Carson Ph., Mumford C. Hazardous Chemicals Handbook (Справочник по опасным химическим веществам)

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168 TOXIC CHEMICALS

This solvent has an ethereal odour with a detection threshold between 5 and 80 ppm. It can be

absorbed orally, by inhalation and through the skin, and small amounts of the compound can be

detected in the breath of humans several days after exposure. Overexposure by inhalation can

cause central nervous system (CNS) depression – characterized by dizziness, light-headedness,

inebriation and difficulty in walking – and liver damage. Minimal CNS effects occur at exposures

of about 100 ppm. Chronic exposure has resulted in peripheral neuropathy. Ingestion of large

doses can cause internal irritation, nausea, vomiting and diarrhoea; it can cause drowsiness or

unconsciousness. Contact with the skin will result in degreasing, resulting in mild irritation

possibly leading to cracking and secondary infection; in extreme cases dermatitis may occur.

Eye contact with vapour above 100 ppm may cause irritation. Liquid splashes produce irritation.

Studies on the carcinogenicity are inconclusive but IARC classify tetrachloroethylene as a

probable human carcinogen (Class 2A – see Table 5.17).

Thermal degradation in contact with flame or red hot surfaces will produce highly-toxic gases,

e.g. acid chlorides and phosgene. Reaction with freshly-galvanized surfaces may produce

dichloroacetylene, which is also highly toxic.

The long-term OES is 50 ppm (8 hr TWA), set to protect against CNS effects, which will also

protect against liver or kidney damage and irritation. The short-term OES is 1000 ppm (15 minute

reference period) to minimize exposures at irritant levels.

Tetratchloroethylene has been detected in the food chain as a contaminant: its volatility prevents

significant bioaccumulation but some transfer to aquatic sediments is possible. At low concentrations

it is slowly degraded under anaerobic conditions.

The precautions for the use of perchloroethylene correspond with those for trichloroethylene

(Table 5.52). The dry cleaning process, and its safety measures comprise:

• cleaning in hot solvent in sealed machines;

• drying with hot air (after centrifugal removal of liquid solvent) which passes over a lint filter

then cooled to condense solvent;

• deodorization to remove last traces of solvent with fresh air with venting to atmosphere;

• solvent recovery by distillation. Normal measures for solvent control use activated charcoal

absorption filters often as disposable cartridges. Still residues are usually removed manually

from each machine at least once per week, or in some machines they are pumped directly to a

waste storage vessel, often a lidded metal container located outside the building.

Table 5.50 Physical properties of perchloroethylene

Boiling point 121°C

Saturated vapour concentration 1.5 × 10

ppm at 20°C

Specific gravity 1.623 at 20°C

Vapour density (air = 1) 5.83 at 74°C

Solubility in water 0.015% w/w at 25°C

(xii) Perchloroethylene (tetrachloroethene, tetrachloroethylene)

Perchloroethylene is a clear, dense, non-flammable volatile chlorinated solvent. It is widely used

for dry cleaning; small quantities are used in adhesives and cleaning agents. It is miscible with

organic solvents but only slightly soluble in water. Relevant physical properties are given in

Table 5.50.

(xiii) Trichloroethylene (trichloroethene)

Trichloroethylene is a colourless non-flammable chlorinated hydrocarbon liquid. It is mainly

used for degreasing of metals in the engineering and electrical appliance industries; other outlets

are as a solvent in inks, in dry-cleaning, in varnishes and adhesives, and as a solvent in the

extraction of fats and oils. Relevant physical properties are given in Table 5.51.

The solvent has a sweetish odour similar to chloroform detectable at about 30 ppm. It is

primarily a depressant of the central nervous system (CNS). Significant impairment of performance

in behavioural tests and some CNS effects have occurred at 1000 ppm but not at 300 ppm;

prenarcotic symptoms have occurred at mean levels of 200 ppm to 300 ppm.

Direct eye contact with liquid produces injury, generally transient, to the corneal epithelium.

The liquid is mildly irritating to the skin due to the degreasing effect; repeated contact may cause

dermatitis. Ingestion of substantial quantities of liquid can damage the mucous membranes, and

produce acute effects ranging from mild discomfort to profound anaesthesia.

