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

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Table 5.12 Cont’d

Threshold limit values (USA) Occupational exposure limits (UK) Air odour

Substance

TWA STEL TWA

(c)

STEL

(c)

threshold

(ppm)

(a)

(mg/m

)

(b)

(ppm)

(a)

(mg/m

)

(b)

(ppm) (mg/m

) (ppm) (mg/m

) (ppm; v/v)

Polyvinyl chloride

Total inhalable dust – – – – – 10 – –

Respirable dust – – – – – 4 – –

Portland cement

Total inhalable dust – – – – – 10 – –

Respirable dust – – – – – 4 – –

Potassium hydroxide – – – 2C – – – 2

Propane –

(d)

–– ––––16000

Propane-1,2,-diol

Total (vapour + particulates) – – – – 150 474 – –

Particulates – – – – – 10 – –

Propane sultone

(e) (e)

Propargyl calcohol,

see

Prop-2-yn-1-ol)

β-Propiolactone 0.5

(e)

1.5

(e)

–– ––––

Propionic acid 10 30 – – 10 31 15 46 0.16

Propoxur – 0.5 – – – 0.5 – 2

Propranolol – – – – – 2 – 6

-Propyl acetate 200 835 250 1040 200 849 250 1060 0.67

-Propyl alcohol SK 200 492 250 614 SK 200 500 250 625 2.6

isoPropyl alcohol – – – – 400 999 500 1250

Propylene

(d)

Propylene dichloride 75 347 110 508 – – – – 0.25

Propylene glycol dinitrate SK 0.05 – – – SK 0.2 1.4 0.2 1.4

Propylene glycol monomethyl ether,

see

1-Methoxypropan-2-ol

Propylene imine SK

(e)

4.7

(e)

–– ––––

Propylene oxide 20 48 – – 5 12 – – 44

-Propyl nitrate 25 107 40 172 – – – –

Propyne,

see

Methyl acetylene

Prop-2-yn-1-ol SK 1 2.3 – – SK 1 2.3 3 7

Pulverized fuel ash

Total inhalable dust – – – – – 10 – –

Respirable dust – – – – – 4 – –

Pyrethrins – – – – – 5 – 10

Pyrethrum – 5 – – – – – –

2-Pyridylamine,

see

2-aminopyridine

Pyridine 5 16 – – 5 16 10 33 0.17

Pyrocatechol,

see

Catechol

Quartz,

see

Silica, crystalline

Quinone 0.1 0.44 – – 0.1 0.4 0.3 1.3 0.084

RDX,

see

Cyclonite

Resorcinol 10 45 20 90 10 46 20 92

Rhodium

Metal – 1 – – – 0.1 – 0.3

(Fume and dust)

Insoluble compounds as Rh – 1 – – – – – –

Soluble compounds as Rh – 0.01 – – – 0.001 – 0.003

Ronnel – 10 – – – 10 – –

Rosin core solder, pyrolysis products – 0.1 – – SEN – 0.05 MEL – 0.15

Rotenone (commercial) – 5 – – – 5 – 10

– 10 (total – –

inhalable dust)

–4––

(respirable dust)

Rubber fume – – – – – 0.6 MEL – –

Rubber process dust – – – – – 6 MEL – –

Rubber solvent (naphtha) 400 1590 – – – – – –

(except

Selenium and compounds as Se – 0.2 – – 0.1 hydrogen – –

selenide)

Selenium hexafluoride as Se 0.05 0.16 – – – – – –

Sesone – 10 – – – 10 – 20

Silane,

see

Silicon tetrahydride

Silica, Amorphous

Total inhalable dust – 10

(f)

–– – 6 – –

Respirable dust – 3

(f)

– – – 2.4 – –

Precipitated – 10 – – – – – –

Silica fume (Respirable) – 2 – – – – – –

Silica fused (Respirable) – 0.1 – – – 0.08 – –

Silica, Crystalline (Respirable)

Cristobalite – 0.05 – –

Quartz – 0.05

(e)

