Carson Ph., Mumford C. Hazardous Chemicals Handbook (Справочник по опасным химическим веществам)
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60. May impair fertility
61. May cause harm to the unborn child
62. Possible risk of impaired fertility
63. Possible risk of harm to the unborn child
64. May cause harm to breastfed babies
65. Harmful: may cause lung damage if swallowed
66. Repeat exposure may cause skin dryness or cracking
67. Vapours may cause drowsiness and dizziness
Examples of combination of particular risks
14/15 Reacts violently with water, liberating extremely flammable gases
15/29 Contact with water liberates toxic, extremely flammable gas
20/21 Harmful by inhalation and in contact with skin
20/21/22 Harmful by inhalation, in contact with skin and if swallowed
20/22 Harmful by inhalation and if swallowed
21/22 Harmful in contact with skin and if swallowed
23/24 Toxic by inhalation and in contact with skin
23/24/25 Toxic by inhalation, in contact with skin, and if swallowed
23/25 Toxic by inhalation and if swallowed
24/25 Toxic in contact with skin and if swallowed
26/27 Very toxic by inhalation and in contact with skin
26/27/28 Very toxic by inhalation, in contact with skin and if swallowed
26/28 Very toxic by inhalation and if swallowed
27/28 Very toxic in contact with skin and if swallowed
36/37 Irritating to eyes and respiratory system
36/37/38 Irritating to eyes, respiratory system and skin
36/38 Irritating to eyes and skin
37/38 Irritating to respiratory system and skin
39/23 Toxic: danger of very serious irreversible effects through inhalation
39/23/24 Toxic: danger of very serious irreversible effects through inhalation and in contact with skin
39/23/24/25 Toxic: danger of very serious irreversible effects through inhalation, in contact with skin and if swallowed
39/23/25 Toxic: danger of very serious irreversible effects through inhalation, and if swallowed
39/24 Toxic: danger of very serious irreversible effects in contact with skin
39/24/25 Toxic: danger of very serious irreversible effects in contact with skin and if swallowed
39/25 Toxic: danger of very serious irreversible effects if swallowed
39/26 Very toxic: danger of very serious irreversible effects through inhalation
39/26/27 Very toxic: danger of very serious irreversible effects through inhalation and in contact with skin
39/26/27/28 Very toxic: danger of very serious irreversible effects through inhalation, in contact with skin and if swallowed
39/26/28 Very toxic: danger of very serious irreversible effects through inhalation and if swallowed
39/27 Very toxic: danger of very serious irreversible effects in contact with skin
39/27/28 Very toxic: danger of very serious irreversible effects in contact with skin and if swallowed
39/28 Very toxic: danger of very serious irreversible effects if swallowed
40/20 Harmful: possible risk of irreversible effects through inhalation
40/20/21 Harmful: possible risk of irreversible effects through inhalation and in contact with skin
40/20/21/22 Harmful: possible risk of irreversible effects through inhalation in contact with skin and if swallowed
40/20/22 Harmful: possible risk of irreversible effects through inhalation and if swallowed
40/22 Harmful: possible risk of irreversible effects if swallowed
40/21 Harmful: possible risk of irreversible effects in contact with skin
40/21/22 Harmful: possible risk of irreversible effects in contact with skin and if swallowed
42/43 May cause sensitization by inhalation and skin contact
48/20 Harmful: danger of serious damage to health by prolonged exposure through inhalation
48/20/21 Harmful: danger of serious damage to health by prolonged exposure through inhalation and in contact with
skin
48/20/21/22 Harmful: danger of serious damage to health by prolonged exposure through inhalation in contact with skin
and if swallowed
48/20/22 Harmful: danger of serious damage to health by prolonged exposure through inhalation and if swallowed
48/21 Harmful: danger of serious damage to health by prolonged exposure in contact with skin
48/21/22 Harmful: danger of serious damage to health by prolonged exposure in contact with skin and if swallowed
48/22 Harmful: danger of serious damage to health by prolonged exposure if swallowed
48/23 Toxic: danger of serious damage to health by prolonged exposure through inhalation
Table 14.3 Cont’d
LABELLING 449
450 MARKETING
48/23/24 Toxic: danger of serious damage to health by prolonged exposure through inhalation and in contact with skin
