastic-like
product (polyisocyanate);
. concentrated sulphuric acid, when mixed with water, may
release large amounts of heat, resulting in vigorous boiling.
3.4.2 Marine environmental hazards and long-term fate
Significant spills could expose first responders and other persons to a

high concentration of a toxic substance for short periods of time. Such
exposures are referred to as acute. Once the release is controlled, and
depending on its properties, the material may either be eliminated or
may persist in the environment for a long period of time. If the
substance does persist, exposure will become a chronic problem.
Various abiotic and biotic processes can modify the toxicity of a HNS,
and must be considered in the planning for chronic hazards. The
concentration, distribution, transformation and long-term fate of a
substance in the marine environment are primarily controlled by:
. the rate of release of the substance into the environment;
. the physico-chemical properties of the substance (see
section 3.3);
. the physico-chemical, meteorological and oceanographical
conditions of the environment; and
. the biodegradation and biotransformation properties of the
ecosystem.
These factors will affect the availability of the toxic substance to the
organisms (bioavailability). Figure 3.11 gives an overview of the factors
affecting the concentrations of some substances.
40

Figure 3.11: Transformation of chemicals in the marine environment

belonging to the major behaviour groups (Source: CEDRE, France)
The following criteria may assist in the evaluation of the hazards of a

HNS to marine organisms:
. acute aquatic toxicity is the ability of a substance to cause
damage to marine organisms within a short specified time. It
is expressed in terms of IC50, EC50 or LC 50 values. These
values are the minimal concentrations likely to cause,
within 72, 48 or 96 hours, inhibitory reproductive or growth
effects (IC50), deleterious effects (EC50) and lethal effects
(LC50) to 50% of the tested organisms.
41

Chapter 3
Table 3h: Acute toxicity data rating and their significance

according to GESAMP
LC50, EC50 or IC50 Significance Toxicity ratings
> 1000 mg/l non-toxic 0
100 – 1000 mg/l practically non-toxic 1
10 – 100 mg/l slightly toxic 2
1 – 10 mg/l moderately toxic 3
0.1 – 1 mg/l highly toxic 4
0.01 – 0.1 mg/l very highly toxic 5
< 0.01 mg/l extremely toxic 6
. bioaccumulation is the phenomenon of a chemical sub-

stance accumulating in an organism, through the food or
water, reaching greater concentrations than that occurring
in the surrounding medium. The tendency of a compound to
partition between water and the fatty tissues of an organism
governs much of its biological activity and potential hazard,
particularly in the long term. When the material is
accumulated from the water phase, it can be expressed as
the bioconcentration factor (BCF). For a wide variety of
organic substances, the log octanol/water partition coeffi-
cient (log Pow) acts as a surrogate, to indicate the tendency of
a substance to bioaccumulate. Low values of log Pow or BCF
indicate low bioaccumulation potential, high values indicate
high potentials. Substances with very high log Pow values
(>7) are presumed to be too insoluble to show any potential
to bioaccumulate, whilst the probability of measurable
bioaccumulation in aquatic species is low for a molar mass
higher than 700.
. tainting is the induction of a foreign flavour or odour in
organisms by conditions in the water to which the organ-
isms are exposed. A substance has a tainting property when:
– a substance is considered to taint seafood if it has been

tested and is found to taint seafood at concentrations at
or below 1 mg/l; and
– a substance is considered to have the potential to taint
seafood if other evidence exists that tainting may occur (e.
g., due to chemical analogy with known tainting sub-
stances, organoleptic properties or data from HNS spil-
lages which have resulted in tainting seafood).
42

Table 3i: Bioaccumulation rating criteria and their significance

according to GESAMP*
Log Pow BCF Significance Rating
log Pow <1 or > 7 no measurable BCF No potential to bioaccumulate 0
log Pow 1 to <2 BCF 1 to <10 Very low potential to bioaccumulate 1
log Pow 2 to <3 BCF 20 to <100 Low potential to bioaccumulate 2
log Pow 3 to <4 BCF 100 to <500 Bioaccumulate to moderate extent 3
log Pow 4 to <5 BCF 500 to <4,000 Bioaccumulate to high extent 4
log Pow >5 BCF >4,000 Bioaccumulate to a very high potential 5
Table 3j: Some examples of substances with tainting properties

Camphor oil Diphenylether
Carboxlic acid Ethylacrylate
Chlorophenols 1-Methylnaphthalene
Creosote (wood tar) 2-Methylnaphthalene
Cresols Naphthalene
1,2-Dichlorobenzene Naphthenic acids
Dichlorodiethylether a-pinene
Dichlorophenols 2,4,6-trichlophenol
. persistence is the ability of a material to stay in the marine

environment without degradation. Substances that either
do not degrade, evaporate, or dissolve very slowly and form
slicks on the sea surface are considered persistent (e.g.,
dodecylbenzene). Inert substances such as mineral ores and
other geologically bound solids might be persistent but, due
to their low solubility and reactivity, produce a smothering
effect. A substance can be considered to be degradable if it is
shown that the substance can be degraded (biotically and/or
abiotically) in the aquatic environment to a level of greater
than 60% to 70% within a 28-day period. Results from
‘‘readily biodegradable’’ studies can be used to indicate the
potential of HNS to be biodegraded. Positive results imply
* Based on the work of the IMO/FAO/UNESCO-IOC/WHO/IAEA/UN/UNEP

Joint Group of Experts on the Scientific Aspects of Marine Environmental
Protection (GESAMP).
43

Chapter 3
primarily rapid removal of the substance as well as a

secondary implication of whether the substance inhibits
microbial activity.
In the context of an accidental HNS spillage, the EC50 or LC50 values,
bioaccumulation, tainting and biodegradation data used singly or in
combination could assist in the evaluation of hazards to the marine
environment.
44

Annex 3-1
Definitions of terms used to describe
hazard characteristics
1 Combustibility describes the ability of a material to burn under

normal conditions. For combustion to occur, oxygen, fuel and an
ignition source must be present.
2 Flammability describes the ease with which a material will ignite,

either spontaneously from exposure to a high temperature, or from
exposure to a spark or open flame. The flammability of a material can
be described by the following properties:
. vapour pressure indicates a substance’s ability to form
vapour. When a substance evaporates, its vapour exerts a
pressure in the surrounding milieu. This is the vapour
pressure. It is expressed in units of pressure at a particular
temperature and atmospheric pressure. The higher a
substance’s vapour pressure, the more it tends to evaporate;
. the flashpoint is the lowest temperature of a substance at
which its vapours will ignite and burn when exposed to an
ignition source, without self-sustaining combustion;
. the fire point is the lowest temperature at which a substance,
once ignited, will continue to burn without any additional
source of energy;
. the lower explosive limit (LEL) or lower flammable limit (LFL)
is the minimum concentration of a gas (or vapour) in air that
will ignite and propagate a flame. It is expressed as a
percentage by volume of gas in air. If the gas percentage is
below the LEL, the atmosphere is described as being ‘‘too
lean’’ to burn;
. the upper explosive limit (UEL) or upper flammable limit (UFL)
is the maximum concentration of a gas (or vapour) in air that
will ignite or propagate a flame. It is expressed as a
percentage by volume of gas in air. If the percentage is
above the UEL, the mixture is described as being ‘‘too rich’’
to burn. When the gas (or vapour) to air ratio is between the
LEL and the UEL, fires and explosions can occur, and the
mixture is said to be within the flammable range;
. the flammable range is the difference between the upper and
lower flammable limits; and
45

Chapter 3
. the auto-ignition temperature is the lowest temperature at

which spontaneous combustion of a substance begins in
the absence of any spark or flame. The closer the auto-
ignition temperature, the greater the risk of a fire or
explosion.
3 Explosivity describes the ability of a substance, either pure or mixed
with other substances, to react rapidly to produce high local
temperatures, and to generate large volumes of gases. When a
flammable material is limited to a confined area and ignited, an
explosion will result.
4 Corrosivity describes the ability of a material to cause electro-
chemical degradation of metals or alloys. It also describes the
destruction of body tissues by acids and bases. The relative strength of
acids and bases is often indicated by the pH scale. A pH value
corresponds to the negative logarithm of the concentration of hydrogen
ions (H+) in water. The pH values of acids are below 7, and the pH values
of bases are above 7. The smaller the pH value, the stronger the acid. A
larger pH value corresponds to a more basic solution. The pH value of a
neutral solution (neither acidic nor basic) is 7. Since pH values are
measured on a logarithmic scale, a change in one unit means a 10-fold
change in strength.
5 Reactivity describes the ability of a material to change chemically, by
processes involving combination, replacement or decomposition.
Chemical reactions may be endothermic, requiring external heat to
keep them running, or exothermic, creating heat in the process.
6 Toxicity is the ability of a material to inflict damage to living tissue,
impair the central nervous system, cause severe illness or, in extreme
cases, cause death when inhaled, ingested, injected or absorbed by the
skin. Toxic HNS have specific effects such as:
. asphyxiant: most often associated with gases that, when
present in sufficient quantities in the working environment,
restrict the amount of oxygen necessary to sustain life.
Examples of asphyxiants and gases that fall into this
category include inert gas (used on many bulk tankers),
carbon dioxide (a byproduct of fire or rusting) and methane
(a HNS cargo). A second group, the chemical asphyxiants,
prevent the transport of oxygen from the lungs or the
transfer of oxygen to the cells (e.g., the highly toxic carbon
monoxide);
. carcinogenic: capable of causing cancerous growths in living
tissues;
. endocrine disruptor: capable of causing adverse health
affects through changes in endocrine function;
. haeomatotoxic: capable of causing injury to the blood and/or
blood-forming tissues;
46

. immunotoxic: capable of causing injury to the immune

system and of interfering with body defence mechanisms;
. irritant: capable of causing local inflammatory response;
. mutagenic: capable of causing molecular injury to the
heredity carrying material;
. neurotoxic: capable of causing neurological damage; and
. teratogenic: capable of causing injury to the foetus resulting
in permanent structural and/or functional malformations.
7 Radioactivity: the ability of a substance to emit alpha–beta particles
or gamma radiation.
47

Chapter 3
Annex 3-2
Example of a chemical compatibility chart
1 This cargo compatibility chart has been developed and is updated

annually by the United States Coast Guard. A full description on the use
of the chart is given in the U.S. Code of Federal Regulations, title 46, part
150.
2 The guide was developed to determine those chemicals which are
safe for adjacent loading on barges and tankers. Chemicals are
considered to be incompatible, if, on mixing, the temperature rise
exceeds 25oC or a gas is evolved. The box formed by the intersection of
the column and row containing numbers contains one of the following:
blank: the two cargoes are compatible
x: the two cargoes are not compatible
A letter other than x: r e a c t i vi t y va r i es a m on g t he g r o u p
members. Refer to the notes set out
below. Unless the combination is
specifically mentioned in the notes, it is
compatible.
Notes to compatibility chart

– Reactivity differences (deviations) within chemical groups
A Acrolein (19), crotonaldehyde (19) and 2-ethyl-3-propyl acrolein

(19) are not compatible with group 1, non-oxidizing mineral acids.
B Isophorone (18) and mesityl oxide (18) are not compatible with
group 8, alkanolamines.
C Acrylic acid (4) is not compatible with group 9, aromatic amines.
D Allyl alcohol (15) is not compatible with group 12, isocyanates.
E Furfuryl alcohol (20) is not compatible with group 1, non-oxidizing
mineral acids.
F Furfuryl alcohol (2) is not compatible with group 4, organic acids.
G Trichloroethylene (36) is not compatible with group 5, caustics.
H Ethylenediamine (7) is not compatible with ethylene dichloride
(36).
48

81089
49
22 12 02 91 81 71 61 51 41 31 21 11 01 9 8 7 6 5 4 3 2 1 )segap suoiverp no seton ot refer sretteL(
34 X X snoitulos retaw suoenallecsiM .34
24 X X X X X sdnuopmocortiN .24
14 X X srehtE .14
04 X X srehte locylG .04
93 enalohpluS .93
83 X X edihplusid nobraC .83
73 X selirtiN .73
63 I H snobracordyh detanegolaH .63
53 X X sedilah lyniV .53

43 X X sretsE .43
33 X serutxim nobracordyh suoenallecsiM .33
23 X snobracordyh citamorA .23
13 sniffaraP .13
03 X X snifelO .03
Compatibility chart
22 X X X X noitulos mutcalorpaC .22

