Investigation of Potencial Exposure To Carcinogens and Respiratory Sensitisers During Thermal Processing of Plastics

Health and Safety
Executive
Investigation of potential exposure to

carcinogens and respiratory sensitisers
during thermal processing of plastics
Prepared by Health and Safety Laboratory
for the Health and Safety Executive 2010
RR797
Research Report
Health and Safety
Executive

John Unwin, Chris Keen & Matthew Coldwell
Health and Safety Laboratory
Harpur Hill
Buxton
Derbyshire
SK17 9JN
This work was carried out in support of HSE’s FIT3 Disease Reduction Programme Cancer Project’s aim to
develop a strategy to reduce the incidence of occupational cancer in Great Britain. As part of this strategy,
HSE has initiated research that aims to deliver evidence that will help to identify carcinogens of concern,
improve control of exposure to carcinogens at work and provide a baseline for evaluating strategies for
intervention.
Earlier, in 2005-7, HSL characterised the exposure profiles of a selected group of occupational carcinogens
and determined baseline exposures with which to compare future levels. The project identified the potential
for exposure to carcinogens in the thermoplastic processing and finishing industries however there was
a scarcity of published quantitative exposure data. A number of laboratory and other studies had shown
that carcinogens could be generated from the processing of thermoplastics in some situations but further
investigation was required to establish the levels of exposure that may originate in the industrial setting.
The report describes the results of sampling for carcinogens and respiratory sensitisers at ten large
processing plants. The measurement strategy used was sufficiently broad in scope to take into account
the presence of respiratory sensitisers and respiratory irritants as well as carcinogens. The findings
demonstrate that compliance with HSE guidance achieves adequate prevention and control of exposure in
the common thermoplastic processes considered. This report will be helpful to smaller plants operated by
small and medium enterprises who undertake the same processes albeit on a smaller scale.
This report and the work it describes were funded by the Health and Safety Executive (HSE). Its contents,
including any opinions and/or conclusions expressed, are those of the authors alone and do not necessarily
reflect HSE policy.
HSE Books
© Crown copyright 2010
First published 2010
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or by e-mail to hmsolicensing@cabinet-office.x.gsi.gov.uk
ii
CONTENTS
1 INTRODUCTION ..............................................................................................1
2 ENGAGEMENT OF INDUSTRY STAKEHOLDERS .....................................5
3 SITE VISITS ......................................................................................................7

3.1 Range of sites visited....................................................................................7
3.2 Measurement protocol ..................................................................................7
4 RESULTS..........................................................................................................9
4.1 Site 1 – PVC compounding and extrusion...................................................9
4.2 Site 2 – PE and PP extrusion and blown film............................................10
4.3 Site 3 – PE and recycled PE extrusion and blown film.............................11
4.4 Site 4 – PE, PP, PS recycling and extrusion.............................................12
4.5 Site 5 – PET extrusion and blow injection moulding.................................13
4.6 Site 6 – ABS vacuum forming of sheet......................................................14
4.7 Site 7 – PVC extrusion................................................................................15
4.8 Site 8 – EPS blow moulding and hot wire cutting .....................................16
4.9 Site 9 - PVC/chlorinated PVC alloy thermoforming ..................................17
4.10 Site 10 – PVC welding ................................................................................18
5 DISCUSSION..................................................................................................20
5.1 Materials and processes investigated .......................................................20
6 CONCLUSIONS..............................................................................................23
6.1 Main findings from the measurement survey ............................................23
6.2 Adequacy of Control Measures..................................................................23
7 REFERENCES................................................................................................25
8 APPENDIX 1 – ADDITIVES AND DEGRADATION PRODUCTS.............27
9 APPENDIX 2 - AIR MONITORING RESULTS.............................................30
10 APPENDIX 2 - SAMPLING AND ANALYTICAL TECHNIQUES............40