48/23/24/25 Toxic: danger of serious damage to health by prolonged exposure through inhalation, in contact with skin and
if swallowed
48/23/25 Toxic: danger of serious damage to health by prolonged exposure through inhalation and if swallowed
48/24 Toxic: danger of serious damage to health by prolonged exposure in contact with skin
48/24/25 Toxic: danger of serious damage to health by prolonged exposure in contact with skin and if swallowed
48/25 Toxic: danger of serious damage to health by prolonged exposure if swallowed
50/53 Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment
51/53 Toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment
52/53 Harmful to aquatic organisms, may cause long-term adverse effects in the aquatic environment
Table 14.4 ‘Safety’ phrases from the Approved List
1. Keep locked up
2. Keep out of reach of children
3. Keep in a cool place
4. Keep away from living quarters
5. Keep contents under . . . (appropropriate liquid to be specified by the manufacturer)
6. Keep under . . . (inert gas to be specified by the manufacturer)
7. Keep container tightly closed
8. Keep container dry
9. Keep container in a well-ventilated place
12. Do not keep the container sealed
13. Keep away from food, drink and animal feeding stuffs
14. Keep away from . . . (incompatible materials to be indicated by the manufacturer)
15. Keep away from heat
16. Keep away from sources of ignition – No Smoking
17. Keep away from combustible material
18. Handle and open container with care
20. When using do not eat or drink
21. When using do not smoke
22. Do not breathe dust
23. Do not breathe gas/fumes/vapour/spray (appropriate wording to be specified by manufacturer)
24. Avoid contact with skin
25. Avoid contact with eyes
26. In case of contact with eyes, rinse immediately with plenty of water and seek medical advice
27. Take off immediately all contaminated clothing
28. After contact with skin, wash immediately with plenty of . . . (to be specified by the manufacturer)
29. Do not empty into drains
30. Never add water to this product
33. Take precautionary measures against static discharges
35. This material and its container must be disposed of in a safe way
36. Wear suitable protective clothing
37. Wear suitable gloves
38. In case of insufficient ventilation, wear suitable respiratory equipment
39. Wear eye/face protection
40. To clean the floor and all objects contaminated by this material use . . . (to be specified by the manufacturer)
41. In case of fire and/or explosion do not breathe fumes
42. During fumigation/spraying wear suitable respiratory equipment (appropriate wording to be specified by the
manufacturers)
43. In case of fire, use . . . (indicate in the space the precise type of fire-fighting equipment. If water increases the risk,
add – Never use water)
45. In case of accident or if you feel unwell, seek medical advice immediately (show the label where possible)
46. If swallowed seek medical advice immediately and show this container or label
47. Keep at temperature not exceeding . . . °C (to be specified by the manufacturer)
48. Keep wetted with . . . (appropriate material to be specified by the manufacturer)
49. Keep only in the original container
50. Do not mix with . . . (to be specified by the manufacturer)
51. Use only in well-ventilated areas
Table 14.3 Cont’d
52. Not recommended for interior use on large surface areas
53. Avoid exposure – obtain special instructions before use
56. Dispose of this material and its container to hazardous or special waste collection point
57. Use appropriate containment to avoid environmental contamination
59. Refer to manufacturer/supplier for information on recovery/recycling
60. This material and/or its container must be disposed of as hazardous waste
61. Avoid release to the environment. Refer to special instructions/safety data sheet
62. If swallowed, do not induce vomiting: seek medical advice immediately and show this container or label
63. In case of accident by inhalation: remove casualty to fresh air and keep at rest
64. If swallowed, rinse mouth with water (only if the person is conscious)
Table 14.4 Cont’d
Information
Suppliers must also provide the customer with more detailed information on the hazards and
safety precautions of their products. If the chemicals are to be used in connection with work this
is usually in a Material Safety Data Sheet. Relevant information from Table 1.10 should be
included and at least cover that listed in Table 14.10.