Evidence to indicate that exposure to trichloroethylene is associated with an increased incidence

of cancer in man or in adverse effects in the offspring of women workers exposed to the compound

Table 5.51 Physical properties of trichloroethylene

Boiling point 87°C

Saturated vapour concentration 7.9 × 10

ppm at 20°C

Specific gravity 1.464 at 20°C

Vapour density (air = 1) 4.54

Solubility in water 0.11% w/w at 25°C

Table 5.52 General safety precautions with trichloroethylene and tetrachloroethylene

Do not

Store liquid in buckets or other open storage vessels.

Lean into any vessel containing liquid or vapour.

Use in any location which is not well ventilated, but avoid extraneous draughts.

Enter any confined space, e.g. any tanks or pits, except in accordance with a permit-to-work system.

Store in the open air if possible, or at least in a well-ventilated area which is not below ground level.

Provide and maintain efficient local exhaust ventilation, if enclosed plant cannot be used.

Avoid smoking in proximity to any open system.

Replace lids on any open-topped tanks.

Wear eye protection if there is any risk of splashing.

Avoid contact with the skin. If hand contact is likely, wear PVC gloves.

Avoid contact of liquid or vapour with naked flames or red-hot surfaces.

In vapour degreaser operation, do:

control vapour at the specified level within the tank;

employ effective l.e.v. and prevent draughts in the workroom, e.g. by suitable screening;

avoid overheating of solvent and uncontrolled vaporization, including prevention by the use of appropriate thermostats;

lower and raise work loads slowly, to minimize vapour displacement;

carefully position, or drain, hollow articles.

When cleaning plant, if plant is within a pit, do:

ensure ventilation draws air from the bottom of the pit;

distil off vapour in accordance with specific operating instructions;

allow any liquid to cool to ambient temperature before drawing off into a suitable receptacle;

remove sludge by raking through sump door, after allowing several hours for ventilation;

restrict any entry, in accordance with the Confined Space Regulations 1997.

SPECIFIC PRECAUTIONS 169

170 TOXIC CHEMICALS

is confused but IARC classify trichlorethylene as a probable human carcinogen, Class 2A (see

Table 5.17).

Decomposition of trichloroethylene can occur upon contact with naked flames, red-hot surfaces,

hot elements of electric heaters, or intense UV light with the generation of acidic and highly-toxic

products. The presence of reactive contaminants, e.g. acids, strong alkalis, highly-reactive metals,

may also result in decomposition to similar products.

The Occupational Exposure Standards imposed for trichloroethylene are Maximum Exposure

Limits of 100 ppm (8 hr TWA) and 150 ppm (15 minute reference period). A skin notation ‘Sk’

is applicable because of the potential for skin absorption. Because of its volatility, trichloroethylene

is not recommended for cold cleaning; it is normally used in partially enclosed vapour degreasing

equipment provided with local exhaust ventilation.

Typical precautions with trichloroethylene are summarized in Table 5.52. An important factor

is that the vapours are much heavier than air; they will therefore spread and may accumulate at

low levels, particularly in undisturbed areas. Because of its volatility, releases to the environment

usually reach the atmosphere. Here it reacts with hydroxyl or other radicals (estimated half-life

for reaction with hydroxyl radicals is less than a week) and is not therefore expected to diffuse to

the stratosphere to any significant extent. There is some evidence for both aerobic and anaerobic

biodegradation of trichloroethylene.

(xiv) Sick building syndrome

When working in certain buildings some workers suffer temporarily from a group of symptoms

including:

• lethargy/tiredness;

• irritability;

• lack of concentration/mental fatigue;

• headaches;

• nausea/dizziness;

• sore throats;

• dry eyes and skin;

• skin rash;

• asthma;

• blocked/runny nose.

The condition is usually non-specific and seldom traced to a single cause. This has been termed

sick building syndrome. Despite much research, little has been proven but the building features

associated with the condition are:

• hermetically sealed, airtight shell;

• mechanical heating, ventilation and air-conditioning;

• use of materials and equipment that emit a variety of irritating and sensitizing toxic fumes and/

or dust;

• fluorescent lights;

• application of energy conservation measures;

• lack of individual control over environmental conditions;

• landscape plants;

• VDUs;

• draughts.

