06 Week Chemical Hazards 1

Occupational Health and Safety
Dr. MÜGE ENSARİ ÖZAY

Chemical hazards:
Chemical hazards: classification and labelling
Chemical hazards, sampling and analysis methods
Particles, fibres, fumes, and mists
Chemical hazards: classification and labelling
Relevant legislation
• The Chemical (Hazard Information and Packaging for Supply) Regulations 2009 (known
as CHIP). CHIP requires that substances and mixtures placed on the market are classified,
labelled and packaged appropriately.
Under CHIP, information on hazards is communicated to users by means of symbols and
risk phrases.
CHIP is in the process of being replaced by a new European Regulation on Classification,
Labelling and Packaging of Substances and Mixtures (CLP Regulation).
• The CLP Regulation was introduced in 2009; will fully replace CHIP in June 2015. The
same classification and labelling system will be used worldwide.
Information on hazards will be communicated to users by hazard symbols and hazard
statements
Classification and labelling of specific substances
• Agreed classification and labelling requirements for substances are contained in Annex VI of the CLP
regulation.
• In the UK, substances hazardous to health are defined under the Control of Substances Hazardous to
Health (COSHH) Regulations 2002. A substance hazardous to health need not be a single substance, but also
includes mixtures of compounds, micro-organisms, allergens, etc.
• A new European Law on chemicals, Registration, Evaluation, Authorization and Restriction of Chemicals
(REACH), came into force on 1 June 2007 (see b p. 554). Under REACH it is a requirement for manufacturers or
importers of substances to register with the Central European Chemical Agency (ECHA). REACH gives greater
responsibility to industry to manage the risks from chemicals and to provide safety information on
substances. For each substance reported in the following pages of this chapter:
• Only the classification and labelling according to the CLP Regs is reported, comprising hazard class and
category (e.g. carc 1B, See Table 2.1) and hazard statement (e.g. H350)
• Classifi cation and labelling entries are for ‘health effects’ only. Those relating to ‘physicochemical
properties’ and ‘environmental effects’ are not reported here, nor are precautionary statements.
Classification and labelling of specific substances
Further information
• http://www.hse.gov.uk/reach/index.htm
• http://www.hse.gov.uk/chip/index.htm
• http://echa.europa.eu/clp_En.asp
• http://echa.europa.eu/reach_En.asp
• All MDHS sampling and analysis methods are available at:
http://www.hse.gov.uk/pubns/mdhs/index.htm
Chemical hazards: sampling and analysis methods
Pollutant types
Airborne chemical pollutant types can be
categorized by their physical form e.g.
fumes, fibres, vapours, etc. Table 2.2 shows
definitions of chemical hazard types
(physical form) together with processes
that generate them.
Pollutant types
Table 2.3 provides a summary of methods for sampling and analysing common chemical pollutants
types. These sampling methods are based on the Methods for the Determination of Hazardous
Substances (MDHS) published by the HSE.
Table 2.3 summarizes the methods for collecting different airborne chemicals.
Coal dust
General substance information
• Exposure to coal dust is regulated under the Coal Mines (Control of Inhalable Dust) Regulations
(CIDR) 2007
• There is no allowance for the effect of respiratory protective equipment (RPE) to be taken in to
account in deciding whether an exposure control limit has been exceeded
• CIDR requires control of inhalable dust exposure and compliance with exposure control limits (ECL)
for respirable dust
• ECL: respirable dust averaged over a reference period of a working week of 40 h:
• respirable dust 3.0mg/m 3
• quartz 0.3mg/m 3
• Physical properties: carbonaceous mineral dust with other minerals, notably crystalline silica
(quartz). Quartz may comprise 10% of the respirable mass. Composition and physical properties (e.g.
hardness) are highly variable.
Coal dust
CLP classification and labelling
Currently no classification.
Uses/occurrence
Exposure occurs during mining and processing of coal.