The information must be provided under the headings shown in Table 14.11 and enable the user
to determine the precautions required when using the chemical.
Where necessary the manufacturer must carry out, or arrange for, safety testing. Many countries
operate mandatory premanufacturing and premarketing notification schemes of which safety
testing is the cornerstone. Within the European Community under Directive 67/548/EEC and its
sixth amendment 79/831/EEC, Competent Authorities must be notified before new substances are
supplied in the marketplace. In the UK this Directive is enacted by the Notification of New
Substances Regulations 1993 (NONS). Exempt are:
• Substances listed on the European Inventory of Existing Chemical Substances (EINECS).
• Medicinal products.
INFORMATION 451
Examples of combination of safety precautions
1/2 Keep locked up and out of the reach of children
3/9/14 Keep in a cool well-ventilated place away from [incompatible materials to be indicated by
manufacturer]
3/9/14/49 Keep only in the original container in a cool well-ventilated place away from [incompatible
materials to be indicated by manufacturer]
3/9/49 Keep only in the original container in a cool well-ventilated place
3/14 Keep in a cool place away from [incompatible materials to be indicated by the manufacturer]
7/8 Keep container tightly closed and dry
7/9 Keep container tightly closed and in a well-ventilated place
7/47 Keep container tightly closed and at a temperature not exceeding [ ]
o
C [to be specified by
manufacturer]
20/21 When using do not eat, drink or smoke
24/25 Avoid contact with skin and eyes
29/56 Do not empty into drains, dispose of this material and its container to hazardous or special waste
collection point
36/37 Wear suitable protective clothing and gloves
37/38/39 Wear suitable protective clothing, gloves and eye/face protection
36/39 Wear suitable protective clothing and eye/face protection
37/39 Wear suitable gloves and eye/face protection
47/49 Keep only in the original container at temperature not exceeding [ ]
o
C [to be specified by
manufacturer]
452 MARKETING
Table 14.5 Classification of and symbols for substances dangerous for supply (Schedule 1 Part I)
Characteristic properties Classification and Symbol
of the substance indication of general
nature of risk
A substance which may explode under the effect of flame or which Explosive
is more sensitive to shocks or friction than dinitrobenzene.
A substance which gives rise to highly exothermic reaction when in Oxidizing
contact with other substances, particularly flammable substances.
A liquid having a flash point <0°C and a boiling point ≤35°C. Extremely flammable
(1)
A substance which Highly flammable
(1)
(a) may become hot and finally catch fire in contact with air at
ambient temperature without any application of energy;
(b) is a solid and may readily catch fire after brief contact with a
source of ignition and which continues to burn or to be
consumed after removal of the source of ignition;
(c) is gaseous and flammable in air at normal pressure;
(d) in contact with water or damp air, evolves highly flammable
gases in dangerous quantities; or
(e) is a liquid having a flash point <21°C.
A substance which is a liquid having a flash point ≥21°C and Flammable
(1)
No symbol required
≤55°C, except a liquid which when tested at 55°C in the manner
described in Schedule 2 to the Highly Flammable Liquids and
Liquefied Petroleum Gases Regulations 1972 does not support
combustion.
A substance which if it is inhaled or ingested or it penetrates the Very toxic
(2)
skin, may involve extremely serious acute or chronic health risks
and even death.
A substance which if it is inhaled or ingested or it penetrates the Toxic
(2)
skin, may involve serious acute or chronic health risks and even
death.
A substance which if it is inhaled or ingested or it penetrates the Harmful
(2)
skin, may involve limited health risks.