12 X X X X X sloserc ,slonehP .12
02 X X X F X X E slocylg ,slohoclA .02
91 X X X X X X X A sedyhedlA .91
81 B X X X senoteK .81
71 X X X X X X X X nirdyhorolhcipE .71
61 X X X X X X X X sedixo enelyklA .61
51 D X X X X slylla detutitsbuS .51
41 X X X X setalyrcA .41
31 X X X X X X etateca lyniV .31
21 X X D X X X X X X X X X X setanaycosI .21
11 X X X X X X X X sedirdyhna cinagrO .11
01 X X X X X X sedimA .01
9 X X X C X X X senima citamorA .9
8 X B X X X X X X X X X X X senimalonaklA .8
7 X X X X X X X X X X X X X X X X senima citahpilA .7
6 X X X X X X X X X X X ainommA .6
5 X X X X X X X X X X X X scitsuaC .5
4 F X X X C X X X X X sdica cinagrO .4
3 X X X X X X X X X X X X X X X X X X dica cirtiN .3
2 X X X X X X X X X X X X X X X X X X X X X dica ciruhpluS .2
1 E A X X X X X X X X X X X X sdica larenim gnizidixo-noN .1
spuorg ograC
sedyhedlA .91
senoteK .81
nirdyhorolhcipE .71
detutitsbuS .51
etateca lyniV .31
sedimA .01
gnizidixo-noN .1
sedixo enelyklA .61
setalyrcA .41
setanaycosI .21
cinagrO .11
matcalorpaC .22
,slohoclA .02
ainommA .6
senimalonaklA .8
sdica cinagrO .4
dica ciruhpluS .2
sloserc ,slonehP .12
senima citamorA .9
senima citahpilA .7
scitsuaC .5
dica cirtiN .3
spuorg evitcaeR
slylla
sdica larenim
sedirdyhna
noitulos
slocylg
Chapter 3
Annex 3-3
A classification flow chart
The figure below shows a flow chart for the behaviour classification
system of HNS spills in water. The system describes the behaviour of
substances spilled in water based on their solubility, density, and
vapour pressure. It includes 12 behaviour groups (G, GD, E, ED, etc.)
for substances and three groups for packages (PF, PI and PS).
50

Chapter 4
Chemical emergency preparedness
4.1 General remarks on emergency response systems

For administrations to ensure a safe, timely and effective response, a co-
ordinating framework and a series of standard operating procedures
must be established. This will facilitate early definition of the specific
commodities involved, reducing the potential magnitude of the incident.
A ‘‘decision tree’’ approach can be used to initially evaluate the
magnitude of the incident and to assign the incident to a specific
category or level. The assigned level may then be used to determine
appropriate response mechanisms and to allocate roles and
responsibilities. Figure 4.1 provides the conceptual framework for the
categorization of response levels as a basis for emergency planning.
Figure 4.1: Framework for categorizing response levels (Source: REMPEC)
The aim of this section is to identify the essential components of an

emergency response system. The following is based on a review of
several national regimes and of the IMO guidance documents.
51

Chapter 4
Key elements identified as being essential to any regime:

. organizational arrangements: to provide a clear identifica-
tion of roles, responsibilities and capabilities;
. planning requirements: to provide specific guidance in
responding to an incident;
. monitoring and reporting: to ensure all incidents are
assessed, evaluated and followed up as appropriate;
. defined operational procedures: to allow a tiered response to
an incident;
. training and exercising: to provide response personnel with
skills necessary to do their jobs effectively and safely; and
. financial and liability arrangements: to determine financial
responsibility and liabilities of the various parties involved.
4.1.1 Organizational arrangements

In any response regime it is essential that the roles, responsibilities, and
capabilities of the various parties be clearly identified. The fundamental
issue with respect to roles and responsibilities is to establish clearly who
has the onus of response. That is, who is responsible for responding to
an incident, including the implementation of response plans.
Consideration must also be given to the many tasks throughout the
development, implementation and maintenance phases. Elements can
be placed in four general categories: prevention, preparedness,
response and recovery/remediation. Some of these tasks are briefly
outlined below.
4.1.2 Prevention
Activities directed toward prevention of incidents and reduction of their
magnitude are critical elements in the emergency response regime. In
addition to providing overall co-ordination, the administration may:
. evaluate existing documentation, policies, guidelines and
legislation, to identify duplication and/or information gaps;
. prepare relevant policies and legislative elements; and
. establish mandatory compliance requirements.
4.1.3 Preparedness
Preparedness activities are meant to enhance the ability to respond to
emergencies. This involves a number of sub-elements such as:
. development of emergency response plans;
. ensuring the availability of certain response resources and
equipment;
. training and exercising of personnel; and
52

. establishment of communication and alert channels,

including, among others, linkage with the media.
Preparedness should take into account the various scenarios relevant to
probable spills, and the organizations and activities likely to be involved.
It should involve the joint planning and training of those who may need
to work together if an accident occurs, including industries and the
surrounding communities.
Administrations should provide plans and expert assistance and should
ensure that an operational centre exists for the collection of routine and
emergency information. Incident monitoring and co-ordination should
also be provided. Specific issues of concern should include:
. to prepare relevant guidelines and policies;
. to define routine and incident reporting requirements;
. to prepare and implement periodic inspection and auditing
protocols, to ensure that appropriate equipment, systems
and procedures are being implemented and adhered to;
. to collect and disseminate information;
. to define emergency response planning requirements,
response capability and preparedness standards for vessels,
facilities and port/harbour authorities;
. to establish information databases pertaining to shipping
information (e.g., stowage plans, bills of lading, ship passage,
ports of call), chemical and physical properties and response
protocols; the level of confidentiality required for this
information must be established in conjunction with the
relevant stakeholders;
. to create a ‘‘pool of experts’’ to act as an advisory group.
Individuals with expertise in the following areas:
– navigation;
– ship technology;
– naval architecture;
– chemical hazards;
– marine biology;
– physical and chemical oceanography;
– dispersion modelling;
– spill response; and
– fire fighting;
. to identify a co-ordination unit made up of individuals with
proven expertise in the areas of emergency, crisis manage-
ment and transfer operations;
53

Chapter 4
. to identify an operation centre to provide access to informa-

tion databases, standard operating procedures, advisory
personnel and communications equipment;
. to identify chemical response units;
. to train the personnel of the chemical response unit; and
. to co-ordinate with IMO, international and national organi-
zations and information sources, both in routine and
emergency situations.
4.1.4 Planning requirements
Planning requirements include the preparation of detailed and specific

plans for responding to a marine incident. International multilateral,
national and local emergency response plans should be prepared to
summarize roles and responsibilities for all parties, providing standard
operating procedures, lists of available resources, etc.
Plans are required at three levels:

. at the international level with the framework of an opera-
tional contingency plan;
. at the national level; and
. at the local (e.g., for terminals and harbours/ports) and area
level.
Should the magnitude of an accident be such that assistance is required,

these plans should be integrated in such a way that it will be easy to
incorporate additional response capabilities. For example, a port
emergency plan should be co-ordinated with neighbouring industrial
facilities’ plans as well as with the national plan.
4.1.5 Monitoring, reporting and record-keeping
A key facet in the preparedness process is the establishment of reporting

procedures which will indicate:
. who is responsible for reporting;
. to whom reports are to be made;
. what format should be used; and
. when reports are to be made.
The reporting procedures should be linked to an appropriate record-

keeping process.
54

4.1.6 Defined operational procedures

To ensure that an appropriate and effective response is initiated in a
timely fashion, it is necessary to develop clearly defined procedures for
the critical assessment of marine accidents. It is of paramount
importance that responsibilities and roles are clearly defined and
operational procedures properly co-ordinated.
4.1.7 Training and exercise

Training standards should be prescribed for all response personnel,
whether performing at the decision-making or operational levels, and
should include:
. specific training content pursuant to individual job perfor-
mance expectations;
. schedules for implementation and compliance dates;
. requirements for the issuing of training certificates and
their specific content;
. requirements for periodic refresher training (e.g., every three
years);
. requirements for exercises or drills, to evaluate response
programme implementation/ effectiveness;
. certification/approval of training delivery organizations; and
. equivalency with international training requirements.
4.2 Optimized response organization

When an accident involving a HNS spill occurs, the first personnel to be
involved will be the ship’s crew. The crew is usually trained for
emergency response on board, but many of the crew members may not
be aware of the potential environmental impact of spills at sea. In the
case of a HNS accident, a ship’s crew may need to take shelter-in-place or
abandon the ship. Thus, each coastal State should have an effective
response organization established to deal with such events.
Response personnel intervening on the pollution are more likely to be
those involved in oil-spill response, and therefore will be aware of certain
environmental concerns. However, they may not be fully familiar with
the hazards from the chemical spilled.
It is essential that there be a well co-ordinated response system to ensure
accident management, including the recovery of lost packages and
combating a HNS spill. This system must be established on a
permanent basis and must identify the personnel who will respond
and perform specific tasks in the event of an accident. They should
also be aware of the emergency procedures to be followed by the ship’s
crew.
55

Chapter 4
4.2.1 Response organization
The number of personnel, organizations and activities involved in res-

ponse can vary greatly. However, to be effective, the various response
personnel and their activities must be organized into a structured unit
capable of conducting the operations required. Advisory and/or assisting
experts from the chemical industry, chemical accident emergency teams
from fire brigades, and civil emergency authorities must be an integrated
part of the response organization.
The primary aim is to establish an organization capable of effectively

managing and directing response activities for the successful
mitigation of an incident. The structure of the organization and the
functions to be performed should be modified on a case-by-case basis,
to meet the requirements imposed by specific situations. However, there
are common features of HNS incidents which can be used to design a
generic organizational structure.
Fundamental elements to be considered are:

. the identification of an agency for overall command and on-
scene co-ordination;
. the definition of responsibilities and functions, including
ship salvage, search and rescue, pollution operations;
. the delineation of authority;
. the establishment of internal and external communications;
. the co-ordination of activities and functions; and
. the identification of resources, including information
sources on HNS response personnel, equipment, chemical
specialists and financial aspects to cover the costs involved.
4.2.2 Response personnel
To manage the various activities required in a response situation,

personnel must be selected and assigned the responsibility for
conducting specific operations. The positions, functions and
responsibilities listed below represent a major response effort, and
should be adapted according to the requirements of a particular
response and the personnel available.
4.2.2.1 Overall commander
The overall commander is responsible for general policy and strategic

decisions. He provides the link to higher Government authority or port
management. In certain cases, the overall commander could also be
responsible for international co-operation if this is required.
56

Lead Agency (LA) . Public affairs

with overall control
(Operational Control Authority)
3 " Assistingadvisors
services and Press releases
. Financial and
contractual support
. Legal support for
compensation
Presentation
. Scientific support
damage assessment -
long-term effects
Advisory Services*
. Chemical industry
! . Port operators of
HNS facilities
On-Scene Commander (OSC)
with tactical control at scene 3 " . Salvage operators
. Chemical tank ship
owners
. Experts from
insurance companies
! ! !
Response team Response team Aerial surveillance
! !
FOL** FOL**
" Salvage unit " Access control unit

" Recovery unit
" Access control unit
" Monitoring and sampling units
" Recovery unit
" Decontaminacion
*Advisory Services: The Advisory Services often have to co-operate very closely with the OSC.
12089
**FOL: Field Operations Leader, if needed in a large operation.
Figure 4.2: Key elements of a response organization

(Source: Special Federal Unit for Marine Pollution, Germany)
4.2.2.2 On-scene commander (OSC)
The on-scene commander (or co-ordinator) is the person responsible for

organizing the local response and co-ordinating the deployment of
required resources. The OSC may be a Government or an industry
representative. The OSC is a decision-maker, a communicator and a
manager of personnel and time. The OSC is responsible for directing
the employment of needed resources. The OSC establishes an
operations centre for the collection of information, incorporating
concerns or sensitivities of the participating organization/public and
media, and is responsible for reporting all aspects of the spill. The staff
of the OSC may include:
57

Chapter 4
. Scientific co-ordinator: responsible for directing and co-

ordinating activities related to the scientific aspects of the
situation, including analysis, remedial actions, sample
collection, field monitoring, and analysis of data.
. Safety officer: provides advice and consultation on all
matters related to the health and safety of those involved
in response operations. He establishes and directs the safety
programme.
. Public information officer: responsible for releasing all
information concerning response activities to the news
media and the public. He should be kept informed of the
latest information on the situation, as well as the strategies
and tactics to be implemented. He is responsible for
verifying press releases.
. Security officer: responsible for general response area
security (will usually be local law enforcement personnel).
. Financial officer: provides financial and contractual support.
. Record-keeper: responsible for the official record of response
activities.
4.2.2.3 Field operation leader (FOL)
The OSC can nominate field operation leaders (FOL) for directing specific
tasks, such as cargo transfer, counter pollution, operations at sea and on
beaches and evacuation control on shore. Each FOL must have clearly-
defined instructions and responsibility to manage and direct the
relevant response operation. The FOL may be responsible for team
leaders, each of whom may have responsibility for:
. entry team(s);
. decontamination;
. sampling;
. monitoring;
. equipment;
. aerial surveillance and photography;
. communications; and
. other specific tasks.
4.3 Response support system (RSS)
The behaviours, hazards, and risks associated with discharges of HNS

are specific to the substance’s properties and to the actual
circumstances of the accident.
58

While oil spill response planning puts much emphasis on physical

containment and mechanical recovery, HNS response requires a more
diverse set of response management tools to be already available before
an accident occurs.
To assist responders and decision-makers in managing the response,

various types of information must be gathered before an accident
takes place. Miscellaneous system formats are possible. Each
organization should develop its preferred system, meeting its own
requirements and capabilities. A response support system (RSS) can
be anything from a list of experts, a decision tree, up to a highly
sophisticated artificial intelligence computer-based system.
Irrespective of the actual physical implementation of the RSS, there are

fundamental elements to be made available to any optimized
organization. This section describes briefly the elements of a RSS.
Some elements relate to planning and assessment, others are
emergency management tools.
Planning and assessment tools include, but are not limited to:
. inventory of the different response plans that can be
activated in different areas, and the procedures required to
activate them;
. inventory of transportation patterns, and commodities
transported in different areas;
. chemical and physical properties of transported sub-
stances;
. toxicological effects, and exposure limits, of substances;
. chemical fate of substances;
. spill scenarios, describing the substances transported for
each sensitive areas;
. possible recovery techniques, and associated resources
required;
. personal protective equipment requirements, and sources;
. identification of population centres in relevant areas;
. notification list;
. a list of public and private response team contacts (i.e.,
specialized response teams, fire brigades, health authori-
ties, etc.);
. container storage, handling and transportation require-
ments;
. air and water sampling/monitoring resource requirements
and existing capabilities.
59