Coal dust
Key health effects
• Pneumoconiosis: the quartz content of freshly generated particles accelerates progression of the
disease (Crystalline silica (quartz); Silicosis)
• Emphysema and chronic bronchitis (see b p. 212, Chronic obstructive pulmonary disease)
• Health surveillance is mandatory under CIDR for ‘significantly exposed’ workers and should
include respiratory symptom questionnaires (including smoking history), spirometry and chest X-
rays.
• Health records should be kept in a suitable form for 40yrs.
Coal dust
Measurement
• MDHS 14/3 Pumped dust sample (total inhalable or respirable sampling head) on to filter,
gravimetric analysis
• MDHS 101 Pumped respirable dust sample on to filter, gravimetric analysis followed by
assessment of quartz content by infrared radiation (IR) spectroscopy or X-ray diffraction (XRD)
• Note: need to determine the respirable quartz content of all samples unless the total respirable
dust in the sample is less than the time-weighted average (TWA) exposure control limit for quartz.
Coal dust
HSE publications
• EH59 Respirable crystalline silica. ISBN 0717614328.t
• HSE L145 (2007). The coal mines (control of inhalable dust) regulations 2007 . HSE, Sudbury.
Available at: http://www.hse.gov.uk/pubns/priced/l145.pdf
• Ionizing Radiation (Medical Exposure) Regulations 2000 . ISBN 0 11 099131 3.
Cotton dust
• Cotton dust is defined by the HSE as ‘the cellulose fibre that grows inside the seed pods (or
bulbs) of the cotton plant’. For purposes of exposure monitoring, HSE defines cotton dust as ‘the
handling of raw and waste cotton including blends containing raw or waste cotton’
• The following are excluded:
• dust from weaving, knitting, braiding, and subsequent processes
• dust from bleached or dyed cotton
• dust from finished articles, e.g. garments
• Occupational exposure limit (as inhalable dust): workplace exposure limit (WEL), 8h TWA of
2.5mg/m 3
• Physical properties: organic fibrous matter.
Cotton dust
Currently no classifi cation.
Uses/occurrence
Manufacture of cotton and cotton-based products.
Key health effects
Byssinosis (‘cotton worker’s lung’), an asthma-like condition thought to
be immunological in origin, although the causal agent is unknown
Measurement
MDHS 14/3 Pumped inhalable dust sample on to filter, gravimetric.
Flour dust
• Defined by HSE as ‘finely ground particles of cereals or pulses (including contaminants) that
result from any grinding process and from any subsequent handling and use of that “flour”. Any
additives are included only where they have been added to the final product mix’
• Occupational exposure limit (as inhalable dust): WEL, 8h TWA of 10mg/m 3 ; short-term exposure
limit (STEL) of 30mg/m 3
• Limit values are currently under review by HSE
• Physical properties: organic dust may be contaminated with bacterial debris.
Flour dust
Uses/occurrence
Exposure occurs widely across the food industry in bakeries and prepared foods. Key tasks include
handling raw material (bagging, weighing, sieving, etc.) product mixing, production, and cleaning
and maintenance.
Flour dust
Key health effects
Acute effects
• Eye irritation
• Irritation of mucous membranes
• Asthma: flour and grain dust currently account for 8% of the incidence of occupational asthma.
Although not clearly understood, high short term exposures are thought to be of significance
Measurement
• MDHS 14/3 Pumped inhalable dust sample on to filter, gravimetric analysis.
Grain dust
• Defined by HSE as ‘dust arising from the harvesting, drying, handling, storage or processing of
wheat, oats, maize and rye, including contaminants’
• Occupational exposure limit (as inhalable dust): WEL, 8h TWA of 10mg/m 3
• Physical properties: organic dust may be contaminated with bacterial debris.
Currently no classifi cation.
Uses/occurrence
Exposure occurs in fl our mills, animal feed manufacture/handling, and the
transport of bulk grain.