A substance which may on contact with living tissues destroy them. Corrosive
A non-corrosive substance which, through immediate, prolonged or Irritant
repeated contact with the skin or mucous membrane, can cause
inflammation.
(1)
Preparations packed in aerosol dispensers shall be classified as flammable in accordance with Part III of this schedule.
(2)
Substances shall be classified as very toxic, toxic or harmful in accordance with the additional criteria set out in
Part II of this schedule.
Table 14.6 Classification of and hazard warning signs for substances dangerous for conveyance (Schedule 2 Part I)
Characteristic properties of the substance Classification Hazard warning sign
A substance which
(a) has a critical temperature <50°C or which at Non-flammable
50°C has a vapour pressure of more than 3 bar compressed gas
absolute and
(b) is conveyed by road at a pressure of more than
500 millibars above atmospheric pressure or
in liquefied form other than a toxic gas or a
flammable gas.
A substance which has a critical temperature <50°C Toxic gas
or which at 50°C has a vapour pressure of more
than 3 bar absolute and which is toxic.
A substance which has a critical temperature <50°C Flammable gas
(1)
or which at 50°C has a vapour pressure of more
than 3 bar absolute and is flammable.
A liquid with a flash point ≤55°C except a liquid Flammable liquid
(1,2)
which
(a) has a flash point ≥21°C and ≤55°C and
(b) when tested at 55°C in the manner described
in Schedule 2 to the Highly Flammable
Liquids and Liquefied Petroleum Gases
Regulations 1972 does not support
combustion.
A solid which is readily combustible under Flammable solid
conditions encountered in conveyance by road
or which may cause or contribute to fire through
friction.
A substance which is liable to spontaneous heating Spontaneously
under conditions encountered in conveyance by combustible
road or to heating in contact with air being then substance
liable to catch fire.
COMPRESSED GAS
TOXIC GAS
FLAMMABLE GAS
FLAMMABLE LIQUID
FLAMMABLE SOLID
SPONTANEOUSLY
COMBUSTIBLE
INFORMATION 453
454 MARKETING
HARMFUL – STOW
AWAY FROM
FOODSTUFFS
A substance which in contact with water is liable to Substance which in
become spontaneously combustible or to give off contact with water
a flammable gas. emits flammable gas
A substance other than an organic peroxide which, Oxidizing substance
although not itself necessarily combustible, may
by yielding oxygen or by a similar process cause
or contribute to the combustion of other material.
A substance which is Organic peroxide
(a) an organic peroxide and
(b) an unstable substance which may undergo
exothermic self-accelerating decomposition.
A substance known to be so toxic to man as to Toxic substance
afford a hazard to health during conveyance or
which, in the absence of adequate data on human
toxicity, is presumed to be toxic to man.
A substance known to be toxic to man or, in the Harmful substance
absence of adequate data on human toxicity, is
presumed to be toxic to man but which is unlikely
to afford a serious acute hazard to health during
conveyance.
A substance which by chemical action will Corrosive substance
(a) cause severe damage when in contact with
living tissue;
(b) materially damage other freight or equipment
if leakage occurs.
DANGEROUS WHEN WET
OXIDIZING AGENT
ORGANIC PEROXIDE
CORROSIVE
TOXIC
Table 14.6 Cont’d
Characteristic properties of the substance Classification Hazard warning sign
A substance which is listed in Part 1A of the Other dangerous
approved list and which may create a risk to the substance
health or safety of persons in the conditions
encountered in conveyance by road, whether or
not it has any of the characteristic properties set
out above.
Packages containing two or more dangerous Mixed hazards
substances which have different characteristic
properties.
(1)
An aerosol which is flammable in accordance with paragraph 2 or Part III of Schedule 1 shall have the classification of a
flammable gas. Other aerosols need not be classified as flammable gas or flammable liquid.
(2)
Viscous preparations which comply with the conditions in Part III of this schedule shall not be required to be classified as
flammable.