10.1 Introduction ..................................................................................................40
10.2 Low volume sampling .................................................................................40
10.3 High volume sampling ................................................................................40
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iv
EXECUTIVE SUMMARY
This work was carried out in support of HSE’s FIT3 Disease Reduction Programme Cancer
Project’s aim to develop a strategy to reduce the incidence of occupational cancer in Great
Britain. As part of this strategy, HSE has initiated research that aims to deliver evidence that
will help to identify carcinogens of concern, improve control of exposure to carcinogens at work
and provide a baseline for evaluating strategies for intervention.
Earlier, in 2005-7, HSL characterised the exposure profiles of a selected group of occupational
carcinogens and determined baseline exposures with which to compare future levels. The
project identified the potential for exposure to carcinogens in the thermoplastic processing and
finishing industries however there was a scarcity of published quantitative exposure data. A
number of laboratory and other studies had shown that carcinogens could be generated from the
processing of thermoplastics in some situations but further investigation was required to
establish the levels of exposure that may originate in the industrial setting.
This study will also inform a parallel programme of work on respiratory disease because the
measurement strategy used was sufficiently broad in scope to take into account the presence of
respiratory sensitisers and respiratory irritants as well as carcinogens.
Objectives
• To make relevant industry contacts and scope out key areas of the thermoplastic
processing to select a suitable number of workplaces to visit
• To investigate the selected sites and carry out screening measurements for carcinogens
and respiratory sensitisers
• Carry out occupational hygiene assessments for each process investigated.
• To assess the analytical data and determine the potential for exposure to carcinogens
and respiratory sensitisers across the thermoplastics processing sector.
Main Findings
• The levels of carcinogens detected in the process fume at the sites investigated were
found to be either low or not detectable.
• Where low levels of carcinogens or potential respiratory sensitisers were found these
were at concentrations 2 – 3 orders of magnitude below any respective WEL.
• The maximum concentrations of carcinogens found at the sites visited were: benzene
(R45) 11 ppb; formaldehyde (R40) 9 µg/m3; naphthalene (IARC 2B) < 100 ng/m3; and,
other carcinogenic polycyclic aromatic hydrocarbons (IARC 1, 2A and 2B) all < 1
ng/m3.
• All substances detected in this study were measured at levels below 10% of their
respective WEL, demonstrating the low levels of process fume encountered.
• The low levels of total inhalable particulate measured (values from all sites were below
1.15 mg/m3) and the low concentration of all other substances measured, demonstrates
v
the low levels of fume generated and the effective temperature control of the respective
thermal processing operations.
• A notable absence of monomers was found in the process fume, which is often a
predictor of polymer degradation, and further supports the evidence for good
temperature control and minimal generation of process fume at the sites investigated.
• At the majority of sites it was not always possible to clearly separate background
environmental levels of contaminants from those generated from other procedures
carried out at the site and those generated from the thermal processing activity of
interest due to the low concentrations found.
• No known respiratory sensitisers (R42) were found at any of the sites investigated.
• Where low levels of respiratory irritants such as aldehydes, ketones and hydrochloric
acid were found these were at concentrations 2 – 3 orders of magnitude below any
respective WEL.
• The principal exposure controls employed at the sites investigated were a combination
of process temperature control and forced mechanical dilution ventilation.
• Most processes at the sites investigated required very little operator intervention, which
in itself reduced exposure risk.
• The use of LEV and RPE to control exposures to airborne contaminants generated by
thermoforming processes was not commonplace at the sites visited.
• The measurement results indicate that no carcinogens, respiratory sensitisers or

respiratory irritants were detected at levels of concern at any of the sites visited. This
indicates that the strategies employed are adequate to control the risks associated with
exposure to these agents.
Recommendations
The report describes the results of sampling for carcinogens and respiratory sensitisers at 10
large processing plants. It is recognised that these plants are not fully representative of the
whole of the plastics processing sector which includes a large number of SMEs. However, the
findings demonstrate that compliance with HSE guidance (HSE, 2002) achieves adequate
prevention and control of exposure in the common thermoplastics processes considered. It will
therefore also do so at smaller plants operated by SMEs who are undertaking the same
thermoplastics processes albeit on a smaller scale.
vi
1 INTRODUCTION
This work was carried out in support of HSE’s FIT3 Disease Reduction Programme Cancer
Project’s aim to develop a strategy to reduce the incidence of occupational cancer in Great
Britain. As part of this strategy, HSE has initiated research that aims to deliver evidence that
will help to identify carcinogens of concern, improve control of exposure to carcinogens at work
and provide a baseline for evaluating strategies for intervention.
HSE characterised the exposure profiles of a selected group of occupational carcinogens and
determined baseline exposures with which to compare future levels at an early stage of the FIT3
Disease Reduction Programme Cancer Project (HSE, 2006). This study identified the potential
for exposure to carcinogens in the thermoplastic processing and finishing industries. HSE
considered there to be however a scarcity of published exposure data for plastics processing
fume.
Thermoplastics are generally processed as pellets, granules or powders, sometimes containing