Grain dust
Key health effects
• Acute effects: eye irritation, irritation of mucous membranes
• Asthma: flour and grain dust currently account for 8% of the incidence of occupational asthma
(Occupational asthma and rhinitis)
• Extrinsic allergic alveolitis (farmer’s lung) may occur where fungal spores are present
(Hypersensitivity pneumonitis).
Measurement
MDHS 14/3 Pumped inhalable dust sample on to filter, gravimetric analysis.
Wood dust
• Wood dust is designated as hardwood (from deciduous trees) or softwood (from coniferous trees)
• Occupational exposure limit, hardwood and softwood dust (as inhalable dust): WEL, 8h TWA of
5mg/m 3
• Limit values are currently under review
• Physical properties: organic dust
• May contain other matter present in wood products, e.g. binders,
coatings.
Wood dust
Uses/occurrence
Exposure may occur in any process involving the working of wood, chipboard,
and fibreboard, including forestry, sawmilling, joinery, construction,
and furniture making. The type of activity determines the nature of exposure
(work intensity, type of dust, magnitude of exposure, and particle
size distribution).
Measurement
• MDHS 14/3 Pumped inhalable dust sample on to filter, gravimetric analysis.
Wood dust
Key health effects
• Dermatitis: may cause contact or allergic dermatitis
• Asthma: many reports of asthmatic and other respiratory symptoms
• Other respiratory effects from chronic exposure:
• alteration in nasal mucosa
• reduced mucociliary clearance (furniture industry)
• anosmia
• Cancer: carcinogenic risk appears to be confined to workers in the
furniture industry with heavy use of hardwoods
• excess adenocarcinoma of nose and sinus cavity
• some evidence of excess lung cancer but confounding effects of
(a) exposure to other occupational agents and cigarette smoke and
(b) high historical exposures.
Crystalline silica (quartz)
Occupational exposure limit
• Silica crystalline (respirable): WEL, 8h TWA of 0.1mg/m 3 . Limit to be kept under review by HSE
• Silica, amorphous, (inhalable): WEL, 8h TWA of 6.0mg/m 3
• Silica, amorphous (respirable): WEL, 8h TWA of 2.4mg/m 3 .
Uses/occurrence
Most important sources of exposure are quarries, mines, ferrous foundries, construction, stone
masonry, and the ceramics, heavy clay, and brick-making industries.
Crystalline silica (quartz)
Key health effects
• Silicosis: usually slow onset over many years or ‘acute silicosis’ following high levels of exposure
over 1–2yrs
• Lung cancer: IARC Group 1, carcinogenic to humans. Possible synergistic effect with smoking
• Other respiratory effects: some evidence that exposed workers may have an excess of
tuberculosis, bronchitis, and emphysema. The role of smoking and the causal mechanisms are
unclear
• Other effects: an excess of autoimmune, immunological, and renal disease has been reported.
Measurement
MDHS 101 Pumped respirable dust sample on to filter, analysis by IR spectroscopy or XRD.
Asbestos
• Asbestos is a group of ‘naturally occurring silicate minerals’ comprising crocidolite, amosite,
chrysotile, fibrous actinolite, fibrous anthophyllite, and fibrous tremolite, or mixtures containing these
• Exposure is regulated by the Control of Asbestos at Work Regulations (CAR) 2006 (see b p. 540,
Control of Asbestos Regulations 2006), and associated ACoPs. L143 and L127. CAR prohibits the
importation, supply, and use of all form of asbestos
• Control limits:
• control limit 0.1fibre/cm 3 (equivalent to 0.1f/mL; all asbestos types).
• STEL of 0.6fibre/mL over 10min
• personal exposure (control) limits cover 10min and 4h periods.
Exceeding a 12wk ‘Action Level’ triggers extra provisions under CAR including health surveillance
• clearance sampling inside the enclosure is required after asbestos removal.