Table 14.7 Criteria for the toxicity classification of substances
Category
(1)
LD
50
absorbed LD
50
absorbed LC
50
absorbed by
orally in rat percutaneously in inhalation in rat
(mg/kg)
rat or rabbit
(mg/kg) (mg/I, 4 hr)
Very toxic ≤25 ≤50 ≤0.5
Toxic >25 to 200 >50 to 400 >0.5 to 2
Harmful >200 to 2000 >400 to 2000 >2 to 20
(1)
‘Very toxic’, ‘toxic’ or ‘harmful’, applied to a dangerous substance not classified in accordance with Schedules 3, 4 and
5, means that the substance has a toxicity falling within the range tabulated for that category.
Note
If a substance produces other effects that make it inadvisable to use the LD
50
or LC
50
value as the principal basis of
classification, the substance should be classified according to the magnitude of these effects.
DANGEROUS
SUBSTANCE
DANGEROUS
SUBSTANCE
Table 14.6 Cont’d
Characteristic properties of the substance Classification Hazard warning sign
Table 14.8 Hazard classification of explosives (UK)*
Division Division No.
Substances and articles that have a mass explosion hazard 1.1
Substances and articles that have a projection hazard but not a mass explosion hazard 1.2
Substances and articles that have a fire hazard and either a minor blast hazard or a
minor projection hazard but not a mass explosion hazard 1.3
Substances and articles that present no significant hazard 1.4
Very insensitive substances that have a mass explosion hazard 1.5
Extremely insensitive articles which do not have a mass explosion hazard 1.6
*See also UN recommendations on transportation of dangerous goods and the IARTA Regulations (page 460).
INFORMATION 455
456 MARKETING
Table 14.9 Compatibility groups for explosives (UK)
Compatibility group Designating letter
Primary explosive substance A
Article containing a primary explosive substance and not containing two or B
more independent safety features
Propellant explosive substance or other deflagrating explosive substance or C
article containing such explosive substance
Secondary detonating explosive substance or black powder or article D
containing a secondary detonating explosive substance, in each case
without means of initiation and without a propelling charge, or article
containing a primary explosive substance and containing two or more
independent safety features
Article containing a secondary detonatng explosive substance, without E
means of initiation and with a propelling charge (other than a charge
containing a flammable or hypergolic liquid)
Article containing a secondary detonating explosive substance, with means F
of initiation and either with a propelling charge (other than a charge
containing a flammable or hypergolic liquid) or without a propelling charge
A substance that is an explosive substance because it is designed to produce G
an effect by heat, light, sound, gas or smoke or a combination of these as a
result of non-detonative self-sustaining exothermic chemical reactions or an
article containing such a substance which is explosive because it is capable
by chemical reaction in itself of producing gas at such a temperature and
pressure and at such a speed as could cause damage to surroundings and an
illuminating, incendiary, lachrymatory or smoke-producing substance (other
than a water-activated article or one containing white phosphorus,
phosphide or a flammable liquid or gel)
Article containing both an explosive substance and white phosphorus H
Article containing both an explosive substance and a flammable liquid or gel J
Article containing both an explosive substance and a toxic chemical agent K
Explosive substance or explosive article presenting a special risk needing L
isolation of each type
Substance or article so packed or designed that any hazardous effect arising S
from accidental functioning is confined within the package unless the
package has been degraded by fire, in which case all blast or projection
effects are limited to the extent that they do not significantly hinder or
prohibit fire-fighting or other emergency response efforts in the immediate
vicinity of the package
• Plant protection products.
• Cosmetics.
• Foodstuffs including additives and flavourings.
• Animal feeding stuffs.
• Radioactive substances.
• Waste substances.
• Substances in transit under customs supervision.