Chapter 4
Response tools include, but are not limited to:

. an incident assessment system;
. a list of experts on maritime and chemical aspects;
. predictive air dispersion modelling, and related monitoring
capabilities;
. predictive water dispersion modelling, and related monitor-
ing capabilities;
. an inventory of incident assessment capabilities;
. access to the ship’s manifest, and loading plan;
. information on the facility or vessel(s);
. salvage, including diving capabilities;
. search and rescue capabilities;
. decontamination techniques for responders and exposed
public;
. disposal techniques, and related regulatory requirements;
. an operations manual.
60

Chapter 5
Response methods and techniques
5.1 General remarks

Countermeasures for oil spills have become highly developed over the
years. The work and attention given to oil spill response systems have
developed a model and knowledge base which are useful for addressing
the less frequent chemical spill incidents. The response mechanisms
and organizational structure for each are similar. At the technical
level, however, new responder skills have to be adapted for the distinct
hazards posed by HNS. The IMO Manual on Oil Pollution is a
comprehensive reference, laying out a basic planning process
applicable to spills involving oil and other hazardous substances. As in
the case of oil, emphasis should be put on prevention followed by:
. the development of plausible scenarios including:
– the identification of the chemical substances, to assess
the impact of possible spills;
– identification and/or development of appropriate re-
sponse countermeasures;
– the identification of required resources; and
. the implementation of a flexible response organization to
deliver safe, effective and co-ordinated response operations.
5.1.1 Definition of response
Response is the effort of minimizing the risks created in an emergency, to
protect people, the environment and property, and to restore normal pre-
emergency conditions.
This chapter provides an overview of available response techniques for
spillages escaping from a ship and spreading beyond its immediate
location. With this information, officials responsible for the
development of contingency plans can develop the procedures and
protocols essential to carry out effective HNS response operations in
the marine environment.
More precisely, this chapter describes a systematic approach to
responding to HNS incidents, followed by general onboard response
considerations, specific responses to gas and vapour releases and
responses to spillages of liquids into waters.
5.1.2 Distinct aspects of marine response
Since several aspects of marine chemical responses differ from other
chemical emergencies, specialized expertise should be made available
to the OSC. Specific elements requiring consideration are:
. the international composition of crews manning a vessel,
which, if, for language reasons they are unable to commu-
61

Chapter 5
nicate clearly with response personnel, can complicate what

might be already a difficult situation;
. currents, tides and waves produce continual movements of
both stricken and response vessels. Equipment, such as
hoses and ladders, may be adversely affected; mooring
systems can be strained to the point of parting. Local eddies
can make it difficult for workboats to maintain their position
and move around fixed constructions. Response personnel
falling overboard may be pulled under by strong currents.
Control of the holding capacity of an anchor will vary with
bottom conditions;
. restricted working space for response personnel and limited
means of escape for responders due to tight exit paths and
the danger of going overboard;
. weather conditions such as high winds, fog, blizzards and
ice can prevent or obstruct response operations; weather
conditions over water can differ from those over land;
. damage to tanks and outflow rates will vary according to the
ship type in a grounding or collision. The transverse stability
will vary with the amount of water taken in or used for
fighting a fire; and
. whether the cargo is in bulk or in containerized form.
5.2 Systematic approach to emergency response

Marine hazardous substances accidents share the following crisis
components:
. large uncertainties;
. important values at risk, including human life;
. tight time constraints;
. outcome is unpredictable and unexpected.
The response to a marine accident is a complex issue requiring highly
specialized skills and technology and the involvement of numerous
organizations. Critical decisions need to be made rapidly to prevent
escalation and turn a developing disastrous situation into a non-
hazardous one.
The decision-making process must be flexible enough to handle a broad
spectrum of different incident-related issues in a timely, efficient and
effective manner. The decisions reached must be simple enough to be
clearly understood by all of those involved in the response operations.
This section proposes a systematic approach originally developed by the
chemical industry to assist the decision makers involved in the
management of HNS emergency situations.* It is a systematic
* Canadian Chemical Producers Association, An Approach to Emergency

Response (video and supporting material).
62

sequence of steps for collecting information and making decisions in a

logical and methodical manner. The four systematic steps of the
decision-making process are:
. the assessment; where all information relating to the
incident is gathered;
. the decision-making; where the information is processed and
interpreted to define priorities, strategies and tactics;
. the implementation; where appropriate response actions are
put into practice; and
. the feedback loop where decisions made and actions
implemented are reassessed against the evolving situation.
The relationship between the four basic steps and the general
preparedness and response framework is shown in figure 5.1.
PREPAREDNESS 3
INCIDENT "
NOTIFICATION
" SITUATION ASSESSMENT

FEEDBACK
~
DECISION-MAKING
IMPLEMENTATION
22089
DEBRIEFING
Figure 5.1: The systematic approach to decision-making and its

relationship to the general preparedness and response framework
(Source: CEDRE, France)
5.2.1 The situation assesment phase

The assessment of the situation will occur in two phases. First an initial
assessment of any maritime casualty will be made to decide whether any
environmental response is needed. Should an HNS response operation
be required, a detailed assessment will follow to identify the best
strategies and tactics and to facilitate their safe implementation.
63

Chapter 5
Figure 5.2: Detailed systematic approach to emergency response

64

As shown in figure 5.2, an appropriate assessment of the situation

involves collecting information on:
– the circumstances of the incident;
– the modifying conditions;
– the potential impact and losses from exposure;
- the response capabilities available;
– the anticipated reactions of interest groups (media, local
communities, etc.).
For data such as chemical and toxicological properties, ship structure,
last port of call, etc., the information is usually available from various
Government agencies, the master, the ship owner, maritime authorities,
international organizations or P&I clubs.
A second type of information can only be obtained by direct observation
from the accident site. The data could be collected either from a distance
(conservative assessment), or by a direct entry into the contaminated site
by an assessment team using adequate personnel protective clothing
and monitoring equipment. The information collected should be
verified and, if necessary, complemented. Special care should be taken
when approaching, by sea or by air, any stricken vessel (see figure 5.3).
Figure 5.3: Helicopter approaching a stricken vessel

5.2.2 The decision-making phase

Based on the description of the problem and of possible losses identified
in the initial assessment phase, the authority in charge may decide,
where feasible and acceptable, to trigger an environmental response
operation. The goals and objectives of the intervention should be
clearly defined, saving lives, preserving the environment and protecting
property being the overall priorities.
65

Chapter 5
The first step in the decision-making process (see figure 5.2) is the
identification of the most critical issues. The more accurate the des-
cription of the accident and of the associated circumstances, the more
adequate will be the understanding of the critical issues. Decisions will
be taken on issues such as:
. whether a response is necessary;
. if the situation warrants a response, what type of action
needs to be taken;
. if the response action is at all possible due to prevailing
conditions; and
. whether the response action has to be postponed due to the
requirement for additional resources.
Response priorities can then be established by taking into consideration
the modifying conditions, the response capabilities at hand and the
reaction of the different interest groups. The priorities should address
both preventive and corrective strategies.
Only then should response activities and tactics be undertaken, taking
into consideration three different forms of action:
. actions on the vessel;
. actions on the cargo; and
. actions on released HNS.
5.2.3 Implementation phase

The implementation phase consists of putting into effect protective and
corrective actions. It is at this stage that field operations are carried out.
5.2.4 The feedback loop

Any HNS incident is a dynamic situation. It requires an ongoing
reassessment of the entire situation to identify new elements arising
which might require changing the original plans and stopping
activities taking place.
The continuous reassessment of the situation and of each of its elements
brings the process back to its first step (feedback loop), allowing the
decision-maker to permanently ensure a safe, effective and efficient
response.
The systematic approach to an HNS incident is a dynamic method which
constantly examines and reassesses the facts and the situation. It
endeavours to anticipate changes to prevent any possible escalation of
the situation.
The systematic approach requires decision-makers to carefully consider
all aspects of the operation, to develop and maintain efficient
communication channels with all response personnel and to keep in
mind any possible eventuality.
66

5.2.5 The effectiveness of the approach

Using this approach, consideration of the following seven critical issues
will ensure substantially positive decisions:
– seeking out a broad spectrum of alternative actions;
– taking into consideration all the possible objectives;
– carefully balancing costs and risks, as well as the positive
and negative impact which could result from every action;
– constantly seeking out new information for the assess-
ment of possible alternatives;
– understanding and taking into consideration any in-
coming information even if it does not corroborate the
initial response strategy;
– before making a decision, reassessing both the positive
and the negative consequences of all alternatives, in-
cluding those initially discarded as unacceptable; and
– ensuring that the plan of action is fulfilled.
5.2.6 Benefits of the method

The main advantage of the systematic approach method is to unite the
various decision-making organizations around a common objective. The
method provides a series of actions for decision making which reduce
the risks of conflicts related to the choice of priorities, or to varying
points of view, concerning the ways in which a situation is managed.
During an exercise or an accident, clear advantages can be obtained
from a systematic approach to decision making:
– a better understanding of the key decisions and of the
decision-making process by all personnel;
– the ongoing reassessment of the situation guarantees
that pertinent facts will not be forgotten;
– the system helps establishing priorities;
– the method enables the best use of resources; and
– the method increases safety for both the response teams
and the public in general.
5.3 Response on board ships
5.3.1 Spillages on board – general remarks

Any ship carrying HNS, whether packaged or in bulk, is faced with the
possibility of a spill, either contained on board or leaking out into the sea.
Such a spill could be life-threatening, harmful to the marine environ-
ment, and could cause the loss of cargo and ship. For accidents at sea,
there is ‘‘no place to run’’, and usually immediate outside assistance is
67

Chapter 5
not readily available. Every effort should be made on board to limit the
release of spilled material from packages or cargo tanks to the external
environment. It is essential that ship personnel be aware of the hazards
of the cargo, and that a specific emergency action plan be in place.
Knowledge of the hazardous properties and characteristics of the
substances can prevent accidents from occurring, as well as aiding in
the response to a spill. Confined space due to compartmentation and the
presence of other cargo may limit the establishment of specific work
areas and zones used in shore-based response (see sections 5.3.2 and
5.5).
The ability to carry out response actions on board will depend upon the
extent and nature of the hazardous conditions. Response activities will
depend upon the extent of the tank damage, the rate of discharge, and the
characteristics of the spilled substance, i.e., volatility, toxicity,
flammability, etc. In any action on board a ship, there must be a safe
area from which to mount response operations. Where the feasibility of
response at sea is questionable, a decision will have to be made whether
response operations should be conducted at sea, or whether the ship
should be brought to sheltered waters for further pollution control
efforts and cargo transfer. In such instances, the following questions
will assist in the decision-making process:
. Is it possible to transfer the cargo at sea?
. What is the extent of damage to the cargo and bunker tanks?
. Is the release continuing or complete?
. If there is progressive tank damage, is threat of further
spillage greater at sea than in sheltered waters?
. Can some action be taken to control/reduce the spillage
while towing to sheltered waters? This might include
transfer to another intact tank on board, or a limited ship-
to-ship transfer.
. Is the risk of moving the ship to sheltered waters accep-
table?
Administrations should encourage harbour authorities (or other
relevant bodies) not to unreasonably deny ships requiring assistance
access to sheltered waters.
Personnel involved in emergency cargo transfer operations must be fully
protected, and aware of the hazards of the materials they are
transferring. Whenever possible, they should be assisted by
experienced hazardous materials response personnel.
The IMO publication Emergency Procedures for Ships Carrying
Dangerous Goods (EmS) provides an outline of emergency procedures
for personnel on board ships at sea which could also be used by shore-
based response personnel (see section 2.5).
68

5.3.2 Gas and vapour releases on board

When a spill on board creates toxic, corrosive or flammable vapours, the
master should manoeuvre the ship, if conditions permit, so that vapours
move away from the ship’s accommodation and operations spaces.
Ventilation may not always be effective for removing gas clouds,
particularly for heavier-than-air gases that settle and accumulate in
low spaces. When dealing with flammable vapours and gases, ignition
sources (e.g., naked lights, electric tools, etc.) must be eliminated.
Where it is known that the atmosphere in an enclosed or confined space
is unsafe, response personnel should only enter if there is a compelling
need to do so. If entry cannot be avoided, the following precautions
should be taken:
. ensuring that the space has been thoroughly ventilated by
natural or mechanical means;
. testing the atmosphere of the space for oxygen deficiency
and harmful vapours (for cargo holders and tanks this
should be carried out at different heights, top, middle and
bottom);
. requiring those entering to wear suitable protective clothing
and self-contained breathing apparatus where there is any
doubt as to the safety of the environment of the enclosed
space;
. ensuring the presence of standby persons at the point of
entrance with proper rescue equipment with clear instruc-
tions that they should only enter a confined space if
essential and when assistance arrives; and
. ensuring that a system of communication and emergency
systems is agreed upon before entry and closely adhered to
on entry between those inside and those on standby.
The Recommendations for entering enclosed spaces aboard ships
prepared by IMO (see appendix F of the BC Code) can be used as a
basis for the general precautions and procedures to be taken by
response personnel when entering enclosed or confined spaces (annex
5-1, Maritime Safety Card, summarizes IMO’s recommendations).
5.3.3 Liquid releases on board