many additives such as fillers, pigments, fire-retardants and stabilisers (see table 1A and
appendix 1). The composition of the fume generated when the plastic is heated may be complex
and will vary depending on the type of plastic, the formulation and the processing conditions.
Tables 2A and 3A in appendix 1 clearly demonstrate the significant difference in type of
degradation products from chemically similar polymers such as polyethylene and polypropylene
degraded under laboratory conditions at typical processing temperatures. Where thermal
processing is poorly controlled and recommended processing parameters such as temperature
and residence time are exceeded then polymer breakdown can occur leading to the potential
release of airborne contaminants resulting in irritation to the eyes, nose and lungs (HSE, 2002).
Laboratory studies involving heating or vaporisation of polymers in processes such as hot gas
welding and laser cutting (Sims et al., 1993) have shown that a range of airborne contaminants
including carcinogens and respiratory irritants may be generated from commonly processed
plastics. The results of this work are summarised in tables 4A and 5A of appendix 1.
Other unpublished laboratory studies carried out at the Health and Safety Laboratory (HSL),
summarised in table 1, show the potential for the release of carcinogens and other emissions
including respiratory sensitisers and irritants at temperatures near to processing temperatures for
some common thermoplastics. Several carcinogens (HSE 2005 and IARC, 2009) are listed
(R45, R40 and IARC categories 1 and 2) in table 1.Although no respiratory sensitisers were
identified (R42) there are a wide range of compounds harmful by inhalation (R20), irritating to
the respiratory system (R37), which may contribute to potential respiratory sensitisation. Other
substances were also detected which may cause other adverse health effects such as sensitisation
by skin contact (R43) and irritation to the eyes and skin (R36/38).
Although the International Agency for Research on Cancer (IARC) classification of a substance
has no regulatory status in the UK, where IARC have classified a substance as carcinogenic the
information is included in this report. The decision to include these carcinogens was made at the
stakeholder workshop (McElvenny et al.,2007) held on 27th - 28th June 2006 to review progress
with the HSE Occupational Cancer Epidemiology project and involved a team of eminent
epidemiologists and statisticians who were evaluating the numbers of cancers in GB attributable
to occupational causes.
Little is known of the potential for generating these emissions under real workplace processing
conditions and there is very limited published research on the composition of plastic process
fume in real workplace situations. One such study involved a number of plastics and processes
1
that detected very low levels of acrylonitrile under certain conditions for the processing of
acrylonitrile-butadiene-styrene (ABS) and benzene when processing nylon but little else of
concern in terms of carcinogens, respiratory sensitisers or irritants (Forrest M et al., 1995).
However, the measurement protocol for this study was very limited and certain classes of
substances, for instance semi-volatile compounds such as polycyclic aromatic hydrocarbons
(PAHs) and potential respiratory irritants such as volatile aldehydes and ketones would not have
been detected. Other, more recent studies (Meijster et al., 2004) have focussed on a limited
range of polymer types and found a wide range of substances in the process fume.
This project has striven to encompass as wide a range of industry as possible within the
resources available and represents an investigation of different processes all utilising
thermoformed plastic in different ways. The plastics thermoforming sector of industry consists
predominantly of SMEs (85%). This report describes visits to a limited number (10) of co-
operative businesses and is not representative of the industry as a whole. The findings of this
work clearly demonstrate however that many common practices occur between large and
smaller concerns and that compliance with HSE guidance (HSE, 2002) is reasonable,
practicable and achievable. The challenge now is for SMEs to control exposures as well as these
businesses.
Analyses of national mortality data by occupational group for the 1980s (Office of Population
Census and Surveys, 1995, and Brown et al. 2007) showed an excess of male lung cancer deaths
among plastics process workers; and an excess of female lung cancer registrations was also
among this occupation during this period. Limitations in the occupational classification have
prevented a more up-to-date assessment of mortality and cancer incidence for this occupation.
Excesses of male deaths due to acute lymphatic leukemia and diabetes, and an excess of male
stomach cancer registrations were also seen among the occupation "plastic goods makers",
however, no excess deaths were seen for these diseases in this occupation in the latest analysis
of deaths during 1991-2000 (Office for National Statistics, 2009).
HSE considered that:

• due to the past excess of cancers reported in the plastics processing industry;
• the potential for exposure to carcinogens in the thermoplastic processing and finishing
industries; and,
• the findings of earlier laboratory studies;
there was a need for the work described in this report.
The objectives of the work were:
• To make relevant industry contacts and scope out key areas of thermoplastic processing
to select a suitable number of workplaces to visit.
• To investigate the selected sites and carry out screening measurements for carcinogens
and respiratory sensitisers.
• To carry out occupational hygiene assessments for each process investigated.
• To assess the analytical data and determine the potential for exposure to carcinogens
and respiratory sensitisers or irritants across the thermoplastics processing industry.
The wide range of polymers, copolymers, additives and thermal processing methods meant that
any study would be restricted to a small sample of manufacturing operations. The principal aim
of the preliminary work, involving stakeholder discussion, was to allow the site visits to focus
on the polymers and processes where it was considered most likely that there was greatest
2
potential for generation of carcinogens, respiratory sensitisers and irritants. The measurement
techniques adopted for the screening of substances found in the fume were of sufficient scope to
capture a range of data on carcinogens, respiratory sensitisers and irritants but could not be
exhaustive because of the potential for a large number of possible analytes.
3
Table 1. Laboratory study of major thermal breakdown products of some
common thermoplastics at 400 OC *
Polymer Type Thermal degradation products Risk Phrases for key health
(Helium atmosphere)** effects (HSE, 2005, IARC,
2009)
Polyvinylchloride Benzene 45, 46, 23, 24, IARC 1.***
(PVC) Hydrogen chloride 23
Methylmethacrylate 37/38, 43.
Toluene 20, 38, 48, 63.
Styrene 36/38.
Naphthalene IARC 2B
Indene -
Methanol -.
Methyl chloride 40, 48/20.
Phenanthrene -
Polypropylene Pentane -
(PP) Propane -
Butane -
Dimethylheptane -
Methylpentane -
Alkenes -
Low density polyethylene Butane -
(LDPE) Butene -
C5- C14 primary alkenes -
C5-C14 n-alkanes -
C2-C7 aldehydes -
1-Pentadecene -
Toluene 20, 38, 48, 63.
Cyclohexanone
Polystyrene Styrene 36/38.
(PS) Benzaldehyde -
Benzene 45, 46, 23, 24, IARC 1.
Toluene 20, 38, 48, 63.
Methystyrene -
Butene -
Acetaldehyde 36/37, 40.
C4-C6 aldehydes -
Ethylbenzene 20.
Polyacrylonitrile-butadiene- Styrene 36/38.
styrene 1,3-Butadiene 45, 46, IARC 1.
(ABS) Acrylonitrile 45, 23/24/25, 37/38, IARC 2B
4-Vinyl-1-cyclohexene -
Polymethyl methacrylate Methylmethacrylate 37/38, 43.
(PMMA) Methanol
*HSL unpublished work. ** Low molecular mass compounds such as formaldehyde and acetaldehyde would not be detected by the
techniques used in this analysis. ***Risk phrases in bold are compounds which may pose a risk of cancer or irritation to the
respiratory system.
Key for risk phrases used in table 1.
R20 - harmful by inhalation
R23 - toxic by inhalation
R24 - toxic in contact with skin
R23/24/25 - toxic by inhalation, in contact with skin and if swallowed
R26 - very toxic by inhalation
R36/37 - irritating to eyes and respiratory system
R36/38 – irritating to eyes and skin
R37/38 - irritating to the respiratory system and skin
R38 - irritating to skin
R43 - may cause sensitisation by skin contact
R40 - limited evidence of carcinogenic effect
R45 - may cause cancer
R46 – may cause heritable genetic damage
R48 – danger of serious damage to health by prolonged exposure through inhalation
R48/20 - harmful: danger of serious damage to health by prolonged exposure through inhalation
R63 - possible risk of harm to unborn child
IARC 1 – IARC classification, carcinogenic (IARC, 2009).
2A - IARC classification, probably carcinogenic to humans (IARC, 2009)
2B - IARC classification, possibly carcinogenic to humans (IARC, 2009)
4
2 ENGAGEMENT OF INDUSTRY STAKEHOLDERS
Involvement of external stakeholders was sought to ensure that the survey effort could be
targeted at key areas of the thermoplastic processing industry. Industry experts consulted were;
• Mr Trevor Oliver (Polymer Training Ltd);
• Dr Bryan Willoughby (Consultant, formerly employed by the Rubber and Plastics