––

– 0.3 – –

Tridymite – 0.05 – –

Tripoli – 0.1 – –

– 10 (total – –

Silicon – 10

(f)

––

inhalable dust)

–4––

(respirable dust)

– 10 (total – –

Silicon carbide – 10

(f)

––

inhalable dust)

–4––

(respirable dust)

Silicon tetrahydride 5 6.6 – – 0.5 0.67 1 1.3











Rouge – 10

(f)

––



























Table 5.12 Cont’d

Threshold limit values (USA) Occupational exposure limits (UK) Air odour

Substance

TWA STEL TWA

(c)

STEL

(c)

threshold

(ppm)

(a)

(mg/m

)

(b)

(ppm)

(a)

(mg/m

)

(b)

(ppm) (mg/m

) (ppm) (mg/m

) (ppm; v/v)

Silver

Metal – 0.1 – – – 0.1 – –

Compounds as Ag – 0.01 – – – 0.01 – –

Soapstone

Respirable dust – 3 – – – – – –

Total dust – 6

(i)

–– ––––

Sodium azide

as sodium azide – – – C0.29 – – – 0.3

as hydrazoic acid vapour – – C0.11 –

Sodium bisulphite – 5 – – – 5 – –

Sodium 2,4-dichloro-phenoxyethyl sulphate,

see

Sesone

Sodium fluoroacetate SK – 0.05 – 0.15 SK – 0.05 – 0.15

Sodium hydroxide – – – C2 – – – 2

Sodium metabisulphite,

see

Disodium disulphite

– 10 (total – –

Starch – 10 – –

inhalable dust)

–4––

(respirable dust)

Stearates – 10 – – – – – –

Stibine,

see

Antimony hydride

Stoddard solvent 100 525 – – – – – –

Strontium chromate – 0.0005

(e)

––

Strychnine – 0.15 – – – 0.15 – 0.45

Styrene, monomer SK 20 – 40 – 100 430 MEL 250 1080 MEL 0.32

Subtilisins (proteolitic enzymes as – – – C0.00006 – 0.00006 – 0.00006

100% pure crystalline enzyme)

Sucrose – 10 – – – 10 – 20

Sulfotep SK – 0.2 – – SK – 0.2 – –

Sulfometuron methyl – 5 – –

Sulphur dioxide 2 5.2 5 13 2 5 5 13 1.1

Sulphur hexafluoride 1000 5970 – – 1000 6070 1250 7590

Sulphuric acid – 1

(e)

–3 – 1 – –

Sulphur monochloride,

see

Disulphur dichloride

Sulphur pentafluoride – – C0.01 – 0.025 0.25 0.075 0.79

Sulphur tetrafluoride – – C0.1 – 0.1 0.4 0.3 1.2

Sulphuryl fluoride 5 21 10 42 5 21 10 42

Sulprofos – 1 – – – – – –

Systox,

see

Demeton

2,4,5-T – 10 – – – 10 – 20











Synthetic vitreous fibres

Continuous filament glass fibres

Respirable – 1f/cc

(h)

––

Inhalable – 5mg/m

Glass wool fibres – 1f/cc

(h)

Rock wool fibres – 1f/cc

(h)

Stag wool fibres – 1f/cc

(h)

Special purpose glass fibres – 1f/cc

(h)

Talc (containing no asbestos fibres) – 2 – – – 1 – –

(respirable dust) (respirable dust)

Talc (containing asbestos fibres) Use asbestos

TLV-TWA

Tantalum metal and oxide dusts – 5 – – – 5 – 10

TEDP,

see

Sulfotep

Tellurium and compounds, as Te – 0.1 – – – 0.1 (except – –

hydrogen telluride)