When a HNS is spilled on deck, the most common response procedure is
to wash the spillage overboard with large quantities of water. The master
must make the decision whether or not to proceed with this type of
disposal. The safety of his crew and his ship must have priority over
pollution concerns. However, to prevent severe marine pollution in
enclosed shallow waters, particularly in the proximity of drinking
water intakes or sensitive areas, consideration must be given to
reducing the amount of hazardous substances spilled overboard. In
addition, some substances may react with air or water to release toxic
69

Chapter 5
or flammable gases (see section 3.3.4). Consequently, threat to human

life and health ashore may require that the spilled substance be
contained and cleaned up entirely on board the ship.
If it can be done safely, spillages should be collected with sorbent
material and stowed in receptacles for ultimate disposal ashore
whenever possible. As an alternative, spillages may be transferred to
empty tanks, using small portable pumps.
In addition to having an emergency plan for dealing with spillages of
hazardous materials, repair and patching equipment specific to the
type of containers and packages carried should be available on board.
Co-ordinated planning between the shipper, owner and master will
ensure a comprehensive and effective response to hazardous materials
incidents on board.
5.3.4 Fire fighting

Fighting fires on board a vessel presents unique problems not typically
encountered with shore-based fires. Some of these problems include:
. the steel construction of a vessel (e.g., bulkheads, decks,
superstructure, etc.) contributes to the hot environment
already present in sizeable fires;
. the limited space available to manoeuvre hoses and other
fire-fighting equipment on board the vessel;
. the spread of fire and smoke, and the possibility of a
‘‘backdraught’’;
. the different requirements for fighting a fire on a vessel, at
berth or at anchor;
. the difficulty in safe and speedy access through narrow
passageways, especially for emergency personnel equipped
with protection equipment;
. the ever-present danger of response personnel being cut off
from an easily accessible escape route; and
. the loss of stability and excessive listing or dangers of
flooding and subsequent sinking following the pumping of
water into the vessel.
The supporting material in IMO’s Model Course no. 2.03, ‘‘Advanced
Training in Fire Fighting’’, provides useful information on the topic of
fire fighting on board vessels.
Obviously, fire considerably complicates the response to a spillage on
board a ship. When fire occurs within the hold of a general cargo ship,
any packages close to the fire should be removed, where possible. If it is
known that heat will adversely change a substance, or affect the integrity
of packages, cooling the packages with water may limit the hazard. When
70

there is a fire within a hold or in other enclosed spaces, securing open

hatchways and doors, shutting down ventilation systems and operating
fixed fire-fighting systems are often the best courses of action.
Water is the most freely available fire-fighting agent on ships and at
terminals. Its use is recommended for most marine HNS fires, even
though it may not always be the first choice for shore-based fire fighting.
For those cargoes which react violently with water, only dry chemical
agents should be used. This would not preclude the use of suitable
powdered inert material, if available in sufficient quantity. When there
is no alternative, large amounts of water can sometimes be used on such
fires. This can have a cooling effect even though a chemical reaction may
be occurring. Fire-extinguishing foam compounds may also be used
when available and if compatible with the burning material. General
fire-fighting recommendations for a number of dangerous goods are
found in IMO’s Emergency Procedures for Ships Carrying Dangerous
Goods (EmS).
5.4 Response options for spills at sea

5.4.1 Selection of measures based on physical properties
Three main categories of techniques are required to safely respond to
HNS incidents, namely, forecasting methods, monitoring techniques
and, finally, recovery systems. Choice of the proper technique should
be based on the specific properties of the HNS involved. This section
describes each technique and shows behaviour groups where it can be
usefully implemented.
Table 5a shows the different response methods useful for each group.
Each method has a specific designation, where F stands for forecast, M
for monitoring, and C for combating. An X indicates that the respective
method is applicable to the corresponding behaviour group. Each
method is described in detail under sections 5.4.2 to 5.4.5.
5.4.2 Responding to releases of gases or volatile liquids

Frequently shipped gases and volatile liquids include: ammonia, vinyl
chloride, chlorine, methane, propane, butane, LPG.
A safe response to gas emergencies requires a detailed knowledge of how
gases are stored, how they behave, how they escape, and how they spread
over large areas.
The use of water sprays is one of the most useful techniques available for
combating gas leaks. They may be used to:
. reduce the risk of fire and explosion by cooling down hot
surfaces, putting out sparks and suppressing flame forma-
tion;
. stop, steer or disperse sparingly water-soluble or insoluble
gas clouds; and
71

Chapter 5
. wash down or knock down water-soluble gas clouds (see

subsection 5.4.2.3).
Table 5a: The application of various response techniques

to different behaviour groups
The table is applicable for Solid Solid

methods against HNS releases only subst subst
F FD D SD S
GAS LIQUID
GROUP G GD E ED FE FED F FD DE D SD S
METHOD
F1 Forecasting the spread in air X X X X X X X
F2 Forecasting the spread on water surface X X X X
F3 Forecasting the spread in water body X X X X X X X
M1 Monitoring the spread in air X X X X X X X
M2 Monitoring the spread in water body X X X X X X X (1)
C1 Combating water soluble gas clouds X
C2 Combating spills that float on water X
C3 Combating spills that dissolve in water X X X X X X X
C4 Combating spills that sink to the bottom X X
52089
(1) It may also be appropriate to monitor sinkers that move over the bottom in the water body.
Group designations:
G gas F floater
GD gas/dissolver FD floater/dissolver
E evaporator DE dissolver/evaporator
ED evaporator/dissolver D dissolver
FE floater/evaporator SD sinker/dissolver
FED floater/evaporator/dissolver S sinker
NB: The above table addresses substances which belong to the 12 groups of the
behaviour classification system described in section 3.4.1.3. The vast majority of
substances which are commonly transported at sea belong to the 12 groups and
behave accordingly. Substances which react with water or in other ways are
briefly discussed in section 3.4.1.5. Spills of reactive substances must be
handled with extreme care and technical expertise.
5.4.2.1 Method F1 – Forecasting dispersion in air of gases

or volatile liquids
Method F1 is applicable to gases and to any liquid volatile enough to
produce a vapour cloud. This includes all groups with a G and E
component in their property groups (i.e., G, GD, E, ED, FE, FED, DE).
Forecasting the spreading of a gas cloud is usually too lengthy a process
to be practical during emergencies, even with the assistance of
computerized air dispersion models. Running several plausible local
scenarios in advance has been shown to be the best way to ensure a
rapid implementation of adequate preventive measures.
72

Forecasting the spread of gas clouds in air can be estimated for groups G
and GD by means of table 5b. Estimates should never be relied on as an
alternative to monitoring, as the combination of substance properties
with specific atmospheric conditions may result in peculiar behaviour
patterns. For example, an accidental release of 10 kg of chlorine at -30oC
combined with unusually stable atmospheric conditions to prevent the
dilution of the chlorine cloud, which moved 10–15 km before dissipating.
Table 5b can also be used for flammable and toxic liquid HNS in groups
E, ED, FE, FED and DE. The spread of evaporated gas from spills can be
estimated by multiplying the values in table 5b by the ratio VP/100,
where VP is the liquid’s vapour pressure in kilopascals (kPa) at
ambient temperature.
Table 5b: Estimated hazardous exclusion zones

for different quantities of HNS spilled
Health risk Fire/Explosion risk
Ammonia, vinyl Methane (LNG), Ammonia, vinyl chloride, methane

Quantity chloride, chlorine propane, butane, (LNG), propane, butane, ethylene,
released ethylene, butylene- butylene-butadiene
butadiene
tonnes metres metres metres
0.1 1,000 200 200
1 2,000 400 400
10 5,000 1,000 1,000
100 10,000 2,000 2,000
1,000 20,000 4,000 4,000
5.4.2.2 Method M 1 – Monitoring the presence of gases in air

It is essential to systematically monitor the concentration of HNS in the
air for the duration of accidents involving gases or vapours. The primary
objective of trace air monitoring is to identify the areas where
unprotected personnel or members of the public should be evacuated.
The technique is used to follow up changes in the status of previously
assessed areas.
Three parameters should be monitored when entering a potentially
hazardous area (see table 5c):
. oxygen concentration;
. combustible or explosive gas levels; and
. toxic substances.
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Chapter 5
Oxygen concentration and combustible gas levels should be monitored

simultaneously, since oxygen deficiency can affect the proper
functioning of the combustible-gas detectors. The presence of toxic
gases can be detected by trace-gas analyzers such as colourimetric
tubes, photoionization and flame ionization detectors, pH and starch
papers. Although these devices can detect very low concentrations of
gases (i.e., a few parts per million), the resulting numbers are
approximations and should only be used as screening tools.
Colorimetric tubes indicate a positive result by undergoing a change of

colour. The air is pumped through a glass tube containing a granular
material coated with a reagent, which changes colour when in the
presence of a contaminant. Photoionization and flame ionization
detectors are portable instruments, which can be calibrated to a
specific substance to determine the appropriate concentration of that
substance. However, the result obtained is valid only if that specific
compound is present and nothing else can interfere. The detection
principle of the photoionization detector is the ionization of the vapour
by ultra-violet light emitted by a lamp. It should be used in conjunction
with another instrument, such as a flame ionization detector, which is
designed to detect organic compounds. Wetted pH papers and starch
papers can be used to detect corrosive and oxidizing atmospheres,
respectively. The dry papers are also used on liquids.
Table 5c: Types of person-portable detectors used

for monitoring HNS in air
Parameter Objective Type of detector
Oxygen To identify oxygen-deficient (less than Oxygen cells

concentration 19.5%) or oxygen-rich (more than 23%)
(%) (v/v) areas, 20.9% being the normal value.
An oxygen-deficient atmosphere
requires the responder to have
supplied air (SCBA).
Combustible or To identify areas where flammable air/ Combustible gas detectors, or
explosive gas fuel mixtures may exist. A value below explosimeters
levels 10% of the LEL is considered safe.
(% gas or %LEL)
Toxic substances To establish the areas where toxic Trace-gas analyzer, colorimetric tube
substances are present and to monitor
their levels. The concentrations allow
the delimitation of the exclusion zone.
Infra-red detectors can also be used to monitor the presence of toxic

gases. These devices are less handy and require trained operators.
Permanently installed continuous gas monitors (e.g., electrochemical
sensor units) may be available on board chemical carriers.
If no monitoring device is available, a safe evacuation area should be

established around the scene until an actual assessment is made.
74

Response personnel should be trained and familiar with the functioning

of their instruments. The initial assessment of the situation should be
performed by fully protected personnel (see section 5.5).
The measurements should be carried out from outside the gas-free area,
inwards towards the site of the incident. The boundary line of the
exclusion zone should be where a first positive reading was recorded. A
map of the exclusion zone area should be drawn from further sampling
around the site of the accident.
Figure 5.4: The outer limit of measurable concentrations and

the area of gas concentrations which are dangerous to health
Gas clouds move irregularly due to air turbulence. Therefore, the

assessment of air content will not give as smooth and uniform a curve
as suggested by figure 5.4. In practice, however, the exclusion zone
boundary line will be drawn through the outermost gas readings.
5.4.2.3 Method C1 – Combating water-soluble gas clouds
This method can be used mainly for group GD water-soluble gases, such
as ammonia. Small and confined GD gas clouds can be ‘‘knocked down’’,
or washed down, by fine scattered water sprays or water mists. This
procedure can be used to protect responders.
When liquefied ammonia gas is discharged into water, part of it will boil
away rapidly (see section 3.4.1.4). However, more than 60% will dissolve
in the water body and form a dangerous alkaline solution. In confined,
vulnerable water areas with low water turnover, mild neutralizing agents
will be required to reduce the damaging effect of ammonia (see method
C3 in section 5.4.4.2).
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Chapter 5
Figure 5.5: Small water-soluble gas clouds can be ‘‘knocked down’’,

or washed down, by water sprays (Source: SIGTTO)
5.4.3 Responding to releases of floaters

When spilled, floating HNS will spread to form a continuously growing
contact interface with air. Depending on its vapour pressure, it can
evaporate rapidly and give a high gas concentration in the air. In
responding to such substances, it is important to monitor air
concentrations, in order to assess the risk of fire, explosion and danger
to health.
Frequently shipped floaters include: amyl acetate, alpha-methyl styrene,
butyl acetate, butanol, butyl acrylate, cyclohexanone, dibutyl phthalate,
dioctyl phthalate, dipentene, ethylhexanol, fish oil, heptane, hexanol,
isodecanol, nonyl alcohol, phthalates, toluene, 1, 2, 3-trimethylbenzene,
turpentine, vegetable oils, vinyl toluene, xylenes.
5.4.3.1 Method F2 – Forecasting the spreading

of floaters on the water surface
This method is applicable for groups FE, FED, F and FD (all groups
with F).
The calculation of the spread or drift can be done by vector diagram
using the same principle as for oil spills (see figure 5.6). However, most
HNS spills belonging to these groups, except for F, will disappear by
evaporation and/or dissolution within approximately 10 hours.
Under opposing current and wind conditions it is critical to consider the
relative forces of wind and current, since these will determine the
position of the spill. In certain cases, a stricken or response vessel
which had an original upwind position may end up downwind.
5.4.3.2 Method C2 – Combating releases of floaters