• Substances classed as ‘no longer polymers’. These are listed polymers which were considered
to be polymers under the NONS 82 definition but not by the NONS 93 version. Unlisted
substances may also be exempt if they could have been considered under NONS 82, or are
not a polymer under NONS 93, or were placed on the market between 1 January 1971 and
1 November 1993.
Table 14.10 Minimum information for a Material Safety Data Sheet
•
Identification
Identification of product by trade name. Supplier’s name and address plus a telephone number (for emergencies).
•
Chemical composition
Chemical composition; details of ingredients, formulae and proportions, including measures to be taken for over-exposure
to eyes/skin or by inhalation/ingestion/absorption. Information for medical treatment.
•
Disposal – normal and emergency spills
General precautions, disposal methods and statutory controls.
Clean-up, neutralization, disposal methods for spills.
•
Fire and explosion hazards and precautions
Flammable limits, flash point, auto-ignition temperature etc.
Reactivity, stability.
Fire-fighting procedures.
•
Health hazards
Acute (short-term) effects and chronic (long-term) effects.
Special hazards.
First detectable signs of over-exposure by all means of entry.
•
Environmental hazards
•
Test data
•
Exposure limits
Threshold Limit Values or Occupational Exposure Limits (preferably with reference to their interpretation, i.e. not as ‘safe’
levels).
For mixtures – reference to prediction, or substance used for basis.
•
Legal requirements
Any legislation applicable to safe handling, storage and use.
•
Control measures
Containment, ventilation, means of limiting exposure generally.
•
Personal protection
Identify requirements and circumstances for use.
Emergency requirements.
•
Storage and handling
Conditions of storage, segregation, materials of construction.
Types of container and handling precautions.
Where relevant, procedures for disposal of containers, e.g. aerosol dispensers, drums when ‘empty’.
•
References
References consulted and further sources of information.
Table 14.11 Headings for information supplied on a Safety Data Sheet
Identification of the substance/preparation and company
Composition/information on ingredients
Hazards identification
First-aid measures
Fire-fighting measures
Accidental release measures
Handling and storage
Exposure controls/personal protection
Physical and chemical properties
Stability and reactivity
Toxicological information
Ecological information
Disposal consideration
Transport information
Regulatory information
Other information
INFORMATION 457
458 MARKETING
• Substances intended solely for scientific research and development in quantities less than
100 kg per year.
• Substances placed on the market for process-orientated research and development with a
limited number of customers registered with the notifier.
The aim of the notification systems is to identify possible risks posed to people and the environment
from placing new substances on the market. A notification comprises:
• data on the chemical identity of the substance;
• an estimate of the quantity of the substance to be placed on the EC market;
• details of the functions and uses of the substance;
Table 14.12 Notification bands*
Type of notification Information Quantity placed on the
requirements market
Deemed to have been notified – 0 kg
REDUCED Acute toxicity 10 kg
Indications for use
Chemical identity
REDUCED Additional acute toxicity 100 kg/annum or 500 kg
Acute daphnia toxicity cumulative
Biodegradability
Physico-chemical properties
BASE SET Mutagenicity 1 t/annum or 5 t cumulative
Toxicity to reproduction
Toxicity to algae
Acute daphnia and fish toxicity
Abiotic and readily biotic
degradability
Additional physico-chemical
properties
‘Lower’ LEVEL 1 Possibly some of the 10 t/annum or 50 t cumulative
information from ‘Upper’
LEVEL 1
‘Upper’ LEVEL 1 Chronic toxicity 100 t/annum or 500 t cumulative
Toxicity in soil and plants
Additional mutagenicity
Long-term toxicity
Bioaccumulation
Inherent biodegradability
Additional abiotic degradability
LEVEL 2 Carcinogencity 1000 t/annum or 5000 t
Additional chronic toxicity cumulative
Additional environmentally
dangerous properties
Toxicity to birds
Long-term toxicity in water and
soil
Degradability simulation tests
Additional abiotic degradability
Mobility in water, soil and air
*A complete list of the information required for each type of notification is given in Schedules 2 and 3 of the Regulations.