Tellurium hexafluoride as Te 0.02 0.10 – – – – – –

Temephos – 10 – – – – – –

TEPP SK 0.004 0.047 – – SK 0.004 0.05 0.01 0.12

Terephthalic acid – 10

Terphenyls – – – C5 – – 0.5 5

1,1,2,2-Tetrabromoethane – – – – SK 0.5 7 – –

1,1,1,2-Tetrachloro-2,2- 500 4170 – – 100 847 100 847

difluoroethane

1,1,2,2-Tetrachloro-1,2- 500 4170 – – 100 847 100 847

difluoroethane

1,1,2,2-Tetrachloroethane SK 1 6.9 – – – – – – 1.5

Tetrachloroethylene,

see

Perchloroethylene

Tetrachloromethane,

see

Carbon

tetrachloride

Tetrachloronaphthalene – 2 – – – 2 – 4

Tetraethyl lead as Pb SK – 0.1 – –

SEE

NOTE (K)

Tetraethyl orthosilicate,

see

Ethyl silicate

Tetrafluoroethylene 2 – – –

Tetrahydrofuran 200 590 250 737 100 300 200 599 2.0

Tetramethyl lead as Pb SK – 0.15 – –

SEE

NOTE (K)

Tetramethyl orthosilicate,

see

Methyl silicate

Tetramethyl succinonitrile SK 0.5 2.8 – – SK 0.5 2.8 2 11

Tetranitromethane 0.005 – – – – – – –

Tetrasodium pyrophosphate

anhydride – 5 – –

decahydrate – 5 – –

Table 5.12 Cont’d

Threshold limit values (USA) Occupational exposure limits (UK) Air odour

Substance

TWA STEL TWA

(c)

STEL

(c)

threshold

(ppm)

(a)

(mg/m

)

(b)

(ppm)

(a)

(mg/m

)

(b)

(ppm) (mg/m

) (ppm) (mg/m

) (ppm; v/v)

Tetryl – 2 – – SK – 1.5 – 3

Thallium, soluble compounds,

as Tl SK – 0.1 – – SK – 0.1 – –

4,4′-Thiobis(6-tert-butyl-

-cresol) – 10 – – – 10 – –

Thioglycolic acid SK 1 3.8 – – 1 3.8 – –

Thionyl chloride – – C1 C4.9 – – 1 5

Thiram – 1 – – – 5 – 10

Tin

Metal – 2 – – – – – –

Oxide and inorganic compounds – 2 – – – 2 – 4

except SnH

, as Sn

Organic compounds as Sn SK – 0.1 – 0.2 SK – 0.1 – 0.2

(except Cyhexin)

– 10 (total

inhalable dust)

–4––

(respirable dust)

Toluene 50 191 150 565 SK 50 191 150 574 2.9

Toluene-2,4-diisocyanate (TDI) 0.005 0.036 0.02 0.14

see

Isocyanates

-Toluenesulphonyl chloride – – – – – – – 5 0.17

-Toluidine SK 2

(e)

8.8

(e)

– – 0.2 0.9 – – 0.25

-Toluidine SK 2 8.8 – – – – – –

-Toluidine SK 2

(e)

8.8

(e)

–– ––––

Toluol,

see

Toluene

Toxaphene,

see

Chlorinated camphene

Tributyl phosphate 0.2 2.2 – – – 5 – 5

Trichloroacetic acid 1 6.7 – –

1,2,4-Trichlorobenzene – – C5 C37 1 7.6 – – 1.4

1,1,1-Trichlorobis (chlorophenyl)ethane – – – – – 1 – 3

1,1,1-Trichloroethane,

see

Methyl

chloroform

1,1,2-Trichloroethane SK 10 55 – –

Trichloroethylene 50 269 100 535 SK 100 550 MEL 150 820 MEL 28

Trichlorofluoromethane – – C1000 C5710 1000 5710 1250 7140 5

Trichloromethane,

see

Chloroform

Trichloronaphthalene SK – 5 – – – – – –

Trichloronitromethane,

see

Chloropicrin

1,2,3-Trichloropropane SK 10 60 – – 50 306 75 460

1,1,2-Trichloro-1,2,2-trifluoroethane 1000 7670 1250 9590 1000 7790 1250 9740 45











Titanium dioxide – 10

(i)

