Chapter 1

Volume 2 Start Chapter 1 Chapter 2 Chapter 3 Chapter 4
 

1          Introduction

1.1          Purpose and scope

International Maritime Organization IMO estimates that more than half of packaged goods and bulk cargoes transported by sea today can be regarded as dangerous, hazardous or harmful to the environment. A great deal of these substances, materials and articles are also dangerous or hazardous from a human safety point of view.

The increasing trend in maritime transport of chemicals and dangerous goods also gives rise to an increasing number of accidents involving such products. This development makes great demands on the personnel who are responsible for actions against such accidents in order to protect man and environment from damage.

The aim of this Manual is to provide information to support proper decisions when responding to accidents in the marine environment involving chemicals and dangerous goods. However, it is not possible to provide turn-key solutions ready to retrieve from the Manual on the scene of the accident. The contents of the Manual must be thoroughly reviewed beforehand and the contents are primarily aimed for personnel who are familiar with the area.

The chapters of this Manual focus on spills and lost packages. Chapters 1 - 2 deal with spill behaviour and drift forecasting. Chapters 3 - 6 address monitoring, sampling and response. The Annexes 1 - 7 contain facts on first response, resistivity of materials, case histories, classification of spills, body protection, labelling, and measurement units. Annex 8 contains references.
 

1.2          General first response
               to chemical accidents

Definition of response: The efforts to minimize the risks created in an emergency by protecting the people, the environment, and property, and the efforts to return the scene to normal pre-emergency conditions.

Spills of chemicals at sea are rarely detected without notice in the same way as oil spills. They are most often involved in maritime accidents and can sometimes be observed, surveyed or monitored in the marine environment close to the site of the accident. Unknown lost packages of dangerous goods are sometimes detected floating at sea or washed ashore. Most often, however, such packages can be connected with known accidents.

Occurred accidents, and spills involving chemicals, as well as lost packages of dangerous goods must be reported to all relevant bodies according to national and international agreements and regulations.

When responding to accidents involving chemicals or dangerous goods some general first steps must often be taken which are the same for many accidents no matter what chemicals are involved or what the circumstances are (cf. Annex 1).

Never rush into a chemical incident, but try to use your common sense and assess the situation carefully. Plan the work on a worst possible case basis. Realize that each chemical is different and that a new incident is not going to be the same as an earlier one. There is nothing like a typical incident.

The following list of advices includes such general routines that often should be applied. In minor incidents it is not necessary to follow some of the advices, or it is quite enough to limit their extent. At major accidents it might be necessary to apply the advices to the fullest possible extent. See also “K. Example of a checklist” at the end of Annex 1.
 

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Get a rapid general view of the situation and judge the need for the most urgent actions to be taken, such as medical care of victims, restriction of access, evacuation, reduction of leakages, etc.
 

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Warn passers-by, seafarers, public, etc. Inform appropriate authorities, agencies and mass media.
 

w

Identify all involved chemicals. Note their mode of transport (bulk, container, palleted goods, etc.) as well as type of spill or discharge (escaped chemicals, lost packaged dangerous goods).
 

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Judge the risk for fire, explosion, leakage as well as health risks and risks for adjacent areas (utilize e.g. the IMDG Code, Material Safety Data Sheets, Chemical Safety Cards, Chemical Information Databases).
 

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Establish restriction areas (risk zones) and restrict access to these areas by guarding the entrances.
 

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Make preparations for procedures regarding decontamination, relieving and replacement of personnel, materials and equipment.
 

w

Make appropriate arrangements for beaches, swimming areas, fishing grounds, fresh water intakes, etc., such as restriction of access or restriction of right to use.
 

w

Use monitoring devices continuously for fire, explosion and health risks.
 

w

Assess emission rates, volumes, properties and reactivity for involved chemicals.
 

w

Assess  initial drift, spread and evaporation (direction, distance, volumes) and calculate these behaviours by modelling programs and make forecast maps.
 

w

Continuously monitor drift and spread in order to assess the risk, and continuously take appropriate actions based on the judgements.
 

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Take appropriate steps to stop or reduce damage to environment and property.
 

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Contact, as soon as possible, relevant environmental bodies and plan for appropriate handling of the hazardous waste that the accident and the operation may yield.
 


1.3         Behaviour of chemicals

1.3.1          General physical behaviour
                  of released chemicals in water

Certain general actions should always be taken when accidents involving chemicals and dangerous goods occur. These actions are often the same for most types of accidents, regardless of the circumstances and materials  involved.