Research Association (RAPRA))
The industry experts possessed an extensive knowledge of the plastics industry and had
contributed to earlier HSE guidance on the thermoplastic processing industry. They were
influential in determining the range of polymers and process methods studied. Advice was also
sought directly from other industry stakeholders such as the Plastics and Films Association
(PAFA), The Welding Institute (TWI), and the Association of Industrial Laser Users (AILU).
Discussions were held with a range of UK companies currently involved in plastics processing
as well as HSE’s Manufacturing Sector.
Suitable processes and materials for investigation were identified by the stakeholders on the
basis of parameters such as:
• Materials in common use
• Potential to generate fume
• Representative range of manufacturing processes and recycling
• Number of workers exposed
• Throughput of polymer
A summary of the outcome of the consultation with stakeholders is given in table 2. These
thermo-polymers and processes formed the basis for the scope of the measurement survey
and were believed to encompass the greatest potential for exposure to fume, the largest
number of potentially exposed workers, and were some of the commonest materials and
processes in use. It was intended that the measurement survey should match these materials
and processes as closely as possible but with the realisation that not all would be fully
captured.
5
Table 2. Materials and processes identified by stakeholders for study
Polymer Type
Polyvinyl chloride (PVC)
Polyethylene (PE)
Polypropylene (PP)
Polystyrene (PS)
Polymethyl methacrylate (PMMA)
Acrylonitrile butadiene styrene (ABS)
Polyethylene terephthalate (PET)
Potential fume generating process
Vacuum forming: Softened polymer sheet is reshaped under vacuum on heated former.
Laser cutting: Polymer vaporisation during cutting.
Extrusion: Molten polymer forced by a screw through a temperature-controlled die.
Sheet, film and bag manufacture: Film blowing after extrusion
Compounding: Hot mixing of polymer resin and additives and extrusion to pellet.
Injection moulding: Extruded molten polymer is forced into a cooled mould.
Welding: Heating of rigid polymer profiles before compression mating of joints
Recycling: Melting of recycled polymers and additives and extrusion to pellet.
6
3 SITE VISITS
3.1 RANGE OF SITES VISITED
Table 3 summarises the processes and materials actually investigated at the sites that
participated in the measurement survey. For each site an Occupational Hygiene Site Visit
Report (referenced in table 3), describing in detail the site, the processes involved, exposure
controls and a summary of the air monitoring data was produced.
Table 3. Description of Plastic Process Fume Sites
Site reference Polymer(s) processed Process OH Report

number Reference No .
1 PVC compounding and OH2008/LET/14

extrusion
2 PE and PP extrusion, blown film OH2008/LET/15
3 PE, recycled PE extrusion, blown film, OH2008/LET/16

welding
4 Recycled PE, PP, PS recycling, extrusion OH2008/LET/17
5 PET extrusion, blow injection OH2008/LET/30

moulding
6 ABS vacuum forming of sheet OH2008/LET/44
7 PVC extrusion OH2008/LET/64
8 EPS blow moulding, hot wire OH2008/LET/45