Significant quantities of group F substances are transported in bulk
around the world. Method C2 can be used for any liquid or solid
substances that float and evaporate or dissolve slowly.
76

Figure 5.6: Calculation of a surface slick’s drift using a vector diagram

Floater spills can be:

. covered with foam to reduce evaporation;
. treated with sorbents or with any other types of treating
agents;
. contained by booms;
. picked up by recovery equipment such as oil skimmers; and
. combatted by any combinations of the above.
Foams: During response operations, special attention must always be
given to health, fire and explosion risks. These risks can be
significantly reduced by covering the spilled material with chemical
foams specially developed to reduce vapour releases. The use of foams
on a floater can restrict its spread on the water surface and facilitate
containment and recovery operations.
Sorbents and gelling agents: Several sorbent types are available on the
market for responding to HNS spills. They have various appearances and
compositions. Most of them were developed and tested for spills on land.
Unfortunately, few are known to work well on the water surface.
Nevertheless, conventional oil spill sorbents can sometimes be used in
HNS response. Their compatibility with the spilled substance must
always be verified prior to use.
Several sorbents are contained in small booms (‘‘sausages’’ or ‘‘socks’’).
Others appear in the form of small ‘‘mats’’ or ‘‘plates’’. Some polymeric
materials are available as foam or felt-like pieces that can be easily
distributed to cover the spill (see figure 5.7).
Granulated or small-particle materials are also available. They may
conveniently be packed as pillows or in cloth cases as ‘‘blankets’’ for
application at sea (see figure 5.8). Some small cubed or pellet-shaped
sorbents are made of plastic foam that can be recycled by systems
developed to extract the substance and regenerate the sorbent for reuse.
77

Chapter 5
Figure 5.7: Treating a HNS spill on the water surface with sorbent plates
or pads (Source: Environment Canada)
Figure 5.8: Treating a HNS spill on the water surface with pillows or
blankets filled with powdered sorbents (Source: Environment Canada)
Powdered or granulated sorbents can be spread by means of an ejector

pipe (see figure 5.12), which facilitates a uniform spreading of the
sorbent. However, there is a risk of clogging the ejector pipe,
particularly when working with fluffy types of sorbents. In light winds,
the sorbent can be effectively spread from hand-held bags.
Low-viscosity HNS spread out rapidly as very thin films on the water
surface. In order to obtain efficient absorption, it is therefore necessary
to apply high sorbent/HNS ratios. The spreading of a spill can sometimes
be confined by booms. This process will be facilitated by pretreating the
spilled substance with sorbents or similar agents. Due to the cost and
practical limitations of using large quantities of sorbents, usage is
normally restricted to small spills.
Low-viscosity floaters may be difficult to recover, due to their rapid
spreading and their tendency to form very thin films on the surface.
For the same reasons, certain low-viscosity floaters may be difficult to
recover with skimmers, although on occasions oil skimmers have been
78

proven to be effective. The collection was facilitated by pre-absorbing the

liquid with a sorbent. However, it should be stressed that not all
skimmers are appropriate for use on pre-absorbed spills and material
compatibility is an important consideration when planning to use any
type of oil recovery equipment with spilled HNS. Skimmers suitable for
HNS response are discussed below:
. Belt skimmers (see figure 5.9) are used for the recovery of
certain HNS, e.g., octanol and dioctyl phthalate. The process
may sometimes be facilitated by pretreatment with sorbents.
Figure 5.9: Recovery of floating HNS on the water surface

with a belt skimmer (Source: Swedish Coast Guard)
. Sorbent rope systems (figure 5.10) can sometimes be used to

pick up HNS spills. For these systems to work well with HNS,
the substance should not be pretreated with any response
agents. The use of sorbent rope systems on octanol and
dioctyl phthalate has resulted in good recovery.
Figure 5.10: Recovery of floating HNS with sorbent rope

. Vortex systems can be used for recovering certain HNS

spread on the water surface behaving in the same way as
light petroleum products (see figure 5.11). The substance
should not be pretreated with response agents.
79

Chapter 5
Figure 5.11: Recovery of floating HNS on the water surface

by a vortex system (Source: Swedish Coast Guard)
Gelling agents are treating agents similar to the substances mixed with
gasoline as ‘‘thickeners’’ to make napalm. A thickener is a substance
soluble in a liquid that increases its viscosity to form a gel. Some
gelling agents have been tested but, as yet (1997), there are no effective
gelling agents for floaters. The gel structure is too fragile to survive the
conditions of marine responses.
5.4.4 Responding to releases of dissolvers

A substance dissolving in water will form a ‘‘cloud’’ or ‘‘plume’’, gradually
growing as the substance dissolves and moves in the water body. It is
important to monitor the concentration in the cloud in order to track the
spreading and the drift, as well as to assess the threat to the
environment, fishery, recreational areas, freshwater intakes, etc.
Frequently shipped dissolvers are: acetone, ethanol, phosphoric acid,
glycols, isopropanol, methanol, methyl ethyl ketone, monoethylamine,
sodium hydroxide solution, propionic acid, propylene oxide, sulphuric
acid, acetic acid.
Table 5d: Distances in metres to reach two concentration levels

for different quantities released
Quantity released Concentration Concentration

(tonne) 1 g/m3 1 mg/m3
1 500 5000
10 1000 10000
100 2000 20000
1000 4000 40000
5.4.4.1 Method F3 – Forecasting the dispersion plume

in water of substances that dissolve
The method described below is applicable for group D only.
80

The spread can be estimated with the use of table 5d, if the current of the
water body is slow and even. This method cannot be used for stagnant (or
almost stagnant) water, for HNS where the density differs too much from
that of water (see section 3.3.1.4 regarding spills of methanol and
sulphuric acid) or for very turbulent water.
5.4.4.2 Method C3 – Combating releases of dissolvers

HNS spills that dissolve in water can sometimes be treated with various
response agents in order to reduce or ‘‘neutralize’’ their harmful effects
on humans or the environment. Examples of chemical treating agents
are:
. neutralizing agents;
. flocculation agents;
. oxidizing agents;
. reduction agents;
. gelling agents;
. activated carbon;
. complexing agents; and
. ion exchangers.
Flocculation agents, gelling agents, activated carbon, complexing agents
and ion exchangers can all be used for treating water solutions recovered
from a spill site and pumped into barges or other storing containers.
Activated carbon is also often used in this way. It has been used in
several situations as a solvent agent for organic substances. However,
there is some uncertainty about the effectiveness of direct chemical
treatment in the marine environment.
Treating agents can be used principally in spills of group D substances,
but they may also be useful against other dissolver groups such as GD,
ED, FED, FD and SD. Ferrous sulphate, a reduction agent, has been used
to treat leaking chromium compounds from a sunken ship. The purpose
of this action was to convert (reduce) the chromium ions to a lower
oxidation state, which is less toxic. The treatment was performed by
emptying 11 tonnes of ferrous sulphate bags from a vessel.
The method may be used for spills of several liquid acids and bases
transported in large quantities, such as ammonium hydroxide,
fluosilicic acid, phosphoric acid, sodium hydroxide solution, propionic
acid, nitric acid, sulphuric acid or acetic acid.
Strong acids (e.g., sulphuric acid) and bases (e.g., sodium hydroxide or
calcium hydroxide), should not be used to neutralize other bases or
acids. Mild acids should be used to neutralize both strong and mild
bases, while mild bases should be used to treat mild and strong acids.
The following two products have been found to be effective choices on
most occasions:
81

Chapter 5
For spills of acids: Sodium hydrogen carbonate

(sodium bicarbonate, NaHCO3)
For spills of bases: Sodium dihydrogen phosphate
(monosodium phosphate, NaH2PO4)
Treating agents should be used in consultation with an appropriate
environmental protection authority, and a chemical expert to advise on
required doses. The agent can be spread out by means of ejector pipes
(figure 5.12) or directly from bags. In case of uncertainty about dosage,
estimate the total weight of spilled HNS and use the amount of
neutralizing agent required in theory, plus a 50% overdose. Spread as
appropriate over the spill site.
Figure 5.12: Use of an ejector jet pipe for application of a treating agent
5.4.5 Responding to releases of sinkers

Releases of sinking substances can heavily contaminate bottom
sediments. On such occasions careful planning should be undertaken
for the decontamination project. A sophisticated system may be needed
to handle and decontaminate the sediments, whilst specialized salvage
operations and equipment are needed when recovering sunken cargoes
or vessels.
A spill involving a sinker will spread over the sea floor. Therefore, it is
important to map the spill in order to guide the responders. A liquid pool
on the bottom has a phase interface which can be recorded by an echo-
sounder. Figure 5.13 shows a recording for a 1,300 m3 pool of ethylene
dichloride under 12 m of water. The length of the pool is about 40 m.
Other types of recordings and more detailed mapping can be obtained by
using submersibles and/or divers. The evaluation of health hazards to
divers needs to be carefully considered and should include compatibility
of HNS with diving equipment.
82

Figure 5.13: Echo-sounder recording of an ethylene dichloride pool

under 12 m of water (Source: Meyer et al., 1984)
Although its solubility may seem very low, a sinker should always be
considered as slightly soluble, due to the enormous amount of water
surrounding the substance. The concentrations in adjacent waters
must be monitored carefully to evaluate the risks to the environment,
fisheries, recreation, fresh-water intakes, etc.
Frequently shipped sinkers are: carbon tetrachloride, carbon disulphide,

ethylene dichloride, ethyl chloride, tetramethyl lead.
5.4.5.1 Method C4 – Combating releases of sinkers

Spilled substances on the bottom can be recovered by different dredging
techniques and by various types of dredges. However, not all dredges are
suitable for picking up HNS from the bottom. Table 5e shows three main
types of dredges: mechanical, hydraulic and pneumatic. Of the three
types, airlift pneumatic dredges have been used successfully in
numerous accidents.
Mechanical dredges: Clamshell and dipper dredges (see figures 5.14 and
5.15) are the most unsophisticated types of equipment that can be used
in shallow waters, with their machinery placed on a barge or nearby quay
or shore. This type of equipment has been successfully used to dredge
sunken phenol from the bottom of a harbour dock.
Figure 5.14: Mechanical dredge of clamshell type

(Source: Hand et al., 1978)
83

Chapter 5
Figure 5.15: Mechanical dredge of dipper type (Source: Hand et al., 1978)
Table 5e: Categories and types
Category Type
Mechanical dredges Mechanical dredges such as grab (clamshell), dipper or
bucket ladder type are designed for hard or soft material and
normally are not self-propelled. It is not advisable to use such
dredges since they tend to scatter the chemicals during
operation
Hydraulic dredges Hydraulic dredges recover materials from the sea-bed through
nozzles connected to suction pumps. Sometimes the nozzles
are equipped with cutterheads to facilitate normal dredging
work. When these dredges are used for removal of sunken
HNS, the cutterheads should be dismounted as, like the
buckets on mechanical dredges, they cause strong bottom
turbulence that tends to scatter the spill.
Pneumatic dredges Pneumatic dredges have pipe systems extending from the
surface to the bottom. Compressed air is injected at the lower
part of the pipe which results in a strong rising flow. Airlift
dredge systems have been used with some success in
chemical accidents.
Hydraulic dredges: Hydraulic dredges are often used to broaden and

deepen channels and harbours. These types of dredges are more
suitable for recovery of HNS from the bottom, where care should be
taken not to scatter the spill over larger bottom areas during the
dredging operation. A common type of hydraulic dredge is shown in
figure 5.16.
Figure 5.16: Hydraulic dredge of plain suction type

84

Some types of hydraulic dredges are equipped with cutterheads in order to

facilitate the work when deepening channels, etc. When these dredges are
used for the removal of sunken HNS, the cutterheads should be dismounted
as, like the buckets on mechanical dredges, they cause strong bottom
turbulence that tends to scatter the spill.
Pneumatic dredges: Figure 5.17 shows a pneumatic dredge that operates
with a submersible air-driven pump, supplied with air from a compressor
on the barge. The pump is designed with three cylinders that alternately fill
with sediment during the dredging operation, making use of hydrostatic
pressure. The sediment is then forced upwards to the surface by the
compressed air. The advantage of this technique compared to that of
hydraulic dredging, is that (1) the mud does need to be fluid but may
contain up to 70% dry matter and (2) there is no limitation regarding
working depth. Figure 5.17 shows a type of pneumatic dredge that was
used, on one occasion, for removing sunken PCB at a depth of 15 m.
Figure 5.17: Pneumatic dredge of ‘‘Pneuma’’ type

Mechanical hydraulic dredges for shallow water: Figure 5.18 shows a
catamaran barge equipped with a suction pump connected to a rotating
and cutting device that dredges the bottom materials. The system can
operate down to 5 m.
Figure 5.18: A simple mechanical hydraulic dredge for operation

in shallow water (Source: Environment Canada)
85

Chapter 5
Bottom suction dredges for shallow water: Figure 5.19 shows a hydraulic
dredge that is designed as a catamaran-based suction pump, for
dredging at depths of about 1 to 3 m. The pump head can be swung
down, between the hulls, to the bottom. Dredged material is pumped
backwards to an adjacent storage container.
Figure 5.19: A simple hydraulic dredge for operation in shallow water

