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

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Methyl formate *

Methyl glycol *

Methyl glycol acetate *

Methyl heptanone *

Methyl iodide *

Methyl isobutylketone 130–15 600 ppm

Methyl mercaptan 0.1–20 ppm

2–1000 ppm

Methyl methacrylate 15 –700 ppm

-Methyl morpholine *

1-Methylpropanol *

2-Methylpropan-2-ol 50 –500 ppm

Methyl propyl ketone 130 –15 600 ppm

-Methylpyrolidone *

α-Methyl styrene 10 –50 ppm

Methyl styrene 10–100 ppm

Methyl-

tert

-butylether *

Methyl vinyl ketone *

Morpholine *

Naphthalene *

Natural gas *

Nickel carbonyl 0.1 –1 ppm

Nickel chloride 0.1 –1 mg/m

Nickel tetracarbonyl 0.1 –1 ppm

Nitric acid 1–50 ppm

Nitroglycerine *

Nitrogen dioxide 0.5 –25 ppm

2–100 ppm

Nitroglycol *

2-Nitropropane *

Nitrous fumes 0.025–10 ppm

2–150 ppm

20–500 ppm

50–2000 ppm

100–5000 ppm

-Nonane 12–360 ppm

500–1000 ppm

iso-Octane 10–200 ppm

10–1500 ppm

-Octane 1–300 ppm

10–2500 ppm

Octene 20 –1000 ppm

Oil 1–10 mg/m

2.5–10 mg/m

Oil (mist and vapour) 2.5 –10 mg/m

Olefins (general) 1 –55 mg/l

Organic arsenic compounds and arsine *

Organic basic nitrogen compounds *

Oxirane 1 –15 ppm

25–500 ppm

Oxygen 5–23 vol %

Ozone 0.05–1.4 ppm

10–300 ppm

2,4-Pentadione *

Pentane 100–1500 ppm

Pentan-2-one 130 –15 600 ppm

Pentyl acetate 200–1000 ppm

Table 10.18(a) Cont’d

Substance Measuring range

TOXIC PARTICULATES 349

350 MONITORING TECHNIQUES

Perchloroethylene 0.1 –4 ppm

0.7–300 ppm

10–500 ppm

Petroleum hydrocarbons (general) 10 –300 ppm

100–2500 ppm

Phenol 1 –20 ppm

Phenylhydrazine *

Phenyl mercaptan 2 –100 ppm

Phosgene 0.02 –1 ppm

0.25–25 ppm

Phosphine 0.01 –1 ppm

0.1–40 ppm

1–100 ppm

25–10 000 ppm

15–3000 ppm

Phosphoric acid ester 0.05 ppm

α-Pinene 10 –200 ppm

Polytest *

Potassium dichromate *

Propanal *

Propane 0.5 –1.3 vol %

Propan-1-ol 100 –3000 ppm

Propan-2-ol 15 –40 ppm

50–4000 ppm

100–3000 ppm

Propargyl alcohol *

Propionic acid 1 –15 ppm

-Propyl benzene 5 –300 ppm

Propylene glycol *

Propylene oxide 4–60 ppm

50–2000 ppm

Pyridine 5 ppm

Pyrrolidine *

Shellsol *

Sodium chromate 0.1 –0.5 mg/m

Strontium chromate 0.2 –1 mg/m

Styrene 10–250 ppm

50–400 ppm

Sulphur dioxide 0.1–3 ppm

0.5–25 ppm

1–25 ppm

20–2000 ppm

50–8000 ppm

Sulphuric acid 1–5 mg/m

Tar from brown coal *

Tar vapours *

Tetrabromoethane *

1,1,2,2-Tetrabromoethane 0.5 –3 ppm

1,1,2,2-Tetrachloro-1,2-difluoroethane *

1,1,1,2-Tetrachloro-2,2-difluoroethane *

1,1,2,2-Tetrachloroethane *

Tetrafluoroethane *

Tetrafluoromethane *

Tetrahydrofuran *

Tetrahydrothiophene 1 –16 ppm

Thioether *

Thionyl chloride 1 –30 ppm

Table 10.18(a) Cont’d

Substance Measuring range

Thiophene *

Toluene 5–300 ppm

50–400 ppm

100–1800 ppm

Toluene diisocyanate 0.02–0.2 ppm