cutting
9 PVC/chlorinated PVC alloy vacuum thermoforming OH2008/LET/70
10 PVC welding OH2008/LET/71
3.2 MEASUREMENT PROTOCOL
The measurement protocol was principally designed to identify the presence of carcinogens,
respiratory sensitisers and irritants generated from the process rather than to assess personal
exposure. On each site visit static sampling at 2 positions in close proximity to the process was
employed. This allowed a broad array of highly sensitive screening techniques to be deployed at
each position. Specific samplers for analytes of particular interest, including vinyl chloride
monomer, butadiene, acrylonitrile and formaldehyde were employed. These analytes were
identified from the literature (Forrest et al., 1995 and Sims et al., 1993) as possible components
in fume generated during thermal processing of polymers. In addition, a range of generic
sampling techniques were used to screen for various classes of substances. This included high
7
volume sampling to target any low concentrations of semi-volatile organic compounds utilising
a flow rate of 200 litres/minute. The measurement protocol is described in detail in appendix 2.
8
4 RESULTS
The results for the static air monitoring carried out at the 10 sites are given in appendix 2. For
comparison purposes the respective 8-hr TWA WEL values, where they exist for that specific
substance are also shown. A summary of the sampling and analytical techniques used is given in
appendix 3.
4.1 SITE 1 – PVC COMPOUNDING AND EXTRUSION
4.1.1 Overview of Process
The compounding operation involves the formulation of PVC compounds by adding a range of
additives to PVC resin. There are 5 distinct compounding production units located in this plant.
At the top floor of the plant the PVC powder (resin) is fed in from an external silo and additives
are either added manually or from automated hoppers into weighing vessels. The mixture is then
transported to a lower level to high-speed mixers. There are also addition points here where
small amounts of additives, for example colorants, can be dispensed into the blend. At ground
level the extrusion plant and the main parts of the cooling and bagging plants are situated. The
blended raw materials are heated (to around 180 OC) in the barrel of the extruder where it is then
passed through the extruder and die plate, cut into pellets and cooled. Following cooling the
pellets are transferred by suction to the bagging plant.
4.1.2 Exposure controls
Local exhaust ventilation (LEV) was applied at the addition points where a contaminant release
hazard was present. There was no requirement to provide LEV to any other part of the process.
Visual observation of the area showed the hoods to provide adequate capture efficiency. There
is a forced mechanical general ventilation system on one of the levels in the production area that
will provide increased air movement. No other forced mechanical general ventilation measure
was present on the other levels. Respiratory protective equipment (RPE) was used for certain
tasks including cleaning and sample taking, but not for general production tasks.
4.1.3 Main findings
• Total inhalable particulate (TIP) levels were in the range 0.39 - 0.64 mg/m3.
• No evidence of exposure to toxic metals was found (all results <0.01 mg/m3).
• The low concentrations of hydrogen chloride (<0.004 mg/m3) aldehydes (<0.08 µg/m3)
and volatile organic compounds (all <0.5 ppm) and other semi-volatile materials were
two or more orders of magnitude below any respective WEL.
• Vinyl chloride monomer was detected at concentrations of 3-20 ppb at values 2 to 3

orders of magnitude lower than the current UK WEL of 3 ppm.
• Several polycyclic aromatic hydrocarbons (PAHs) were detected at very low