(Source: Environment Canada)
Peripheral injector jet suction pumps (PIJESP): Figure 5.21 shows a simple
hydraulic dredge which has been supplemented, inside the head, with
nozzles pointing inwards. With this system, it is possible to add
pressurized hot water to facilitate the dredging of lumpy or highly
viscous HNS. It has been used in winter conditions for the removal of
sunken oil after an accident.
Figure 5.20: Peripheral injector jet suction pump (PIJESP), which can be
operated by divers (Source: HELCOM Combating Manual, vol. III)
Airlift: An airlift dredge is a simple pneumatic dredge which, in principle,

consists of a tube extending from the support vessel down to the bottom
(see figure 5.21). A compressor on the support vessel transfers
86

compressed air in a separate hose, either down to the head of the main
tube or to an inlet manifold placed somewhere on the tube. The rising air
expands and causes a strong current in the tube. The stronger the
current, the greater the working depth.
Figure 5.21: A small pneumatic (airlift) dredge

An airlift dredge is useful for the recovery of sunken HNS in water depths
from 10 to 20 m. In theory, the system has no depth limitation. The
dredging efficiency improves with water depth. A practical limiting
factor, however, is the compressor, which has to be bigger (and more
expensive) for greater depths. Furthermore, the tube is more difficult to
manoeuvre at greater depths, as the lateral forces become stronger. The
risks for divers are also greater at increasing depths, because of the
enormous suction forces close to the airlift head. Airlifts are
sometimes used for dredging tonnes of material down to depths of 60
to 70 m, but it is unlikely that airlifts could be used operationally at such
depths for dredging sunken HNS.
Practical arrangements for the use of an airlift system: Figure 5.22 shows
a suitable system for the practical operation of an airlift system. A
surface vessel (e.g., barge) is positioned above the dredging site, and an
air compressor on board the vessel supplies the diver and his airlift on
the bottom with compressed air. The barge can also receive the dredged
material in built-in tanks or in separate containers on board. The diver
operates the airlift tube, which is stabilized by a weight, to neutralize the
strong lateral movements that strengthen with increasing working
depth. The diver can also adjust the compressed air flow by means of a
knob on the tube.
87

Chapter 5
Figure 5.22: Practical arrangements for operating an airlift

(Source: Borlen, 1977)
Experiences of airlift systems: An airlift was used with success in case

history 5 (see chapter 6) where 16 tonnes of pentachlorophenol (PCP)
were dredged from the bottom of a river. A special application of an
airlift system was demonstrated in another case in a response
operation where a sunken barge with sulphuric acid was emptied (see
figure 5.23).
Figure 5.23: A sunken vessel with a cargo of concentrated sulphuric acid

was emptied by an airlift and the acid was released into the river in a
supervised and controlled way (Source: Swedish Coast Guard)
5.4.6 Disposal
5.4.6.1 General remarks

Disposal processes include the methods by which HNS and HNS-
contaminated wastes are disposed of or finally eliminated. Although
recycling of the HNS should be considered as a first option, this might
not be possible because there might be no chemical facility in a position
to handle the large quantity involved. Some disposal methods are used at
the site of accident; most are used at special facilities, after
transportation of HNS. The disposal of HNS and its wastes needs to be
carried out in accordance with national regulations. The main groups of
disposal methods are briefly discussed below.
88

5.4.6.2 In situ burning

Many HNS emit highly toxic vapours when burning. This method is
therefore used in exceptional cases only, and approval is generally
required from appropriate authorities. Floating spills on the water
surface are normally difficult to ignite, and usually require special
ignition techniques such as incendiary bombs containing thermite,
flame-throwers or air curtains.
5.4.6.3 Incineration
High-temperature burning in a special combustion chamber gives
complete oxidation, if the burning is performed under carefully
controlled conditions. There are various types of incinerator systems,
based on either fixed or moving bed designs. Generally, incineration is
a very efficient technique for the disposal of a wide range of HNS, as the
process gives minimum pollution.
5.4.6.4 Wet air oxidation

Wet air oxidation of HNS under moderate temperatures and elevated
pressure, with proper combinations of temperature, pressure and
reaction time, can give complete oxidation of HNS in specially designed
equipment. The process is energy-conserving with a proper HNS feed,
and the oxidation reaction, once started, is thermally self-sustaining.
5.4.6.5 Pyrolysis
Pyrolysis is a combustion process based on insufficient oxygen supply. It
is intended for complex waste mixtures that are converted by heat into
solid, easy-to-handle char in a pyrolysis chamber that contains no
oxygen. The volatile fractions are given off to a fume incinerator.
5.4.6.6 Landfill
HNS waste can be buried in ground cavities or in excavated trenches.
The material should be pretreated according to applicable regulations, in
order to reduce the content of certain components. Many States prohibit
landfill of certain HNS.
5.4.6.7 Deep-well storage

Underground storage requires the selection of a geologic formation and
the drilling of a well to an appropriate depth. The method is often strictly
regulated and surrounded by requirements regarding low seismic
activity, low site value as a resource, careful geologic investigation and
perfect encapsulation technique.
5.5 Health and safety strategy

The wide range of toxicological and physical properties of HNS increases
the need to increase the protection of first responders to a chemical
emergency. Chemical emergency-response personnel may not realize
89

Chapter 5
that they are being exposed to chemicals. In some cases, a very low
exposure level may generate major or delayed effects. Very strict
response procedures are necessary to protect personnel and the
public, and measures should be taken to systematically decontaminate
personnel and equipment, so as to halt the spread of contamination.
5.5.1 Health and safety officer

When an on-scene commander is appointed, one of his first duties is to
designate a health and safety officer for all response-related work. The
officer should set up a site safety plan for each work station, specific to
the HNS spilled or used, and ensure that safety procedures are effectively
being carried out. He should re-evaluate the risk levels periodically or as
the need arises and, if necessary, set up new safety procedures during
the operation.
The officer should set up a medical team, including at least one
physician, to ensure periodic checkups of workers exposed to HNS and
to other dangers during operations.
The officer should disseminate all useful information about the spilled
HNS to the medical team likely to come into contact with contaminated
personnel, and to all workers who could possibly come directly into
contact with the spilled materials, as well as ensuring that the devices
necessary for monitoring and detecting, for example, explosive or toxic
substances, are available, adequately calibrated and in good working
condition.
5.5.2 Site safety plan

The purpose of the site safety plan is to establish requirements for the
protection of team members during all activities conducted at an
incident. It should contain safety information, instructions and
procedures.
The plan must be prepared by qualified personnel, and should address
each activity of the HNS event. Before operations commence, safety
requirements must be written and posted or distributed to all
responders, and discussed with them. The site safety plan must be
periodically reviewed to ensure it is up to date.
5.5.3 Classification of work areas

Work areas should be divided into three categories with regard to the
level of risk for workers and the level of training and protection required.
Figure 5.24 represents a possible arrangement of work areas for an
incident. Since no fixed format can adequately address all accidents,
figure 5.24 is to be used only as a reference and must be adapted to
the specific requirements of each incident.
90

Figure 5.24: Diagram of control zones on board a vessel with an identified

exclusion area limit and a decontamination station
5.5.3.1 Exclusion zone

This area immediately surrounds the contaminated zone. It must extend
far enough to prevent adverse effects from releases of hazardous
substances on people outside the zone. Only trained personnel
wearing appropriate protective clothing should be permitted access to
this zone.
5.5.3.2 Contamination reduction zone

This is the area where personnel and equipment decontamination
occurs, and where support is provided to workers entering the
exclusion zone. This area should have controlled entry points in order
to limit access to authorized personnel only, thereby reducing the spread
of contamination.
Persons working inside this zone should have adequate training, as
recognized by national standards, and wear appropriate protective
clothing.
5.5.3.3 Support zone

This zone contains the command post and other support functions
necessary to control the incident, such as first aid, equipment
maintenance, offices and administration, laboratory, etc. Personnel
entering this zone may wear street clothes or conventional work
clothes, and their training should be related to their duties.
5.5.4 Individual protection

The individual protection of response personnel constitutes a key
element of the health and safety strategy.
91

Chapter 5
Personal protective equipment provides vital protection for the chemical

accident responder. The level and type of protection required will be
governed by the type (e.g., fire, toxicity, corrosivity, volatility,
radioactivity) and severity of the chemical hazards, as well as the
circumstances encountered. Personal protective equipment includes
respiratory apparatus and protective clothing. It shields or isolates
response personnel from the physical, chemical and/or thermal
hazards at the incident scene.
Figure 5.25: Examples of personal protection clothing (Source: IMO)
5.5.4.1 Respiratory equipment
Protection of the respiratory system is required until the incident site is

confirmed to be free of airborne contaminants, or when:
. the surrounding atmosphere is contaminated, or can
potentially become contaminated, with particulates,
vapours or gases;
. the surrounding atmosphere is deficient in oxygen. The
normal oxygen content in air should be close to 21% by
volume;
. a combination of the above two factors is present at the spill
site.
Protection of the respiratory system is achieved through the use of a

respirator. A respirator is a device worn over the mouth and nose, or
covering the entire face or head. It is intended to protect against
airborne physical and chemical hazards, either by removing the
contaminant from the air or by supplying an independent source of
clean air. A device that removes the contaminants is called an air-
purifying respirator. This type of respirator does not supply oxygen
and, therefore, should never be used in an oxygen-deficient
92

atmosphere. Unless the specific hazard is known, and an air-purifying

respirator has been determined to be appropriate, this type of respirator
should not be used in a response situation.
The open-circuit self-contained breathing apparatus (SCBA), an air-
supplying type respirator, is the basic breathing apparatus for
chemical response.
An open-circuit SCBA exhausts the exhaled air into the atmosphere. Air
is inhaled from a compressed air tank, passing through a regulator,
which reduces the pressure for delivery to the face piece. Two types of
open-circuit SCBAs are available, ‘‘demand’’ and ‘‘pressure-demand’’.
With the demand system, air flows into the face piece only upon the
inhalation, or ‘‘demand’’, of the wearer. The danger of a demand system
is that the negative pressure in the face piece caused by inhalation (felt
by the wearer as suction) not only triggers air flow from the regulator but
also could draw ‘‘bad’’ atmospheric air through leaks around the face
piece.
The pressure-demand system causes a small continuous flow of air to be
passed into the face piece through the regulator. Regardless of whether
the wearer is inhaling or not, there is air and positive pressure in the face
piece. By this system, contaminated air from the atmosphere is not
drawn in by negative pressure (suction) through leaks around the face
piece. A face piece with an exhalation valve designed for demand
operation should never be used with a pressure-demand system, as air
will continually flow out of the exhalation valve, quickly exhausting the
air supply.
Almost all open-circuit SCBAs are considered to be demand systems. A
demand-type SCBA should never be used in an atmosphere considered
to be immediately dangerous to life or health. A pressure-demand SCBA
must be used instead.
All SCBAs must be worn with full face pieces. Many are designed to fit
inside a fully encapsulating suit. Condensation on the visor may give rise
to visibility problems.
5.5.4.2 Protective clothing

Protective clothing ensembles range from safety glasses, hard hat and
safety shoes to fully encapsulating suits, with a supplied source of
breathing air. It also includes disposable coveralls, fire-retardant
clothing, splash suits and many other types of clothing utilizing
different materials to provide a barrier against the hazard.
The primary safeguard of any protective clothing is the material from
which it is manufactured. The six main characteristics of a material to
be considered for acceptable performance are:
. strength: resists damage;
. chemical resistance: resists degradation and permeation;
93

Chapter 5
. thermal resistance: protects under adverse heat conditions;

. flexibility: facilitates activity, ease of movement;
. cleanability: facilitates cleaning and decontamination; and
. ageing resistance: durable over time.
5.5.4.3 Protection levels

Personal protective equipment is essential to prevent the exposure of a
responder, yet it may also inconvenience or disable the wearer by:
. inducing claustrophobia;
. inducing heat stress;
. inducing rapid fatigue;
. impairing communication;
. limiting vision;
. giving a false sense of protection; and
. overprotecting, causing needless hardship.
Thus, the selection of appropriate protection equipment suitable to the
circumstances of the incident is essential. Equally important, the
response personnel who use personal protective equipment should be
monitored closely, in particular during the course of the response, for
physiological and psychological changes in, for example:
. pulse rate;
. body temperature;
. skin colour;
. mental alertness;
. blood pressure; and
. body weight/fluid balance.
Selecting the appropriate protection equipment for a HNS spill can be a
confusing and daunting task. The following factors should be
considered:
. resistance of the materials or fabric to the chemical(s)
spilled;
. respiratory support requirements;
. heat stress;
. reaction by-products when other chemicals are present;
. the gamut of protective equipment configurations to choose
from; and
. the phase of response.
The task is manageable if the decision is taken to select a level of
protection in relation to a predetermined degree of hazard.
94