-Tolidine 1 –30 ppm

Tributylamine 2.5 –50 ppm

1,2,4-Trichlorobenzene *

Trichlorotoluene *

Trichloroethane 50–600 ppm

Trichloroethylene 2 –250 ppm

50–500 ppm

Trichlorofluoromethane 100–1400 ppm

Trichloronitromethane 1 –15 ppm

1,2,3-Trichloropropane *

1,1,2-Trichloro-1,2,2-trifluoroethane *

Triethylamine 5 –60 ppm

Triethylene diamine *

Triethylene tetratriamine *

Trifluorobromomethane *

Trimethylamine 0.25–3 ppm

5–60 ppm

Trimethyl benzene 10–100 ppm

Trimethyl phosphate *

Turpentine oil *

Undecane 10 –200 ppm

Vinyl acetate *

Vinyl bromide 0.7–300 ppm

Vinyl chloride 0.5 –30 ppm

1–50 ppm

100–3000 ppm

Vinyl ethyl ether 20 –300 ppm

Vinylidene chloride 2.5–25 ppm

Vinyl trimethoxy silane 100–1000 ppm

Water vapour 0.05–1 mg/l

0.5–18 mg/l

1–40 mg/l

White spirit 30–200 ppm

100–1600 ppm

Xylene (all isomers) 10 –400 ppm

Zinc chromate 0.2 –1 mg/m

* Consult with supplier.

Table 10.18(a) Cont’d

Substance Measuring range

TOXIC PARTICULATES 351

352 MONITORING TECHNIQUES

Table 10.18(b) Dräger tubes for long-term measurements – with pump

Dräger tube Range of measurement for

maximum period of use

Acetic acid 5/a-L 1.25–40 ppm

(4 hr)

Acetone 500/a-L 63–10 000 ppm

(8 hr)

Ammonia 10/a-L 2.5 –100 ppm

(4 hr)

Benzene 20/a-L 5 –200 ppm

(4 hr)

Carbon dioxide 1000/a-L 250 –6000 ppm

(4 hr)

Carbon disulphide 10/a-L 1.3–100 ppm

(8 hr)

Carbon monoxide 10/a-L 2.5 –100 ppm

(4 hr)

Carbon monoxide 50/a-L 6.3 –500 ppm

(8 hr)

Chlorine 1/a-L 0.13 –20 ppm

(8 hr)

Ethanol 500/a-L 63 –8000 ppm

(8 hr)

Hydrocarbon 100/a-L 25–3000 ppm

(4 hr)

Hydrochloric acid 10/a-L 1.3 –50 ppm

(8 hr)

Hydrocyanic acid 10/a-L 1.3 –120 ppm

(8 hr)

Hydrogen sulphide 5/a-L 0.63 –60 ppm

(8 hr)

Methylene chloride 50/a-L 13 –800 ppm

(4 hr)

Nitrogen dioxide 10/a-L 1.3 –100 ppm

(8 hr)

Oxides of nitrogen 5/a-L (NO + NO

) 1.3–50 ppm

(4 hr)

Oxides of nitrogen 50/a-L (NO + NO

)13–350 ppm

(2 hr)

Perchloroethylene 50/a-L 13 –300 ppm

(4 hr)

Sulphur dioxide 5/a-L 1.25 –50 ppm

(4 hr)

Sulphur dioxide 2/a-L 0.5 –20 ppm

(4 hr)

Toluene 200/a-L 25 –4000 ppm

(8 hr)

Trichloroethylene 10/a-L 2.5–200 ppm

(4 hr)

Vinyl chloride 10/a-L 1 –50 ppm

(10 hr)

Table 10.20 Examples of chemicals for which paper-tape colorimetric instruments are available

Ammonia Hydrogen selenide

Arsine Hydrogen sulphide

Chlorine Isocyanates

Diborane Nitrogen dioxide

Germane

-Phenylene diamine

Hydrazines Phosgene

Hydrogen chloride Phosphine

Hydrogen cyanide Silane

Hydrogen fluoride Sulphur dioxide

Table 10.19 Selected sources of inaccuracy in use of colour detector tubes

Failure to break both ends of the sealed tube before insertion of the tube into the pump housing.

Insertion of the tube incorrectly into the pumphousing (the correct direction is indicated on the tube).