concentrations (<1ng/m3). Other than naphthalene (IARC 2B), none of the other 4
compounds detected are reported to exhibit carcinogenicity (IARC 2009).
• Azodicarbonamide (R42), an intermittently used additive was not detected in any air
sample (<0.04 mg/m3).
9
• Few of the other additives in use were detected (e.g. butylated hydroxytoluene <1ng
m3).
4.1.4 General Conclusions
The low levels of TIP, VCM, hydrogen chloride and PAHs together with the absence of
benzene, which is indicative of catastrophic PVC degradation, demonstrates that good
temperature control of the compounding and extrusion processes was achieved. It is not
clear whether the VCM originated from the process fume or from the adjacent PVC
manufacturing plant. The company report there to be < 2 ppm residual free VCM trapped in
the polymer resin from the manufacturing process which may potentially be released on
thermal-processing. The levels of VCM found were typical of the environmental
concentrations reported by the company for PVC manufacture. There was a notable low
occurrence of semi-volatile materials, which potentially could have arisen from the use of
additives in the compounding process as well as the process fume. The PAHs, usually
associated with combustion processes were found at typical urban levels (UK Air quality
Archive, 2008). There is no strong evidence to suggest that significant levels of
carcinogens, respiratory sensitisers or irritants are being generated in the process fume.
4.2 SITE 2 – PE AND PP EXTRUSION AND BLOWN FILM
4.2.1 Overview of process
The company extrudes and blows molten polyethylene and polypropylene into a thin film
suitable for use in food packaging. The extrusion hall comprises nine extruders. On the day of
the visit only one of these was running polypropylene. There were a further 4 extruders running
polyethylene. The bulk plastic pellet is stored in a number of external storage silos and is hard
piped into the extrusion hall. The additives are stored within the main building in smaller silos.
Small mobile hoppers are filled from these and located close to the extruders. The raw materials
are automatically dosed and mixed (under heating at 180-200oC) in a rotary screw extruder and
the blend passed through a filter plate which creates a pressure increase. It is then blown out
into a continuous thin tubular shaped cylindrical film, which is air cooled and passed through
rollers forming a double thickness sheet. The sheet is cut to separate and then passed over
rollers where it is electrostatically charged to provide a “key” which aids the printing process.
The finished film is wound and stored on large rolls.
The extrusion hall has a forced mechanical ventilation system. There is no LEV in place for the
processes observed. RPE is not worn for general production tasks.
4.2.3 Main findings
• Total inhalable particulate levels were in the range <0.27 - 0.43 mg/m3.
• No evidence of exposure to toxic metals was found (all results <0. 01 mg/m3).
• Low levels of formaldehyde (2.3–3.4 µg/m3) were detected. This may be associated
with thermal oxidation of the polymers, although there are other common sources of
this substance.
• Several solvents (all <1ppm) were identified which may have originated from printing,
laminating or other processes carried out in adjacent areas of the plant.
10
• The concentrations of aldehydes, VOCs and other semi-volatile materials were
generally several orders of magnitude below any WEL .
• Several PAHs were detected at typical urban concentrations (<1ng/m3), other than
naphthalene (IARC 2B) none of these are reported to be carcinogenic (IARC 2009).
The low levels of oxygenated compounds such as aldehydes, ketones and alcohols found,
demonstrate the lack of polymer degradation through thermal oxidation. This indicates
effective temperature control of the extrusion and film blowing processes. Low
concentrations of additives, no more than 2-3% by mass, are added to the polymer and are
encapsulated in granulated polymer beads prior to melting and extrusion. This results in
minimal release of these substances into the working environment. There is no evidence to
suggest that significant levels of carcinogens, respiratory sensitisers or irritants are being
generated in the process fume.
4.3 SITE 3 – PE AND RECYCLED PE EXTRUSION, BLOWN FILM AND

WELDING
The company manufacture polyethylene bags using some recycled polymer in a blown film
extrusion process similar to site 2.
The extrusion hall comprised of 12 extruders, 9 of these have the capability to apply text using
water-based inks. The printable lines are all located on one side, with the non-printable lines
opposite. The site typically extrudes 70 tonnes of material daily. The company produce the
bags in a batch process. Raw materials are delivered in granular form in 1 tonne quantities in
fibreboard containers. The containers are taken to the rear of the extruders and a feed pipe is
inserted. Chalk is added as a filler. The process involves typical blown film extrusion where the
raw materials are heated to around 180 OC and mixed by a rotary screw mechanism and
extruded and blown out into a thin cylindrical film. This is then air cooled and passed through a
series of rollers, cutters and a welder to produce the finished bags that are stored on a large roll.
There is a forced mechanical general ventilation system in the extrusion hall. There is no LEV
in place. RPE is not worn for general production tasks.
4.3.3 Main findings
• Total inhalable particulate levels were in the range <0.05 - 0.15 mg/m3.
• No evidence of exposure to toxic metals was found (all <0. 01 mg/m3).
• Low levels of formaldehyde (0.2–1.7 µg/m3) were detected. These are 3 to 4 orders of
3
magnitude lower than the WEL of 2.5 mg/m .
• Several solvents (all <0.5ppm) were identified which may have originated from
cleaning or other processes carried out in other areas of the plant.
• The concentrations of aldehydes, VOCs and other semi-volatile materials were