Some response organizations define four distinct levels of protection:
. Level A is designed to provide the highest level of eye, skin

and respiratory protection possible from a chemical threat.
The responder’s entire body is shielded at this level, and
protection is achieved by using a SCBA inside a totally
encapsulating suit. It should be used when the potential for
highly concentrated chemical vapours or gases exists, when
the possibility of skin exposure from splashing by an
aggressive liquid or contact with a solid is to be absolutely
avoided or when the circumstances of the accident are not
well defined. The wearer must be trained extensively in its
use, and must act as part of a two-man (minimum) entry
team during the response, with a back-up team on standby.
Unfortunately, its bulky design not only can impair the
wearer’s vision but also removes a fair degree of mobility and
agility from the user, who may already be encountering a
difficult situation. Tight spaces, vessel movement, bad
weather, level of physical effort required, air autonomy and
fire source are some of the conditions likely to seriously
hamper its use. A hot day will rapidly cause heat exhaustion;
on the other hand, cold temperatures may stiffen the
garment and drastically impair mobility. The proximity of
flames may ignite certain types of chemical protective
clothing.
Figure 5.26: Level A personal protection equipment

. Level B is designed to provide splash protection while still

using SCBAs for maximum respiratory protection. It affords
adequate protection in situations where the concentration
of known substances involved requires full respiratory
protection, while presenting a lesser hazard for the skin. It
is selected for entering oxygen-deficient atmospheres, as it is
less bulky and gives more manoeuvrability to its user.
95

Chapter 5
Figure 5.27: Level B personal protection equipment

. Level C is designed for situations where a sufficiently low
concentration of a known substance allows the use of air-
purifying respirators. The body is protected through the use
of disposable liquid-splash-protection suits or disposable
clothing, a hard hat, gloves and goggles/face shields.
Figure 5.28: Level C personal protection equipment

. Level D represents the minimum level of protection. There is
no special protection against vapours or liquids. Depending
on the working environment, the use of a hard hat, gloves
and eye protection may be supplemented by dust masks.
Figure 5.29: Level D personal protection equipment

Annex 5-2 further elaborates on the above approach and provides more
information on the recommended equipment for the different levels of
protection, giving details of the circumstances when equipment should
be used and the extent of its limitation during use. It must be
emphasized that the information on equipment design specification in
96

annex 5 must be accompanied by performance expectation data, to

ensure that there are no shortcomings when selecting personal
protective equipment.
It should be noted that situations may arise where the level of chemical
protection required will in fact place responders at an unacceptably high
risk of injuries by factors that are totally independent from the chemical
threat. In such cases, reconsideration of the approach will be necessary,
and may in fact lead to no intervention until the situation reaches a point
where remedial action becomes possible. Responders should ensure
high safety standards on site by following proper site entry procedures,
as well as appropriate decontamination protocols prescribed by the level
of protection selected and the nature of the product involved. The
selection, acquisition and maintenance of equipment, the preparation
of decontamination protocols and the familiarization and training of
response personnel in the use of personal protective equipment
require planning which should be carried out at the preparedness phase.
5.5.5 Decontamination
There is an increased risk of spreading contaminants outside the
exclusion zone whenever personnel enter and exit a contaminated
zone. Adapted decontamination protocols must be developed, reflecting
the levels of hazards presented by spilled materials.
An area within the contamination reduction zone should be designated
the contamination reduction corridor (CRC). The CRC controls access
into and out of the exclusion zone and confines decontamination
activities to the limited area, as shown in figure 5.24. The size of the
corridor depends on the number of stations in the decontamination
procedure, the overall dimensions of work control zones and the
amount of space available at the site. Whenever possible, it should be
a straight path.
The CRC boundaries should be conspicuously marked, with entry and
exit restricted. The far end is the boundary between the exclusion zone
and the contamination reduction zone. Personnel leaving the exclusion
zone must go through the CRC. Anyone in the CRC should be wearing the
level of protection designated for the decontamination of personnel and
portable field equipment and for the removal of contaminated clothing,
etc. All activities within the CRC should be confined to decontamination.
Personal protective clothing, respirators, monitoring equipment and
sampling supplies should all be maintained outside the CRC.
97

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a25089
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TS I L K C EH C Y T E F A S
Chapter 5
25089
98
Annex 5-2
Levels of protection for pre-determined levels
of hazards
Level of Equipment Protection Should be used when: Limiting criteria

protection provided
A Recommended: The highest . The chemical substance . Fully

. Pressure-demand, full available level of has been identified and encapsulating
face-piece SCBA or respiratory, skin, requires the highest level suit material
pressure-demand and eye of protection for the skin, must be
supplied air respirator protection eye and respiratory compatible
with escape SCBA system based on either: with the
. Fully encapsulating – measured (or potential substance
chemical resistant suit for) high concentration involved
. Inner chemical of atmospheric
resistant gloves vapours, gases or
. Chemical resistant particulates; or
safety boots/shoes – site operations and
work functions
Optional: involving a high
. Cooling unit potential for splash,
. Coveralls immersion or exposure
. Long cotton to unexpected
underwear vapours, gases or
. Hard hat particulates of
. Disposable gloves materials that are
and boot covers harmful to skin or
capable of being
absorbed through the
intact skin
. Substances with a high
degree of hazard to the
skin are known or
suspected to be present,
and skin contact is
possible
. Operations must be
conducted in confined,
poorly ventilated areas,
until the absence of
conditions requiring
level A protection is
determined
99

Chapter 5

protection provided
B Recommended: The same level of . The type and . Use only when
. Pressure-demand, full respiratory atmospheric the vapours or
face-piece SCBA or protection, but concentration of gases present
pressure-demand less skin substances have been are not sus-
supplied air respirator protection than identified, and require a pected of
with escape SCBA Level A high level of respiratory containing
. Chemical-resistant protection but less skin high concen-
clothing (overalls and It is the minimum protection. This involves trations of
long-sleeved jacket; level recommend- atmospheres: chemicals
hooded one- or two- ed for initial site – with IDLH that are harm-
piece chemical splash entries, until the concentrations of ful to skin or
suit; disposable hazards have specific substances capable of
chemical-resistant been further that do not represent a being
one-piece suit) identified severe skin hazard; or absorbed
. Inner and outer – that do not meet the through the
chemical-resistant criteria for use of air- intact skin
gloves purifying respirators. . Use only when
. Chemical-resistant . Atmospheres containing it is highly
safety boots/shoes less than 19.5 % oxygen unlikely that
. Hard hat . Presence of the work
. Two-way radio incompletely identified being done
communications vapours or gases is will generate
indicated by a direct either high
Optional: reading of the organic concentration
. Coveralls vapour detection of vapours,
. Disposable boot instrument, but are not gases, part-
covers suspected of containing iculates or
. Face shield high levels of chemicals splashes of
. Long cotton harmful to the skin or material that
underwear capable of being will affect
absorbed through the exposed skin
intact skin
100


protection provided
C Recommended: The same level of . The atmospheric . Atmospheric

. Full face-piece air- skin protection as contaminants, liquid concentration
purifying canister- level B, but a splashes or other direct of chemicals
equipped respirator lower level of contact will not must not
. Chemical-resistant respiratory adversely affect any exceed IDLH
clothing (overalls and protection exposed skin levels
long-sleeved jacket; . The types of air . The
hooded, one- or two- contaminants have been atmosphere
piece chemical splash identified and must contain
suit; disposable concentrations at least 19.5%
chemical-resistant measured, and a canister oxygen
one-piece suit) is available that can
. Inner and outer remove the contaminant
chemical-resistant . All criteria for the use of
gloves air-purifying respirators
. Chemical-resistant are met
safety boots/shoes
. Hard hat
. Two-way radio
communications
Optional:
. Coveralls
. Disposable boot
covers
. Face shield
. Escape mask
. Long cotton
underwear
D Recommended: No respiratory . The atmosphere . This level

. Coveralls protection. contains no known should not be
. Safety boot/shoes Minimal skin hazard worn in the
. Safety glasses or protection. . Work functions preclude exclusion
chemical splash splashes, immersion or zone
goggles the potential for . The
. Hard hat unexpected inhalation of atmosphere
or contact with must contain
Optional: hazardous levels of any at least 19.5%
. Gloves chemicals oxygen
. Face shield
. Escape mask
Source: EPA/OSHA
101

Chapter 6
Case histories
6.1 General remarks

Considering the total number of HNS shipments, the number of
incidents involving spillage is relatively small. This is, to a large extent,
due to the safety measures found on vessels. Nonetheless, accidents do
occur and can have serious consequences. Since the effect of an accident
involving a vessel carrying HNS on the crew, the environment and
property may differ from that of an oil spill, the response will also
differ. The scope of this chapter is to describe, briefly, credible accident
scenarios based on documented examples of accidents involving vessels
carrying HNS which have occurred throughout the years. In this regard,
it is beyond the scope of the chapter to make reference to flag States,
coastal States and names of vessels. The accidents are representative of
some of the situations which may be encountered by a country
experiencing similar events. However, readers should carefully
consider, for their own needs, the range of potential HNS spills they
may experience, the type of vessels that might be involved, spill
circumstances, environments that might be affected and the avail-
ability of preparedness and response measures to deal with similar
future events in their region.
6.2 Case history 1

Narrative: A gas tanker carrying more than 1,300 tonnes of vinyl
chloride monomer (VCM) sank to a depth of 82 m, some 15
miles from a port town. The sinking took place in a semi-
enclosed area surrounded by numerous small islands, on
the outer rim of a natural reserve.
VCM is toxic, and forms explosive/flammable mixtures in air
over a broad concentration range (3.6 to 33.0% v/v). It is
considered carcinogenic. VCM is a highly volatile sub-
stance (behaviour classification system category G) and
under the circumstances would have escaped from the
water into the atmosphere. The residence time of VCM in
the surface water layer would therefore have been short.
However, in this case, the residence time of the VCM in the
water column was increased due to temperature strat-
ification and the depth of the wreck. The solubility of VCM
also increased with the increase in pressure (depth).
Response: The options considered by the authorities in charge were:
. encasing the wreck in concrete on the sea bottom at the
site of sinking;
103

Chapter 6
. transforming the VCM into an inert product (PVC) by the

addition of a polymerization initiator into the tanks;
. releasing the VCM by explosive destruction of the tanks;
. releasing the VCM in a controlled manner;
. pumping the VCM into another vessel from the depth of
82 m; and
. raising the wreck to a depth of 30 m and pumping the
VCM into another vessel.
Given all considerations, the last option was considered the most
appropriate. The wreck was lifted to a depth of 30 m and the VCM was
pumped into another tanker. Seven hundred tonnes of cargo were
recovered. When empty, the wreck was lifted to the sea surface and
transported to a shipyard. A monitoring programme for VCM in the
seawater and air was carried out until the wreck and its cargo were
salvaged. Due to inclement weather and safety considerations, salvage
operations started in the summer of one year and could not be completed
until the following spring.
During the initial stages of the salvage operation, VCM was detected at
the sea surface as the wreck was being righted on its keel. This led to the
assumption that at least one of the tanks had been damaged and was
releasing VCM. It was also suspected that some of the substance which
had leaked out of the tank was trapped between the port side and the
deck plating. In order to avoid a sudden release of a large quantity of VCM
during the salvage operation, holes were drilled into the deck plating and
PVC pipes were connected to carry the VCM to the sea surface, where it
dispersed naturally or was burnt.
6.3 Case history 2

Narrative: A small chemical carrier loaded with 547 tonnes of
acrylonitrile and 500 tonnes of dodecylbenzene sank,
following a collision 52 miles from the coast near deep-
draught shipping lanes.
Acrylonitrile is a liquid which, if spilled, will dissolve and
evaporate (behaviour classification system category DE). It
is highly flammable. According to GESAMP, it is considered
moderately toxic to marine living resources. It is not
considered to bioaccumulate. It is assigned a MARPOL
category of B.
Dodecylbenzene is a liquid, which if spilled, will float
(behaviour classification system category F). It is not
considered flammable. According to GESAMP, it is not
considered to be acutely toxic to marine living resources
and does not bioaccumulate. Dodecylbenzene falls outside
104

Case histories
the A, B, C and D MARPOL pollution categories, and hence

does not warrant the application of the requirements of the
IBC Code, which is mandatory under MARPOL 73/78.
Acrylonitrile was considered to be more harmful to the
marine environment. It was given priority. The authority in
charge therefore gave the order to recover the acrylonitrile
from the vessel.
Response: An 18 km shipping and a 200 m airspace exclusion zone
were enforced around the wreck.
The salvage operation was to lift and manoeuvre the vessel
over the submerged main deck of a semi-submersible barge,
and then transport the wreck to port. In the first righting and
lifting attempt, the cables broke and the ship sank again. It
was then decided to saw the ship in two, to trans-ship,
underwater, the acrylonitrile from the leaking tank, and to
lift the two sections separately.
The salvage company assigned to recover the wreck and the
chemicals mobilized a fleet. It included a floating crane,
which acted as an accommodation base, a semi-submersible
barge, a vessel outfitted as an emergency hospital with a
medical evacuation helicopter and a technical support/
chemical monitoring vessel. Salvage workers were equipped
with protective equipment (i.e., clothing and SCBA). The
crane was equipped with an automatic gas alarm system.
Chemical specialists also formed part of the salvage team.
Navy frigates controlled the area.
The entire operation lasted 73 days, of which only 25 were
productive working days. Delays were caused by bad
weather and high concentrations of chemicals in the atmo-
sphere. Sampling of the seawater and air around the area of
the wreck showed dangerous levels of acrylonitrile, indicat-
ing that a tank might have been breached.
6.4 Case history 3