 

When responding to a chemical spill in the aquatic environment, it is important that the measures are adjusted for the chemical’s physical behaviour in water. The patterns of spill behaviour in water of various chemical groups and packages are discussed in this Section. Figure 1 - 1 illustrates the principle ways of behaviour of chemicals when spilled into water. However, it should be stressed that this picture is simplified. A chemical spill may exhibit more than one of these properties at the same time.  For example, it may float on the water surface and at the same time evaporate and/or dissolve. It may also react with water. A graphical illustration of the system is given in Figure 1 - 2. The denominations (G, GD, E, etc.) in this figure are explained in subchapter 1.4 and in Annex 4.

 

 

 

 

 

 

 

 

 

 

Figure 1 - 2
 Graphical illustration of the behaviours of chemicals and dangerous goods in water

(the designations G, GD, E, ED, etc. are further explained in Figure 1 - 12 below and in Annex 4).

 


Figure 1 - 1   Principal behaviours of chemicals

when spilled into water.
 

 

 

1.3.2          Chemicals that react with water

General actions should be taken according to Section 1.2 above.

It is impossible to give general guidance on how to respond to chemicals that react with water. The response must be planned from case to case with extreme consideration to the reactivity of the substance.

Of commonly transported chemicals only a few react rapidly with cold water. Such chemicals, that react chemically with water, may in theory fit into any of the Property Groups of Annex 4 with regard to solubility, density and vapour pressure. But as they react with water, their pattern of behaviour does not correspond to the principles of the Property Groups. Some commonly transported chemicals, that react with water, are briefly described below.
 

 

 

Figure 1 - 3Examples of substances that react with water

  

 

 

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, 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 hydrochloric acid.

Toluene diisocyanate (TDI - an often used acronym) is a sinking liquid which reacts slowly with cold water to form carbon dioxide and a plastic-like product (polyisocyanate).

Concentrated sulphuric acid and oleum when mixed with water, may release large amounts of heat, resulting in extremely vigorous boiling.

 

1.3.3          Predicting the reactivity when mixing chemicals
 

Violent reactions may occur when certain chemicals are mixed because the chemicals are incompatible. Classes of incompatible chemicals should be segregated from each other during transportation and storage. By using Figure 1 - 4 (Ref. 62) it could be determined which chemicals can not be mixed together because of possible reactions.

 

#

REACTIVITY

GROUP NAME

 

 

 

 

 

 

 

EPA's Chemical Compatibility Chart

This chart gives indications of some of the hazards that can be expected on mixing chemicals. It is not possible to make such a chart complete. The chart cannot be assumed to ensure compatibility of all chemicals in the class, nor do any blanks necessarily mean that the mixture cannot result in a hazard reaction.

1

Acids, Mineral, Non-oxidizing

1

 

 

 

 

 

 

2

Acids, Mineral, Oxidizing

 

 

2

 

 

 

 

 

3

Acids, Organic

 

G

H

 

3

 

 

 

 

4

Alcohols and Glycols

H

H

F

H

P

 

4

 

 

 

5

Aldehydes

H P

H F

H P

 

5

 

 

6

Amides

H

H

GT

 

 

 

 

6

 

7

Amines, Aliphatic and Aromatic

H

H

GT

H

 

H

 

 

7

 

Example on how to use the table: Is acetone compatible with nitric acid?

8

Azo Compounds,

Diazo Compounds and Hydrazines

H

G

H

GT

H

G

H

G

H

 

 

 

8

 

 

Acetone is a ketone (Class 19) and nitric acid is an oxidizing mineral acid (Class 2). Find the square where column 2 meets row 19.

9

Carbamates

H

G

H

GT

 

 

 

 

 

G

H

 

9

 

10

Caustics

H

H

H

 

H

 

 

 

H

G

10

 

 

The codes H (heat) and F (fire) indicate that these two chemicals are incompatible (in fact they may react explosively).

11

Cyanides

GT

GF

GT

GF

GT

GF

 

 

 

 

G

 

 

11

 

12

Dithiocarbamates

H,F

GF

H,F

GF

H,GT

GF

 

GF

GT

 

U

H

G

 

 

 

12

 

 

 

13

Esters

H

H

F

 

 

 

 

 

H

G

 

H

 

 

13

 

 

 

 

 

 

 

 

  Code  Consequence

 

 

 

 

 

 

 

 

 

 

14

Ethers

H

H

F

 

 

 

 

 

 

 

 

 

 

 

14

 

 

 

 

 

 

 

 

H    Heat Generation

F    Fire

G    Innocuous and non-flammable gas generation

GT  Toxic Gas formation

GF  Flammable Gas formation

E    Explosion

P    Violent Polymerization

S    Solubilization of toxic substance

U    May be hazardous, but Unknown

15

Fluorides, Inorganic

 