Reuse of previously used tubes. It is advisable not to reuse tubes even if previous use indicated zero.

Leaks in sample lines, or insufficient time allowed to lapse between pump strokes when extensions are used.

Use of tubes beyond expiry of the shelf-life. Tubes should be stored under refrigerated conditions but allowed to warm to

ambient temperature prior to use.

III-defined stain format because it is irregular, diffuse or has failed, i.e. not at right angles to tube wall. (This can be caused

by poor quality of granular support medium used by manufacturer.) It is advisable to read the maximum value indicated.

Use of tubes under conditions of temperature, pressure or humidity outside the range of calibration.

Blockages or faulty pumps. Pumps should be checked periodically as instructed by the manufacturer. They can be calibrated

using rotameters or bubble flowmeters. Unless pumps possess a limiting orifice they should be calibrated with the air

indicator tube in position.

Misuse of the pump, e.g. incomplete stroke or wrong number of strokes.

Mismatch of tubes with type of pump.

Interference due to the presence of other contaminants capable of reacting with the tube reagent. This can result in over- or

under-estimation of concentrations. The former is the more likely and hence errs on the side of safety.

Tube blockage caused by airborne dusts, affecting the flow rate.

Table 10.18(c) Direct-indicating Dräger diffusion tubes – no pump required

Substance Measuring range Max. operating time (hours)

Acetic acid 10/a-D 10–200 ppm × hr 8

Ammonia 20/1-D 20–1500 ppm × hr 8

Butadiene 10/a-D 10–300 ppm × hr 8

Carbon dioxide 500/a-D 500–20 000 ppm × hr 8

(1%/a-1) 1–30 vol % × hr 360

Carbon monoxide 50/a-D 50–600 ppm × hr 360

Ethanol 1000/a-D 1000–25 000 ppm × hr 8

Ethyl acetate 500/a-D 500–10 000 ppm × hr 8

Hydrochloric acid 10/a-D 10–200 ppm × hr 8

Hydrocyanic acid 20/a-D 20–200 ppm × hr 8

Hydrogen sulphide 10/a-D 10–300 ppm × hr 72

Nitrogen dioxide 10/a-D 10–2000 ppm × hr 24

Olefines 100/a-D 100–2000 ppm × hr 8

Perchloroethylene 200/a-D 200–1500 ppm × hr 8

Sulphur dioxide 5/a-D 5–150 ppm × hr 10

Toluene 100/a-D 100–3000 ppm × hr 8

Trichloroethylene 200/a-D 200–1000 ppm × hr 8

Water vapour 5/a-D 5–100 mg/l × hr 8

TOXIC PARTICULATES 353

354 MONITORING TECHNIQUES

particles of respirable dimensions from non-respirable fractions include horizontal elutriation and

centrifugation. Equipment for personal monitoring comprises a lapel-mounted filter holder connected

to a portable pump with a flow rate of about 3 litres/min. Respirable matter can be separated by

use of a small cyclone. In order to ensure uniformity of fractionation, smooth and constant flow

rates are essential. The dust collection and analytical stages are separate operations. For background

monitoring, miniaturization is unimportant and as a consequence equipment incorporates pumps

of higher flow rates, typically ≤100 1/min. This enables sampling times to be short and larger

samples to be obtained (e.g. for laboratory analysis). Both direct-reading and absolute methods

are available.

The main principles of instrument design are summarized in Table 10.23. In filtration, e.g. for

gravimetric analysis, selection of filter material (Table 10.22) requires careful consideration in

terms of application, strength, collection efficiency, compatibility with pump, water uptake, etc.

Humidity-controlled balance rooms, microbalances and careful handling techniques may be required.