Asbestos
CLP classifi cation and labelling
Carcinogen (Carc) (1A), STOT/RE (1); H350, 372.
Uses/occurrence
• Formerly lagging for pipes and boilers; cement pipes, sheets, and tiles
• Now mainly encountered in demolition and renovation operations.
Key health effects (see b p. 214).
• Asbestosis,
• mesothelioma,
• lung cancer.
Asbestos
Measurement
Surveys should be carried following the HSE guidelines
• HSG 264: covers survey planning, sampling, and assessment of asbestos
containing materials, quality assurance, and survey reports
• HSG248: provides information on air and bulk asbestos sampling.
Pumped dust sample using specified cowled sampler onto filter, filter visualization by light
microscopy and counting fibres of length >5μm, width <3μm, and a length/width ratio of at least
3:1.
Machine-made mineral fibre
• Machine-made mineral fibre (MMMF): machine-made vitreous (silicate) fibres, e.g. mineral wools
(rock and glass wool) with alkaline oxide and alkali earth oxide content greater than 18% by weight.
Refractory ceramic fibres and special purpose fibres have a separate WEL and classification
• Occupational exposure limit: WEL, 8h TWA of 5mg/m 3 and 2 fibres/mL.
except refractory ceramic fibres and special purpose fibres; WEL, 8h TWA of 5mg/m 3 and 1
fibres/mL)
• Physical properties: individual fibres have a diameter of 10 μ m, with median diameter of 3–4 μ m.
Majority of airborne MMMF clouds have a median diameter of <1 μ m
• MMMF: Carc (2), skin irrit (2); H351, 315
• Refractory ceramic fi bres: Carc (1B), Skin irrit (2); H350i, 315.
Uses/occurrence
• MMMF materials have excellent thermal and acoustic insulation, as well as fireproofi ng, properties,
and are widely used in commercial and residential property and in industry
• MMMF materials are highly workable, and exposure may occur during fitting or removal. Depending
on the application, and whether materials are bonded or unbonded, preformed or applied in situ ,
exposure may be predominantly in the form of relatively coarse matted fragments or as respirable
fibres; hence the dual WEL.
Key health effects
• Irritant: highly irritant to the eyes and skin
• Cancer: evidence for excess lung cancer is equivocal; may be partly
dependent on particle size distribution.
Measurement
Gravimetric
• MDHS 14/3 Pumped inhalable or respirable dust sample on to filter, gravimetric
• Airborne fibre concentration
• MDHS 59 Pumped, non size-selective dust sample on to filter, filter visualization, fibre counting by
phase- contrast light microscopy. Fibre defi ned as particles length >5μm, width <3μm, aspect ratio
>3:1.
Diesel engine exhaust emissions
• Diesel engine exhaust emissions (DEEE) are a complex mixture of gases, vapours and submicron
particulate matter emitted from diesel engines
• Occupational exposure limit: none
• The German MAC value of 100μg/m 3 for elemental carbon may be useful as a guidance value
• Physical properties: gases include a wide range of compounds, including acrolein, formaldehyde,
oxides of nitrogen, and sulphur dioxide (the latter much reduced by use of low sulphur fuel).
Particulate matter is comprised of a carbonaceous core (elemental carbon) with adsorbed semi-
volatile organics, including polycylic aromatic hydrocarbons (PAHs) and hydrocarbon species (organic
carbon).
• Currently no classification for DEEE under CLP Regulations. However, IARC classify diesel engine
exhaust as carcinogenic to humans (Group 1), based on suffi cient evidence that exposure is associated
with an increased risk of lung cancer.
• Diesel fuel (liquid: CAS no.68334-30-5): Carc (2), Asp tox (1), Sk irrit (2), Acute tox 94). STOT RE(2);
H351, 304, 325, 332, 373.
Uses/occurrence
Exposure arises from work with road vehicles (garages, test centres, bridge or motorway toll booths)
and off-road vehicles (mines, manufacturing and distribution industry, construction).