Whilst the causative agent(s) have not been established it is thought to be multifunctional and

possibilities include physical factors (humidity, temperature, lighting), static electricity,

electromagnetic radiation, air ion concentrations, fungi, noise, psychological stress, and chemicals.

Chemicals which are not those involved in the normal work processes can become trapped within

the building, albeit at concentrations below those known to cause ill-health effects, if:

• liberated from materials of construction or furnishings; or

• they could enter from outside.

Examples of common pollutants are given in Table 5.53.

Table 5.53 Common pollutants that may be found in buildings

Chemical Source

Ammonia Cleaning solutions

Printers

Cigarette smoke

Asbestos Pipe lagging

Air duct linings

Ceiling and roof tiles

Asbestos cement sheeting

Benzene Synthetic fibres

Plastics

Cleaning solutions

Tobacco smoke

Biocides Air-conditioning systems

Water treatment

Humidifiers

Disinfectants

Carbon dioxide Exhaled breath

Vehicle exhausts

Smoking chimneys

Portable heaters

Carbon monoxide Tobacco smoke

Gas cookers

Gas and oil heaters

Vehicle exhausts from loading bays or diesel trucks

Detergent dust Carpet cleaners

Ethyl alcohol Duplicating fluids

Fibre glass Insulation

Formaldehyde Insulation material

Ceiling tiles

Particle board

Plywood

Office furniture

Carpet glues

Various plastics

Synthetic fibres and rugs

Upholstery and other textiles

Pesticides

Paint

Paper

Tobacco smoke

Hydrocarbons Paints, adhesives

Solvents

Synthetic materials

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172 TOXIC CHEMICALS

Floor and furniture polishes

Vehicle exhausts

Hydrochloric acid Electric stencil cutting machines

Methyl alcohol Spirit duplicating machines

Micro-organisms Duct work

Humidifiers

Oxides of nitrogen Vehicle exhausts

Tobacco smoke

Gas heaters

Ozone Electrical discharges from equipment such as photocopiers, electrostatic

precipitators, fluorescent lights

Paint fumes Paint

PCBs Transformers

Ageing VDUs

Fluorescent lights

Pesticides Plant, timber and fabric treatments

Air conditioning/ventilation units

Photochemical smog Reaction between chemicals and ozone

Radon Soil

Concrete

Stone

Water supply

Solvents Typist correction fluids

Adhesives, glues

Cleaning fluids

Paint

Felt-tip pens

Stencil machines

Inks

Sterilant gases Humidifiers

Air-conditioning units

Sulphur dioxide Coal fires

Power stations

Chimneys

Vehicle exhausts

Vinyl chloride Plastic PVC pipes

Light fittings

Upholstery

Carpets

Table 5.53 Cont’d

Chemical Source

Because the cause is unknown precautions are difficult to specify but general guidance includes

that in Table 5.54.

Temporary problems of building pollution may occur during construction and engineering

activities, refurbishment, painting and decorating, and cleaning in internal, or sometimes external,

areas. The sources are, generally, more easily traced.

(xv) Synthetic resins

Synthetic resins are extensively used, e.g., in surface finishes, in the fabrication and repair of boat

and motor vehicle bodies, in the manufacture of laminated boards, for electrical components, in

pattern making and in paints and varnishes. Non-rubber adhesives made from fish glues and from

cotton derivatives (e.g. cellulose acetate) tend not to be sensitizing but, depending upon composition

and the manner of use, many other types may pose significant dermatitic and fume hazards.

Table 5.54 Precautions to avoid ‘sick buildings’

• Avoid nuisance noise

• Provide adequate ventilation

• Avoid high uniform temperatures

• Avoid lack of air movement

• Provide adequate humidity

• Avoid uniform dull lighting and décor

• Provide natural lighting: avoid tinted glass

• Ensure staff are motivated

• Consider possible cause at building design, construction and commissioning stages

• ‘Bake out’ buildings to drive out pollutants

• Investigate complaints, especially if there are pockets of complaints, or epidemics with related symptoms.