––

Tricyclohexyltin hydroxide,

see

Cyhexatin

Tridymite,

see

Silica, crystalline

Triethanolamine – 5 – –

Triethylamine 1 3 15 62 10 42 15 63 0.48

Trifluorobromomethane,

see

Bromotrifluoromethane

1,3,5-Triglycidyl-s-triazinetrione – 0.05 – –

Triglycidyl iso-cyanurate – – – – – 0.1 – –

Trimellitic anhydride,

see

Benzene-

1,2,4-tricarboxylic acid 1,2-anhydride

Trimethylamine 5 12 15 36 10 25 15 37 0.00044

Trimethyl benzene 25 123 – – 25 125 – – 0.55

3,5,5-Trimethylcyclohex-2-enone – – – – – – 5 29

Trimethyl phosphite 2 10 – – 2 10 – – 0.00010

2,4,6-Trinitrophenol,

see

Picric acid

2,4,6-Trinitrophenylmethylnitramine,

see

Tetryl

2,4,6-Trinitrotoluene (TNT) SK – 0.1 – – – 0.5 – –

Triorthocresyl phosphate SK – 0.1 – – – 0.1 – 0.3

Triphenyl amine – 5 – – – – – –

Triphenyl phosphate – 3 – – – 3 – 6

Tripoli,

see

Silica, crystalline

Tungsten as W

Insoluble compounds – 5 – 10 – 5 – 10

Soluble compounds – 1 – 3 – 1 – 3

Turpentine 100 566 – – 100 566 150 850

Uranium (natural)

Soluble and insoluble compounds – 0.2

(g)

– 0.6

(g)

– 0.2 – 0.6

as U

-Valeraldehyde 50 176 – – – – – – 0.028

Vanadium pentoxide as V

0.5 (total

– inhalable dust) – –

Respirable dust and fume – 0.05 – – 0.04 (Fume

– and respirable – –

dust) as V

Vegetable oil mists – 10 – – – – – –

Vinyl acetate 10 35 15 52 10 36 20 72 0.50

Vinyl benzene,

see

Styrene

Vinyl bromide 0.5

(e)

2.2

(e)

–– 5 20 – –

Vinyl chloride 1

(g)

2.6

(g)

–– 7

(l)

– MEL – – 3000

Vinyl cyanide,

see

Acrylonitrile

Vinyl cyclohexene dioxide SK 0.1 0.6 – – – – – –

Vinyl fluoride 1

(e)

–––











Table 5.12 Cont’d

Threshold limit values (USA) Occupational exposure limits (UK) Air odour

Substance

TWA STEL TWA

(c)

STEL

(c)

threshold

(ppm)

(a)

(mg/m

)

(b)

(ppm)

(a)

(mg/m

)

(b)

(ppm) (mg/m

) (ppm) (mg/m

) (ppm; v/v)

Vinylidene chloride 5 20 20 79 10 40 MEL – – 190

Vinylidene fluoride 500 – – –

Vinyl toluene 50 242 100 483 – – – – 10

VM & P naphtha 300 1370 – – – – – –

Warfarin – 0.1 – – – 0.1 – 0.3

Welding fumes (NOC) – 5

(i)

–– – 5 – –

White spirit – – – –

see

EH 40 for calculation

Wood dust (certain hardwoods e.g. – 1

(g)

– – SEN – 5 MEL – –

beech, oak)

Softwood – 5 – 10 – 5 MEL – –

Wool process dust – – – – – 10 – –

Xylene

-isomers 100 434 150 651 SK 100 441 150 662 1.1 (meta)

Xylene α, α′-diamine SK – – – C0.1 – – – –

Xylidine, mixed isomers SK 0.5

(e)

2.5

(e)

– – SK 2 10 10 50 0.056

(2,4-Xylidine)

Yttrium, metal and compounds, as Y – – – – 1 – 3

Zinc chloride fume – 1 – 2 – 1 – 2

Zinc chromates as Cr – 0.01

(g)

–– ––––

Zinc distearate

Total inhalable dust – – – – – 10 – 20

Respirable dust – – – – – 4 – –

Zinc oxide

Fume – 5 – 10 – 5 – 10

Dust – 10 – – – – – –

Zirconium and compounds, as Zr – 5 – 10 – 5 – 10

C Ceiling limit

MEL Maximum exposure limit

NOC Not otherwise classified

SEN Capable of causing respiratory sensitization; skin sensitizers have not been given a separate notation

SK Can be absorbed through skin

This table is a useful guide but because standards are continually under review and many caveats apply reference should be made to the most recent edition of HSE EH

40 and the AGGIH TLV list for current values and their interpretation. Often carcinogens are not assigned a hygiene standard.