Narrative: A coaster collided with a chemical tanker at the entrance to a
port. The impact of the collision resulted in damage to the
number 2 wing tank, which contained 310 tonnes of styrene
monomer. A tear in the tank resulted in 230 tonnes of the
styrene being spilled.
Styrene, when spilled, will float and evaporate (behaviour
classification system category FE). It is considered flam-
mable. According to GESAMP, the substance is considered
slightly toxic to marine living resources. It is not considered
to bioaccumulate and is also biodegradable. However, it can
taint marine living resources. It has a MARPOL category of B.
105

Chapter 6
Response: The styrene remaining in the damaged tank was transferred

to another tank. Wooden plugs were placed by divers to
reduce the leakage. Booms placed around the tanker were
unable to corral the spilled material. Tainting tests were
carried out to ensure that seafood had not been affected.
6.5 Case history 4

Narrative: A small chemical carrier loaded with 549 tonnes of
acrylonitrile and 3,013 tonnes of ethylene dichloride sank
16 miles off the coast. The wreck was lying in approximately
110 m of water.
The properties of acrylonitrile have been described in case
history No. 2.
Ethylene dichloride is a liquid which, if spilled, will sink. It is
partly miscible with water (behaviour classification system
category SD). It is also flammable. According to GESAMP, it
is practically non-toxic to marine living resources. No
evidence suggests that it will either bioaccumulate in
marine organisms or taint seafood.
The authority in charge gave the order to recover the
substances from the vessel.
Response: The area was closely observed for any abnormal phenomena,
e.g., excessive fish kills.
The sea was monitored at the surface and at various depths
to check for any changes in water quality.
Three companies were assigned to recover the cargo. A
diving support vessel acted as a base for a team of 20 divers.
A marine survey ship served as a floating accommodation
vessel and as a hospital. This was also equipped with a
helideck suitable for use in a medical evacuation. Other
units on site included mobile pumping systems, as well as a
barge outfitted as a floating pumping station.
An underwater survey using a remotely operated vehicle
showed the vessel with its bow buried in the bottom mud.
The wreck’s stern sat clear off the bottom. The survey also
showed leakage of acrylonitrile from a coupling flange on the
cargo line of one of the tanks. Deep-sea divers used special
seals to stop the acrylonitrile leakage.
The survey also revealed that the wreck had a list of 12o to
port and that the empty wing tanks had collapsed due to the
water pressure. Recovery of the wreck was not an option,
since the structure of the vessel had been compromised.
Priority was given to the recovery of acrylonitrile, due to its
greater toxicity and potential for dispersion if released in the
environment. The cargo was pumped into two different
106

Case histories
tankers, one receiving the acrylonitrile, the other the

ethylene dichloride. Five months elapsed from the time of
the sinking to the time the recovery operations were
completed.
6.6 Case history 5
Narrative: A containership carrying a mixed load of dangerous goods

collided with an inbound bulk carrier in the gulf of a river,
just over 1 km from a populous area. Some containers from
the containership were knocked overboard in an 11 m deep
muddy-bottomed channel, while others were extensively
damaged. Among the containers which fell overboard, the
contents of greatest concern were 16 tonnes of penta-
chlorophenol (PCP) packed in 23 kg paper bags in one of
the containers, and three receptacles containing hydro-
bromic acid. Shortly after the collision, a white haze with a
pungent odour enveloped the ship. The crew secured the
ship’s ventilation system and took shelter below deck.
PCP is a solid (behaviour classification system category S)
with a phenolic odour and is used as a pesticide. The
substance demonstrates both acute and latent toxicity to
humans, and may be absorbed into the body by inhalation,
ingestion and through the skin. Inhalation can cause lung
oedema. According to GESAMP, the substance is considered
to bioaccumulate to a significant extent and is highly toxic
to aquatic life.
Hydrobromic acid is a colourless to yellow liquid (behaviour
classification system category ED) with a pungent odour. It
turns dark on exposure to air and light. The substance is
corrosive to the eyes, skin and respiratory tract. It gives off
corrosive hydrogen bromide gas and generates heat when
mixed with water. Evolving fumes consist of a mixture of
acid in air and acid vapour.
Response: The local authority evacuated 75 residents from their homes

in the nearby village when they complained of a strong
odour.
A safety zone was established, closing the channel to all non-
emergency traffic.
Heavy equipment was dispatched (e.g., derrick and hooper
barges) to stabilize the vessel’s deck cargo, to recover
containers from the water and to remove any damaged
containers. The water was analysed to determine if it was
safe for divers.
107

Chapter 6
A search was carried out to locate the sunken cargo using a

recording fathometer, a magnetometer and a sidescan
sonar. The search was successful after eight days using a
colour video fishfinder.
The lost containers were recovered. The receptacles of
hydrobromic acid were salvaged first and overpacked. The
container storing the PCP had been flattened, and the PCP
bags were scattered over the bottom. The paper bags showed
signs of deterioration in the water and crumbled when
handled. To determine the size of the area over which the
bags were scattered, a grid was established, demarcated by
long piles sunk into the bottom and rising above the water
surface. The PCP was recovered by an air-lift dredge. The
dredged mud-water mixture was cleaned by settling, floccu-
lation and active carbon filtration in a series of specialized
barges. The cleaned water was tested before being returned
to the environment. Solids were separated and sent to a
disposal centre.
A biological monitoring programme was introduced to
establish the impact during clean-up, as well as the
potential impact of PCP.
Communication with the public and the media was con-
sidered an integral part of the management of the crisis. The
response operation, including the recovery of products from
the muddy bottom sediment, subsequent soil treatment and
contaminated material disposal, lasted 35 days.
6.7 Case history 6

Narrative: A barge loaded with liquefied chlorine broke its towline close
to a river dam which formed part of a hydroelectric complex.
Drifting backward, the barge struck a pillar of the dam and
the hull was pierced by submerged concrete projections.
Four tanks held a total of 640 tonnes of liquid chlorine,
capable of releasing a gas cloud which would have affected
a town just downwind.
Chlorine is a gas (behaviour classification system category
G) with a pungent odour. Its vapours are heavier than air
and may travel along the ground. It is not considered
flammable, but it is toxic. Moist chlorine gas is strongly
corrosive and will attack most metals. It also reacts violently
with many organic compounds.
Response: The barge was secured to a large salvage vessel by cables to
prevent it from going over the dam.
The chlorine was transferred to another barge by slowly
reducing the pressure inside the tanks. Released gas was
neutralized by bubbling it through a caustic solution. A
108

Case histories
high-pressure spray of water was set up on the super-

structure of the dam and directed downward towards the
tanks as an added precaution. The spray forced any leaking
chlorine back into the water and washed down any chlorine
cloud. The air and water were monitored, and part of the
town was evacuated.
6.8 Case history 7

Narrative: A gas carrier entered port to offload 553 tonnes of anhy-
drous ammonia to a fertilizer manufacturing company in
the port complex. During the offloading process, a hose
ruptured, due to incompatibility between the construction
material of the hose and the ammonia. As a result, 180
tonnes of the cargo leaked within 50 minutes. A large
cloud enveloped the vessel and moved along the wind
direction towards a shipyard. There were no people in the
shipyard at the time.
Ammonia is lighter than air and is difficult to ignite
(behaviour classification system category GD). It is a strong
corrosive and a very reactive material, and will attack certain
metals.
Response: The fire service used water sprays to wash down the cloud,
so that the valve at the leakage point could be shut. Fire
service personnel equipped with protective clothing went
on board to close the valve on the discharge line. After
dispersion of the ammonia cloud, two crew members were
found dead on the quay. The investigation showed that they
had been showered in liquid ammonia.
6.9 Case history 8

Narrative: A vessel loaded with general cargo and a significant quantity
of dangerous goods ran aground in bad weather, after a fire
in her cargo spaces had caused the crew to abandon ship.
Only 8 of the 31 crew members who abandoned ship were
saved. The ship ran aground close to an inhabited area of
20,000 people.
The cargo aboard the ship included about 1,000 tonnes of
packaged HNS as well as 750 tonnes of bunker fuel. Of the
23 different kinds of substances, only IMDG Code classes 1
(explosives), 5 (oxidizing substances) and 7 (radioactive
materials) were not represented. The presence of 126 tonnes
of sodium metal, together with 600 tonnes of highly
flammable liquids and 750 tonnes of fuel, created an
explosive/flammable cocktail as in the case of sodium–
water contact. Many of the drums containing sodium were
damaged, resulting in fire and explosions.
109

Chapter 6
Response: It was decided that refloating would be too difficult due to

the bottom damage caused by the grounding. The vessel was
therefore discharged in situ, albeit with difficulty due to bad
weather.
The following plan of action was prepared as a result of a
survey done on board:
. discharge the sodium drums from the deck;
. discharge the hold containing the other drums of sodium;
. unload the dangerous goods located on deck, giving
priority to the most polluting substance;
. transfer the bunker fuel; and
. unload the goods from the holds, beginning with the most
dangerous hazardous materials.
Sea and air monitoring were conducted at the start of the
salvage operation. The recovery of the dangerous goods was
completed within three months.
One main problem that arose during the emergency was the
issue of dealing with the media. Uninformed declarations
made by individuals and different authorities led to panic
among the population living in the vicinity of the coast. This
resulted in a massive evacuation of people living in the
proximity of the accident.
6.10 Summary of measures

Table 6 is a summary of response methods based on the short
descriptions given for the different case studies.
Although an oil spill contingency plan can provide a basic framework for
preparedness for and response to HNS accidents, the range of chemical
and toxicological properties of HNS carried in bulk and in package form
is very wide. Such events necessitate intricate and prolonged salvage
operations, the development of novel response techniques and
specialized training for response crews and others involved in the
response.
110

Case histories
Table 6 : Summary of response methods
Case Case Case Case Case Case Case Case

history history history history history history history history
1 2 3 4 5 6 7 8
Pump and/or transfer the x x x x x x x

cargo
Plug stop/stop the leak/ x x x
release
Restrict access to/use of x x x x
area + warning
Air and/or sea water x x x x x x
monitoring
Controlled release of x x x x
cargo
Knock down gas cloud x x
with water spray or fog
Containment with booms x x
Salvage the vessel x x x
Overpack containers x
Evacuation of local x x x
population
Underwater survey x x x
Dredging bottom x
sediment
111.

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El

B INTERNATIONAL MARITIME ORGANIZATION

Licensed to Anglo-Eastern Group for 1 copy. © IMO

Sales number: EA630E

Sales number: IA630E

Copyright # International Maritime Organization 1999

Copyright # International Maritime Organization 1999

All rights reserved.

Licensed to Anglo-Eastern Group for 1 copy. © IMO

This publication, prepared by the Marine Environment Protection

Licensed to Anglo-Eastern Group for 1 copy. © IMO

Licensed to Anglo-Eastern Group for 1 copy. © IMO

Licensed to Anglo-Eastern Group for 1 copy. © IMO

Broadly defined, hazardous and noxious substances (HNS) are those

* Brian Mansfield, ‘‘Can Overboard’’, Technical Seminar on Chemical Spills,

Licensed to Anglo-Eastern Group for 1 copy. © IMO

Table 1: Examples of accidents involving ships carrying HNS

Location (Year) Vessel HNS Quantity Accident type

Licensed to Anglo-Eastern Group for 1 copy. © IMO

. oil spill response technology is well developed; this is not the

Licensed to Anglo-Eastern Group for 1 copy. © IMO

2.1 General remarks

HNS cargoes may be carried at sea either in bulk or in package form.

2.2 Principal conventions of

The two most important international conventions covering the sea

Licensed to Anglo-Eastern Group for 1 copy. © IMO

. the International Convention for the Prevention of Pollution

2.3 HNS in bulk

2.3.1 Bulk liquid HNS

Figure 2.2: A typical fully refrigerated LPG carrier

Licensed to Anglo-Eastern Group for 1 copy. © IMO

Ships designed to carry liquefied gases in bulk are regulated by IMO’s

2.3.2 Bulk solid HNS

The hazards associated with shipment of solid bulk products include:

Figure 2.3: Schematic diagram of a bulk carrier

Licensed to Anglo-Eastern Group for 1 copy. © IMO

2.4 HNS in package form (dangerous goods)

Licensed to Anglo-Eastern Group for 1 copy. © IMO

The International Maritime Dangerous Goods Code (IMDG Code) is used

Table 2: Classes and types of substances according to the IMDG Code

3 Flammable liquids Ethyl alcohol

4 Flammable solids (including self-reactive solids Calcium carbide

5 Oxidizing substances and organic peroxides Sodium chlorate

6 Toxic and infectious substances Sodium cyanide

7 Radioactive substances Radium

8 Corrosives Sodium hydroxide (caustic

9 Miscellaneous dangerous substances and Polychlorinated biphenyls

Licensed to Anglo-Eastern Group for 1 copy. © IMO

not contain detailed occupational health and safety information or data

2.5 Emergency precautions on board

In operational environments, no matter how closely regulations are

IMO has developed response procedures for incidents involving

Figure 2.6: Examples of an EmS and of a MFAG table (Source: IMO)

Licensed to Anglo-Eastern Group for 1 copy. © IMO

2.6 Notification and report of accidents causing

Licensed to Anglo-Eastern Group for 1 copy. © IMO

. description of packages including identification marks;

Licensed to Anglo-Eastern Group for 1 copy. © IMO

1 This annex contains an example of a POLREP system for use

A summarized list of POLREP is given below:

Introduction Address from....... to.......

Part 1: 1 Date and time

40 Date and time