The monomers, catalysts or hardeners, or plasticizers can include chemicals with the potential

to irritate the skin, mucous membranes or respiratory tract. Some can promote skin or respiratory

sensitization. The range of chemicals in use is extremely wide, so that reference should be made

to the Materials Safety Data Sheet for each specific formulation or variation of it identifiable by

reference to the supplier’s proprietary name and code number. Some common resin types are

summarized in Table 5.55.

Table 5.55 Synthetic resin types

Type Examples

Acrylic Polymethyl methacrylate

Amino Melamine formaldehyde, urea formaldehyde, furfuryl alcohol – urea formaldehyde

Epoxy Epichlorohydrin with bisphenol A. The curing agents may pose significant health hazards, e.g.

amines (triethylamine,

-phenylenediamine, diethylenetriamine) or acid anhydrides (pyromellitic

dianhydride)

Phenolic Phenol formaldehyde. Formaldehyde is a respiratory irritant but is not classified as asthmagen.

Polyester Powder coatings containing triglycidyl isocyanurate are possible asthmagens (unclassified)

Polyurethane An organic isocyanate (MDI or a pre-polymer) with a hydroxy compound. The isocyanates are potent

respiratory sensitizers, the risk increasing with volatility

Vinyl Polyvinyl chloride, polyvinyl acetate.

With the exception of epoxy resins, when a resin is fully polymerized it loses any irritant

properties. However, associated materials, e.g. glass fibre used as a filler, or the dust from

plywood or veneers, may promote irritation. Partially-cured resins will retain some irritant properties.

Traces of cutaneous or respiratory sensitizers liberated, e.g. by heating or machinery, may be

problematic.

Epoxy resins are often mixtures of the epoxy resin, a curing agent (hardener), solvents, reactive

diluents, antioxidants and filler. Examples are given in Table 5.56. Curing agents usually comprise

peroxides, amines or anhydrides. These may cure at room temperature or require elevated

temperatures. They may be irritant or damage skin, eyes or lungs; certain amines and peroxides

are sensitizers. The solvents such as acetone, methyl ethyl ketone, toluene, xylene, glycol ethers,

and alcohols pose both health and fire hazards. Glycidyl ethers are used as reactive diluents while

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174 TOXIC CHEMICALS

Table 5.56 Typical exposure effects associated with epoxy resin systems

Resin type Examples Skin contact Inhalation Ingestion

Liquid epoxy based on the • mild to moderate • low volatility, low toxicity

resin reaction product of irritants exposure unlikely

epichlorohydrin • mild to moderate unless heated,

and bisphenol A or sensitizers sprayed, or spread

bisphenol F over large

unventilated surface

Solid epoxy resins based on the • mild to moderate • low volatility, low toxicity

reaction product of irritants and mild exposure unlikely

epichlorohydrin and sensitizers unless crushed or

bisphenol A or • not readily ground

bisphenol F absorbed through

skin

Modified liquid liquid epoxy resins • mild to moderate • low volatility, low toxicity

epoxy resins with added reactive irritants exposure unlikely

diluents or solvents • moderate to unless heated,

strong sensitizers sprayed, or spread

over large unventilated

surfaces

Aliphatic and – • irritants, sensitizers, • respiratory irritants high toxicity

cycloaliphatic corrosive, absorbed

amine curing through skin

agents

Aromatic amine – • sensitizers, long- • respiratory irritants moderate to

curing agents term health • sensitizers high toxicity

effects, absorbed

through skin

Anhydride curing – • corrosive, severe • dusts may be high toxicity

agents sensitizers sensitizers

Reactive diluents glycidyl ethers • moderate to • moderate low toxicity

strong sensitizers volatility, exposure

possible

Solvents acetone, methyl • defats and dries • high volatility, low to high

ethyl ketone (MEK), skin exposure possible toxicity, long-

toluene, xylene, • some may be • irritation term effects

glycol, ethers, absorbed • central nervous

alcohol • may carry other system depression

components (e.g. dizziness, loss

through skin of coordination)

Fillers fibreglass, silicas, • some may be • dust inhalation low toxicity

calcium carbonate, absorbed

powdered metal • potential

pigments primary irritant

phenols, phosphites, amines and thiobisphenols are employed as antioxidants in, e.g., polypropene,

polyethylene and polystyrene resins. Typical precautions are summarized in Table 5.57.