(a)

Parts of vapour or gas per million parts of contaminated air by volume at 25°C and 760 torr (1.013 bar).

(b)

Milligrams of substance per m

air.

(c)

Value shown is OES unless otherwise indicated as MEL.

(d)

Simple asphyxiant. Some gases and vapours present at high concentrations act as asphyxiants by reducing the oxygen content of air. Many of these are odourless and

colourless. Many also pose a fire or explosion risk, often at values below which asphyxiation can occur. (Although capable of asphyxiation, they are not considered to

be substances hazardous to health under COSHH.)

(e)

Suspected human carcinogens –

see

TLV Appendix A, Category A2 (below).

(f)

The value is for total dust containing no asbestos and <1% crystalline silica.

(g)

Confirmed human carcinogen –

see

TLV Appendix, A, Category A1 (below).

(h)

Fibres longer than 5

m and with an aspect ratio ≥3:1 as determined by the membrane filter method at 400–450X magnification (4 mm objective) phase contrast

illumination.

(i)

Welding fumes cannot be classified simply. The composition and quantity of both are dependent on the alloy being welded and the process and electrodes used.

Reliable analysis of fumes cannot be made without considering the nature of the welding process and system being examined; reactive metals and alloys such as

aluminium and titanium are arc-welded in a protective inert atmosphere such as argon. These arcs create relatively little fume, but they do create an intense radiation

which can produce ozone. Similar processes are used to arc-weld steels, also creating a relatively low level of fumes. Ferrous alloys also are arc-welded in oxidizing

environments that generate considerable fume and can produce carbon monoxide instead of ozone. Such fumes generally are composed of discrete particles of

amorphous slags containing iron, manganese, silicon, and other metallic constituents depending on the alloy system involved. Chromium and nickel compounds are

found in fumes when stainless steels are arc-welded. Some coated and flux-cored electrodes are formulated with fluorides and the fumes associated with them can

contain significantly more fluorides than oxides. Because of the above factors, arc-welding fumes frequently must be tested for individual constituents that are likely to

be present to determine whether specific TLVs are exceeded. Conclusions based on total fume concentration are generally adequate if no toxic elements are present in

welding rod, metal, or metal coating and conditions are not conducive to the formation of toxic gases.

Most welding, even with primitive ventilation, does not produce exposures inside the welding helmet above 5 mg/m

. That which does, should be controlled.

(j)

UK control limits for asbestos:

Chrysotile 0.3 fibres/ml of air averaged over any continuous 4 hr period

0.9 fibres/ml of air averaged over any continuous 10 min period

Any other form of asbestos, 0.2 fibres/ml of air averaged over any continuous 4 hr period

alone or in mixtures 0.6 fibres/ml of air averaged over any continuous 10 min period

Action levels for cumulative exposures within a 12 week period:

(

for chrysotile, 72 fibre hours/ml of air

(

) for any other form of asbestos, alone or in mixtures, 48 fibre hours/ml of air

(

) for both types of exposure at different times within the period, a proportionate number of fibre hours/ml

The lack of limits should not be taken to imply an absence of hazard. In the absence of a specific OEL for a particular dust, exposure should be adequately controlled

and where there is no indication of the need for a lower value, personal exposure should be kept below both 10 mg/m

8 hr TWA total inhalable dust and 4 mg/m

8 hr TWA respirable dust.