Table 10.22 Examples of filter material for collection of particulates

Filter Material Application Characteristics

• Cellulose Washing of samples to High flowrates, low pressure

determine water soluble fraction drop, low impurity levels

or for ashing to determine

organic content

• Glass fibre High-flow samplers for High efficiencies, high flowrates,

gravimetric assessment high wet strength, good

temperature stability, low

pressure drop

• Mixed celluloses, e.g. nitrate, Microscopy (asbestos); metal Low levels of metal impurities;

ester content (by atomic absorption, oxidizable during digestion

atomic emission, fluorescence

and infra-red spectrometry)

• Polycarbonate Optical microscopy; organic Transparent grades available,

content non-hygroscopic, low ash

content, solvent resistant

• PTFE Sampling for HPLC or UV Inert, hydrophobic

analysis. PAHs

• PVC Gravimetric analysis, carbon Acid and alkali resistant; low

black, quartz, silica water pick-up

• Silver membrane Crystalline materials for X-ray Costly. High collection

diffraction efficiency. Uniform pore size

Table 10.21 Considerations when using instruments with catalytic detection

Portable instrument should be of explosion-proof design; fixed point systems may rely on remote sensing heads

For zero adjustment, place instrument in uncontaminated air or use activated charcoal filters to remove flammable vapours

Sources of error include:

Inadequate calibration

Drift due to age

Design not fail-safe (i.e. no indication of component failure)

Poisoning of Pellistor by, e.g., silicones, halocarbons, leaded petrol

Too high a sampling rate (causing cooling of the elements)

Sampling lines and couplings not airtight

Condensation of high-boiling-point components in the line between sample head and sensor

Hostile environment

Table 10.23 Particulates monitoring – principles of apparatus

Principle Examples Collection Sampling Collection Analysis Advantages

disadvantages

rate efficiency

(l/min) (%)

Impinger Midget impinger By bubbling Microscopy Aggregates broken up; only particles >1 µm collected. In wet

through liquid impingers particles must be water insoluble.

phase

Impactor 1. Konimeter Impaction on 60–100 Built-in Underestimates small particles,

gel-coated microscope overestimates large particles. Particles

disc Microscopy between 0.5 and 5.0 µm collected.

2. Cascade Impaction on 1–37

impactor 4 stages on (depending

glass disc on type)

3. Andersen Impaction in

sampler 8 stages onto Gravimetric or Instrument inflexible.

glass or metal chemical

discs

Electrostatic Casella thermal Deposition on 1–85 90–100 Microscopy Poor for large particles. Collection

or thermal precipitator glass slides or efficiency increases as particle size

precipitation discs decreases.

Filtration 1. Fibrous filter 1–50 85–100 Gravimetric or Fibrous filter good for gravimetric analysis

Depends on chemical for a range of particle sizes

particle size (fast and relatively easy).

values stated

2. Membrane for those Microscopy, Membrane filter good for microscopy

filter usually gravimetric or identification of particles and counting

encountered chemical where required.

Respirable 1. Hexhlet Fibrous filter 1–50 60–100 Gravimetric or Instrument must be kept horizontal for

dust (horizontal chemical sampling; relatively large quantities of

separation elutriator) dust collected in short period.

2. Casella Fibrous or Gravimetric, The only instrument for carrying out

cyclone membrane microscopy or personal respirable dust sampling.

filter chemical

3. Anderson Selective inlet 16.7 Gravimetric Can be used for unattended operations

sampler 2 dust fractions

(<10 µm and <2.5 µm)

Beta Impaction on Attenuation of Provides short- or long-term TWA (e.g. up

attenuation disc or beta radiation to 8 hr, depending on model) of dust or

filtration Direct reading fume mass concentration.

Suitable for unattended automated continuous methods.





















Photometry 1. Number Light scattered Gives automatic particle sizing but accuracy

concentration, on to a only guaranteed if calibrated for

e.g. Royco photomultiplier particulate of interest.

Direct reading

2. Mass Light scattered Very versatile – only accurate continuous

concentration onto a long-term mass monitoring instrument;

e.g. Simslin photomultiplier sample may also be collected on a filter.

Direct reading Suitable for automated operations.

Piezoelectric Electrostatic

frequency of Change in Unsuitable for ambient air monitoring.

crystal. Direct resonant

reading frequency

Table 10.23 Cont’d

Principle Examples Collection Sampling Collection Analysis Advantages

disadvantages

rate efficiency

(l/min) (%)

Table 10.24 Selected British Standards relating to ambient air pollution measurements