Key health effects
• Lung cancer: plausible mechanistic basis for diesel fumes as a carcinogen,
but epidemiological evidence is weak, confounded by poor exposure
assessment and co-exposure to cigarette smoke and asbestos
• Other respiratory effects: some evidence of a cross-shift decrement in
lung function
• Irritation of mucous membranes, particularly the throat.
Measurement
• It is difficult to determine which component should be measured to represent exposure to DEEE.
One method favoured is to collect airborne diesel soot using a respirable cyclone sampler on to a
quartz filter. The filter is then analysed for elemental carbon (EC), which is a good surrogate measure
for DEEE
• Levels of carbon dioxide (CO2) above 1000ppm 8-h TWA in the workplace, may indicate poorly
maintained or faulty control systems
• Respirable dust levels can be measured to assess the particulate exposure. However, the levels
measured will include particulates from all sources and not just the DEEEs. NIOSH 5040 pumped
submicron sample on to filter in single-stage impactor, elemental carbon analysis.
Rubber process dust/fume
• HSE have assigned functional definitions to rubber dust and fumes:
• rubber dust—‘dust arising in the stages of rubber manufacture where ingredients are handled,
weighed, added to or mixed with uncured material or synthetic elastomers’
• rubber fume is ‘fume evolved in the mixing, milling and blending of natural rubber and rubber or
synthetic elastomers, or of natural rubber and synthetic polymers combined with chemicals, and in
the processes which convert the resultant blends into finished products or parts thereof, and including
any inspection procedures where fume continues to be evolved’
• Occupational exposure limit:
rubber process dust —WEL, 8h TWA of 6mg/m 3
rubber fume —WEL, 8h TWA o f 0.6mg/m 3 ; this limit relates to the cyclohexane soluble material
• Where other substances are present in the dust/fume, any WELs for such substances also applies.
Currently no classification for rubber fume.
Uses/occurrence
Exposure may occur in the production of vehicle tyres, components in the automotive industry and a
range of other industries, footwear, and domestic appliances.
Measurement
• Rubber dust—MDHS 14/3 Pumped inhalable dust sample on to filter, gravimetric analysis
• Rubber fume—MDHS 47/2 Pumped inhalable dust sample on to filter, cyclohexane extraction,
gravimetric analysis.
Key health effects
• Cancer: workers in rubber industry have a risk of excess cancers at a number of sites—bladder, lung,
stomach, colon, prostate, liver, and oesophagus. There is a lack of epidemiological evidence to
support a causal link at all sites. In particular, complex exposures occurring in the industry (solvents,
plasticizers, accelerators, etc., in addition to polymers) are poorly characterized. Currently, IARC have
concluded that ‘sufficient’ evidence exists only for leukaemia and bladder cancer
• Respiratory effects: emphysema, reduction in lung function, dyspnoea, and chest tightness have all
been reported. Cases of respiratory sensitization are attributed to co-exposure to isocyanates
• Dermatitis: there are several reports of contact dermatitis among rubber workers. Eczema and
vitiligo have also been reported
• Reproductive effects: studies of pregnancy outcome are inconclusive and are further limited by lack
of exposure data.
Rosin-based solder flux fume
• CAS No. 8050–09–7
• Occupational exposure limit. Rosin-based solder flux fume:
• WEL, 8h TWA of 0.05mg/m 3
• STEL of 0.15mg/m 3 .
2 Note: compliance with WELs for other components of the fume is
required as appropriate (e.g. cadmium in silver soldering).
Rosin-based solder flux fume
Uses/occurrence
Rosin (colophony) is widely used in solder fluxes in the electronics and other industries (also in paper
products, adhesives, paints, varnishes, printing inks, plasticizers, cosmetics, and medical devices).
Alternatives to rosinbased fluxes exist, and where these are used, the WEL is not applicable.