Numerous alternatives to low-solid, solvent-based coatings traditionally used by, e.g., the

wood furniture industry are shown in Table 5.58 with the estimated reduction in volatile organic

compound emissions.

Table 5.57 General precautions with synthetic resins

Substitution using non-irritant resins and constituents, or less hazardous or less volatile constituents.

Limitation of skin contact, e.g. by covering benches, pre-mixing of resins, good housekeeping, mechanization.

Prevent or limit dust and vapour production.

Partial enclosure with local exhaust ventilation, or local exhaust ventilation, of working position: separate hazardous processes

from other work, e.g. spray-painting with epoxy-containing sensitizing and carcinogenic compounds,

Enclose curing and mixing rooms.

Consider in advance procedures to be used for cleaning tools used in the process.

Provision and use of protective clothing, e.g. gloves, gauntlets, armlets, long-sleeved overalls; storage apart from ordinary

clothing.

Provision and use of appropriate barrier cream.

Health surveillance on a regular basis covering skin inspections, enquiries/tests relating to respiratory function: consider the

need to screen out staff with medical histories of allergic reactions.

Provision of first-aid treatment even for trivial injuries to the skin.

Provision of adequate washing facilities including resin-removal cream; enforce high standards of personal hygiene.

Limitation of the use of respiratory protection to those situations where control of exposure by inhalation cannot be

controlled by other means.

Provision of a good standard of general ventilation.

Prohibition of eating, drinking, smoking or application of cosmetics in the workplace.

Plan and organize collection and disposal of waste.

Limit stocks, some ingredients such as MbOCA and MEK have potential for major accidents.

Table 5.58 Alternative wood glues

Coating type VOC reduction (%)

Aqueous base 90–95

High solids (e.g. nitrocellulose) 17–40

UV cured 80–100

Polyester 80–100

Polyurethane 80–100

(xvi) Welding fume

Almost all welding, brazing, gas cutting, burning and similar processes produce polluting fume

and gases which can be harmful. The composition of the fume varies and the quantity generated

depends upon the type of process. A summary of the possible emissions is given in Figure 5.4.

Generally the fume will comprise very fine particles of metals and their oxides. Gases such as

carbon monoxide and nitrogen oxides may be generated and mix with any inert shielding gases

used. The hazard may be increased if the metal is painted (e.g. if lead-based paint is present the

fume will contain lead oxide) or coated (e.g. plastic coatings will emit thermal degradation

products). (Examples are given in Table 5.48.) Metal coatings will also emit thermal degradation

products, e.g. zinc oxide fumes from galvanized steel, lead oxide from steel painted with red lead

for corrosion protection.

Measures to control welding fume include process modifications, engineering controls, system

of work and administrative action as summarized in Figure 5.5.

SPECIFIC PRECAUTIONS 175

176 TOXIC CHEMICALS

Pneumoconioses

Carbon dioxide

Carbon monoxide

Non- pulmonary

Gases

Primary pulmonary

Welding fumes and gases

Particulates

Pulmonary

irritant or

toxic inhalants

Harmful

Relatively

harmless

Fibrotic Nonfibrotic

Silica

Asbestos

Copper

Beryllium

Carbon

Tin

Iron

Aluminium

Cadmium

Chromium

Fluorides

Lead

Manganese

Magnesium

Mercury

Molybdenum

Nickel

Titanium

Vanadium

Zinc

Ozone

Oxides of nitrogen

Phosgene

Phosphine

Figure 5.4

Possible constituents in welding fumes and their effects

Figure 5.5

Measures to control welding fume

Monitor

effectiveness

Assess welding process:

is control of exposure

needed?

YES

Can fume be

controlled by process

modifications?

YES

Modify

process

Make

improvements

Can improved

work methods

reduce fume?

Use ventilation to

control fume as far

as reasonably

practicable

General

ventilation

Local

exhaust

ventilation

Partial

enclosures

LEV

hoods

‘On-gun’

extraction

Conventional

hoods

Is exposure

adequately

controlled?

Train welders in

the use of all

control measures

Ensure

adequate

fit for RPE

Select

suitable

RPE

Assess

requirements

for RPE

YES

SPECIFIC PRECAUTIONS 177