GT

 

GT

 

GT

 

 

 

 

 

 

 

 

 

 

 

15

 

 

 

 

 

 

 

16

Hydrocarbons, Aromatic

 

H

F

 

 

 

 

 

 

 

 

 

 

 

 

 

16

 

 

 

 

 

 

17

Halogenated Organics

H

GT

H,F

GT

 

 

 

 

H

GT

H

G

 

H

GF

H

 

 

 

 

 

17

 

 

 

 

 

18

Isocyanates

H

G

H,F

GT

H

G

H

P

 

 

H

P

H

G

 

H,P

G

H

G

U

 

 

 

 

 

18

 

 

 

 

19

Ketones

H

H

F

 

 

 

 

 

H

G

 

H

H

 

 

 

 

 

 

 

19

 

 

 

20

Mercaptans and

Other Organic Sulfides

GT

GF

H,F

GT

 

 

 

 

 

H

G

 

 

 

 

 

 

 

 

H

H

H

20

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

21

Metals, Alkali and

Alkaline Earth, Elemental

H,F

GF

H,F

GF

H,F

GF

H,F

GF

H,F

GF

GF H

GF

H

GF

H

GF

H

GF

H

GF

H

GF,H

GT

GF

H

 

 

 

H

E

GF

H

GF

H

GF

H

21

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

22

Metals, Other Elemental & Alloys

as Powders, Vapors, or Sponges

H,F

GF

H,F

GF

G

F

 

 

 

 

H,F

GT

U

GF

H

 

 

 

 

 

 

H

E

GF H

 

H,F

GF

 

22

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

23

Metals, Other Elemental & Alloys

as Sheets, Rods, Drops, etc.

H,F

GF

H,F

GF

 

 

 

 

 

H,F

G

 

 

 

 

 

 

 

 

H

F

 

 

 

 

 

23

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

24

Metals and Metal Compounds, Toxic

S

S

S

 

 

S

S

 

 

S

 

 

 

 

 

 

 

 

 

 

 

 

 

24

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

25

Nitrides

GF

HF

H,F E

H

GF

H,E

GF

GF

H

 

 

U

H

G

U

GF H

GF

H

GF H

 

 

 

GF H

U

GF H

GF H

E

 

 

 

25

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

26

Nitriles

H,GT GF

H,F GT

H

 

 

 

 

 

 

U

 

 

 

 

 

 

 

 

 

 

H P

 

 

S

GF H

26

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

27

Nitro Compounds, Organic

 

H,F GT

 

 

H

 

 

 

 

H

E

 

 

 

 

 

 

 

 

 

 

H,E GF

 

 

 

H,E GF

 

27

 

 

 

 

 

 

 

 

 

 

 

 

 

 

28

Hydrocarbons, Aliphatic, Unsaturated

H

H

F

 

 

H

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

H E

 

 

 

 

 

28

 

 

 

 

 

 

 

 

 

 

 

 

 

29

Hydrocarbons, Aliphatic, Saturated

 

H

F

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

29

 

 

 

 

 

 

 

 

 

 

 

 

30

Peroxides and Hydroperoxides, Organic

H

G

H

E

 

H

F

H

G

 

H

GT

H,F E

H,F GT

 

H,E

GT

H,F

GT

 

 

 

 

H

E

H

E

H,F GT

H

E

H G

 

H G

H,E

GF

H,P GT

 

H

P

 

30

 

 

 

 

 

 

 

 

 

 

 

31

Phenols and Cresols

H

H

F

 

 

 

 

 

H

G

 

 

 

 

 

 

 

 

 

H

P

 

 

GF

H

 

 

 

GF

H

 

 

 

 

H

31

 

 

 

 

 

 

 

 

 

 

32

Organophosphates, Phosphothioates,

Phosphodithioates

H

GT

H

GT

 

 

 

 

 

U

 

H

E

 

 

 

 

 

 

 

 

 

 

H

 

 

 

 

 

 

 

 

U

 

32

 

 

 

 

 

 

 

 

 

33

Sulfides, Inorganic

GT

GF

HF

GF

GT

 

H

 

 

E

 

 

 

 

 

 

 

 

 

H

 

 

 

 

 

 

 

 

 

 

 

H GT

 

 

33

 

 

 

 

 

 

 

 

34

Epoxides

H

P

H

P

H

P

H

P

U

 

H

P

H

P

 

H

P

H

P

U

 

 

 

 

 

 

 

H

P

H

P

H

P

 

H

P

H

P

 

 

 

 

H

P

H

P

U

H

P

34

 

 

 

 

 

 

 

101

Combustible and

Flammable Materials, Miscellaneous

H

G

H,F GT