Key health effects
• Asthma: rosin is the third most common cause of occupational asthma in the UK (Occupational
asthma and rhinitis)
• Other respiratory effects: evidence for reductions in respiratory function are equivocal
• Dermatitis
Measurement
MDHS 83/2 Measured volume of air drawn through a membrane filter in a sampling head (non-size
selective). The filter is desorbed, the resin acids derivatized and then analysed by GC with FID.
Welding fume
• CAS No. 8050–09–7
• Occupational exposure limit: none for total welding fume
2 Compliance with WELs for components of the fume (metals and inorganic gases) is required as
appropriate (e.g. Cr VI , Ni, Mn, O3).
• Check WELs for fume components.
Measurement
• BS EN ISO 10882–1:2011 Sampling of air borne particles (welding fume).
Welding fume
Uses/occurrence
• The most important substrates are mild and stainless steel, and their
alloys, and aluminium and its alloys. The main types of welding are:
• manual metal arc (MMA)
• flux cored arc (FCA)
• metal inert gas (MIG)
• tungsten inert gas (TIG)
• The composition of fume is influenced by the many process factors including material to be welded,
composition of the consumable electrode /flux and the welding technique. In general, MMA and FCA
are more likely to produce high levels of fume than MIG or TIG welding. The most important
applications are in engineering (e.g. boiler, tank, and vessel assembly), shipbuilding, and construction.
Welding fume
Key health effects
• Lung cancer: welding of stainless steel has been associated with an increased risk of lung cancer.
However, HSE consider there is no significant risk under present conditions, i.e. in the absence of high
historical exposures
• Asthma: mainly due to welding stainless steel (exposure to Cr VI )
• Chronic obstructive pulmonary disease
• Acute effects: irritation of eyes and throat, tightness in the chest at higher exposures, metal fume
fever
• Asphyxia: asphyxiant properties of inert shield gases (Argon) in confined spaces should also be
considered in MIG and TIG welding.
Oil mist (metal working fluids)
• Metal working fluids (MWFs) are neat oils or water-based fluids used for lubrication and cooling
when machining metals
• Occupational exposure limit: currently no classifiation
• Physical properties: variable composition and viscosity.
CLP classifi cation and labelling
Uses/occurrence
Exposure to MWFs occurs via inhalation, through direct contact with unprotected skin, and through
cuts and abrasions. The cutting operation may generate a mist from the fluid, and splashes may result
in dermal exposure. Exposure to micro-organisms, including endotoxins, and antimicrobials may also
occur.
Key health effects
• Dermatitis: irritant and allergic contact dermatitis have been widely
reported in exposed workers (see b p. 242, Dermatitis 1)
• Cancer: excess cancers of the larynx, rectum, pancreas, skin, scrotum,
and bladder have been reported in exposed workers. However, high
historical dermal and inhalation exposures have now been reduced
because of improved control methods and the use of highly refined
MWFs that are much reduced in carcinogenic substances (e.g.
polycyclic aromatic hydrocarbons)
• Respiratory conditions: asthma, extrinsic allergic alveolitis, chronic
bronchitis, and acute airway irritation have all been reported (see b
p. 198, Occupational asthma and rhinitis, b p. 206, Hypersensitivity
pneumonitis).
Measurement
• Mineral oil-based MWFs of viscosity greater than 18mm 2 /s—- MDHS 84
Pumped inhalable sample on to filter, gravimetric (after subtraction of
cyclohexane soluble matter)
• Water-mix MWFs—MDHS 95/2 (elemental marker method) Airborne
inhalable pumped sample (collected on a fi lter) and a sample of oil
(from sump) are both analysed using a suitable marker (sodium,
potassium or boron) by, atomic absorption spectroscopy (AAS) or
inductively coupled plasma spectrometry (ICP).
Thank you
Safety first…

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Occupational Health and Safety

Dr. MÜGE ENSARİ ÖZAY

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