(k)

UK limits for lead are 8 hr TWA concentrations as follows:

Lead other than lead alkyls – 0.15 mg/m

of air

Lead alkyls – 0.1 mg/m

of air

These are ceiling values that must not be exceeded when calculating 8 hr TWA. They should be read in conjunction with biological limits for lead.

(l)

As measured by the vertical elutriator cotton-dust samples.

(m)

Polytetrafluoroethylene decomposition products: thermal decomposition of the fluorocarbon chain in air leads to the formation of oxidized products containing

carbon, fluorine and oxygen. Because these products decompose in part by hydrolysis in alkaline solution, they can be quantitatively determined in air as fluoride to

provide an index of exposure. No TLV is recommended pending determination of the toxicity of the products, but air concentration should be minimal. (Trade names:

Algoflon, Fluon, Teflon, Tetran.)

(n)

In the UK vinyl chloride is also subject to an overriding annual maximum exposure limit of 3 ppm.

(o)

As sampled by a method that does not collect vapour.

TLV Appendix A: Carcinogens (excerpts)

The Chemical Substances Threshold Limit Values Committee classifies certain substances found in the occupational environment as either confirmed or suspected human

Table 5.12 Cont’d

carcinogens. The present listing of substances that have been identified as carcinogens takes two forms: those for which a TLV has been assigned and those for which

environmental and exposure conditions have not been sufficiently defined to assign a TLV. Where a TLV has been assigned, it does not necessarily imply the existence

of a biological threshold; however, if exposures are controlled to this level, we would not expect to see a measurable increase in cancer incidence or mortality.

Two categories of carcinogens are designated:

A1 –

Confirmed Human Carcinogens

. Substances, or substances associated with industrial process, recognized to have carcinogenic potential.

A2 –

Suspected human carcinogens

. Chemical substances, or substances associated with industrial process, which are suspect of inducing cancer, based on their limited

epidemiological evidence or demonstration of carcinogenesis in one or more animal species by appropriate methods.

Exposures to carcinogens must be kept to a minimum. Workers exposed to A1 carcinogens without a TLV should be properly equipped to eliminate to the fullest extent

possible all exposure to the carcinogen. For A1 carcinogens with a TLV and for A2 carcinogens, worker exposure by all routes should be carefully controlled to levels

as low as reasonably achievable

(ALARA) below the TLV.

Flammable chemicals

Certain chemicals pose fire and explosion risks because:

• They ignite easily. Vapours often travel a considerable distance to an ignition source remote

from the point of chemical escape.

• Considerable heat is generated. Many volatile substances liberate heat at a rate some ten times

faster than burning wood.

• The fire spreads easily by, e.g., running liquid fire, a pool fire, a fire ball, heat radiation or thermal

lift (convection).

• Explosion: a confined vapour cloud explosion (CVCE) can result from ignition of vapour

within a building or equipment; a boiling liquid expanding vapour explosion (BLEVE) can

result when unvented containers of flammable chemicals burst with explosive violence as a

result of the build-up of internal pressure; unconfined vapour cloud explosion (UVCE) can

result from ignition of a very large vapour or gas/air cloud.

Clearly, flammable chemicals also pose a health risk if the substance or its thermal degradation

or combustion products are toxic, (e.g. carbon monoxide) or result in oxygen deficiency because

oxygen is consumed. Hot smoke and other respiratory irritants, e.g. aldehydes, are also produced.

Ignition and propagation of a flame front

Normally flame propagation requires

(a) fuel, gas or vapour (or combustible dust) within certain concentration limits,

(b) oxygen supply (generally from air) above a certain minimum concentration, and

All three, represented by the three corners of a triangle (Figure 6.1), must generally be present.

But no ignition source is needed if a material is above a specific temperature (see p. 214), and no

additional oxygen is required if an oxidizing agent is present or in a few cases when oxygen is

within the fuel molecule (e.g. ethylene oxide).

Fuel

Liquids and solids do not burn as such, but on exposure to heat vaporize or undergo thermal

degradation to liberate flammable gases and vapours which burn. Some chemicals undergo

spontaneous combustion (see page 214).