British Standard Subject Method

BS 893 Particulate matter in ducts

BS 1747 Deposit gauges

Particulate matter

Sulphur dioxide Thorin spectrophotometry

Directional dust gauges

Sampling equipment for determination of

gaseous sulphur

Nitrogen dioxide in ambient air Modified Griess–Salzman method

Nitrogen oxides in ambient air Chemiluminescence

Sulphur dioxide in ambient air Tetrachloromercurate/pararosaline

Black smoke index in ambient air

Ozone Chemiluminescence

Particulate lead in aerosol Collected on filter with atomic

absorption spectrometry

BS 1756 Flue gases General methods

BS 2811, 2742 Smoke monitoring

BS 3048 Flue gases Continuous and automatic

BS 3405 Particulate matter including grit and dust

BS 3406 Particle size distribution Various including microscopy

BS 4995 Gas mixtures Preparation

BS 5243 Airborne radioactive gases and Various

particulates

BS 5343 Long-term gas detector tubes

BS ISO 6768 Nitrogen dioxide Modified Griess–Salzman

BS ISO 10312 Asbestos Direct-transfer transmission

Electron microscopy

BS ISO 10498 Sulphur dioxide Ultra-violet fluorescence

BS ISO 10473 Particulate mass on filters Beta-ray absorption

BS ISO 12884 Polycyclic aromatic hydrocarbons Collection of filters with gas

chromatography/mass

spectrometry

BS ISO 13794 Asbestos Indirect-transfer transmission

Electron microscopy

BS ISO 13964 Ozone Ultra-violet photometry

BS ISO 14965 Non-methane organics Flame ionization

BS ISO 16000 Indoor formaldehyde and other carbonyl Active and diffusive sampling

compounds

BS EN 12341 Suspended matter Reference and field methods

BS EN 13528 Gases and vapours Diffusive samplers

Official methods

Regulatory and advisory bodies publish methods for ambient air analysis such as those issued by

the British Standards Institute and the US Environment Protection Agency (Tables 10.24 and

10.25, respectively). Methods for assessment of workplace air are published by the Health and

Safety Executive. Some of these are generic methods (Table 10.26) whilst others are compound

specific (Table 10.27). Examples of other official methods for monitoring workplace air quality

are those published by the British Standards Institute (Table 10.28), and the US National Institute

of Occupational Safety and Health (Table 10.29). Table 10.30 provides additional guidance on

analytical techniques for a selection of substances.

OFFICIAL METHODS 357

358 MONITORING TECHNIQUES

Table 10.25 Selected EPA standard methods for air monitoring (Code of Federal register-protection of the environment

section, 40)

Subject Method reference (see original reference)

Part 60 Appendix A

• Various measurement techniques for sample and velocity 1, 1A, 2, 2A, 2B, 2C

from stationary sources, stacks, ducts, pipes

• CO

oxygen, excess air, dry molecular weight 3

• O

and CO

• Moisture from stacks 4

• Particulate 5

– stationary sources 5A

– asphalt 5B

– non-sulphuric acid matter 5D

– from positive pressure fabric filters 5E

– wool fibre-glass 5F

– non-sulphate matter 5G

– wood heaters 5H

– in-stack filtration method 17

• SO

from stationary sources 6

– fossil fuel 6A, 6B

– stationary sources 6C

• NO

from stationary sources 7 (various methods 7A–7E)

• Sulphuric acid mist and SO

from stationary sources 8

• Visual opacity 9

• CO from stationary sources 10, 10A, 10B

• H

S (refineries) 11

• Inorganic lead 12

• Total fluoride 13A, 13B

• Fluoride (aluminium plants) 14

• H

S, COS, CS

• Total reduced sulphur (sulphur recovery plants) 15A

• Sulphur 16

• Total reduced sulphur (stationary sources) 16A, 16B

• Gaseous organics 18

• SO

, particulates and NO

emission rates 19, 20

• Volatile organic leaks 21

• Visual assesssment of fugitive emissions from material sources 22

and smoke from flares

• Chlorinated dioxins and dibenzofurans 23

• Volatile content, water, density, volume and weight of surface coatings 24, 24A

• Total gaseous organics 25, 25A, 25B

• HCl 26

• Vapour tightness of gasoline delivery tanks 27

Part

61 Appendix B (Hazardous air pollutants)

• Particulate and gaseous Hg 101, 101A, 102

• Beryllium 103,104

• Vinyl choride 106

• Gaseous and particulate arsenic 108

• Benzene 110

• Polonium-210 111

• Radionuclide 114

• Radon-222 115