generally several orders of magnitude below any exiting WEL. 1,3-Dichlorobenzene
11
was also identified (< 0.5 ppm) although its origin could not be identified. A range of
PAHs were also detected at very low levels (<1ng/m3) a number of these described as
carcinogens; benzo(a)pyrene (IARC category 1), dibenz(a,h)anthracene (IARC 2A),
benzo(b)fluoranthene, benzo(k)fluoranthene and naphthalene (IARC 2B) although
occurring at levels too low to be of concern and may or may not arise from the process
fume.
The low levels of oxygenated compounds such as aldehydes, ketones and alcohols indicate the
low level of polymer degradation through thermal oxidation suggesting effective temperature
control of the extrusion and film blowing processes. Several carcinogenic PAHs were detected
at very low levels (<1ng/m3). No significant levels of carcinogens, respiratory sensitisers or
irritants were detected in the air samples at sufficient levels to be of concern.
4.4 SITE 4 – PE, PP, PS RECYCLING AND EXTRUSION
The company recycle used plastics to form pelletised material for resale. Waste material is
cleaned, sorted and shredded prior to extrusion. Five of the six extrusion lines were running on
the day of the visit which were processing high impact polystyrene, polypropylene (3
extruders), high density polyethylene and polypropylene. Recycled plastics are purchased in
bales that are sorted, cleaned, shredded and stored in silos for use as raw material for extrusion
into pellet. The shredded plastics are transported by piping into the extrusion hall and fed into
the barrel of the extruder where they are mixed at 180 OC. Moisture and volatile compounds are
removed under vacuum. The blended mixture is extruded through a die plate into pellets that
are quenched in water, dried and fed to a bagging plant in the adjacent storage area.
There are three roof-mounted fans within the extrusion hall that provide increased air
movement. LEV is fitted to the screen changing units. RPE was available for various cleaning
tasks.
4.4.3 Main findings
• Total inhalable particulate levels were in the range 0.44 - 1.03 mg/m3.
• Low levels of formaldehyde (3.1–7.2 µg/m3) were detected. These are 2 to 3 orders of
3
magnitude lower than the UK WEL of 2.5 mg/m .
• Styrene was found in all air samples (< 0.5 ppm) that could have arisen from thermal
degradation of the polystyrene during extrusion.
• A wide range of hydrocarbons, VOCs and solvents were present at low levels (all < 0.5
ppm).
• The concentrations of aldehydes, VOCs and other organic compounds were typically at
least 1-2 orders of magnitude lower than any respective WELs. A range of PAHs were
also detected at very low levels (<1ng/m3) a number of these described as carcinogens;
benzo(a)pyrene (IARC category 1), dibenz(a,h)anthracene (IARC 2A),
12
benzo(b)fluoranthene, benzo(k)fluoranthene and naphthalene (IARC 2B) although
occurring at levels too low to be of concern.
The general low levels of VOCs present demonstrate effective temperature control of the
extrusion process and the absence of significant polymer degradation. A wide range of VOCs
were detected at low levels which may not all be attributable to the extrusion process. A range
of other activities such as raw material preparation and cleaning operations were conducted in
areas adjacent to the extrusion lines. The VOCs may originate from contaminants on the
recycled material in use and may account for the strong odour at the site. No significant levels
of carcinogens, respiratory sensitisers or irritants were detected in the air samples at levels
thought to be of concern.
4.5 SITE 5 – PET EXTRUSION AND BLOW INJECTION MOULDING
The site manufactures a variety of small to medium sized plastic items, such as food and drink
containers, primarily from PET using injection blow moulding. Pellets of virgin PET are
brought onto site by road tanker, and offloaded into storage silos. From here it is hard piped
using a sealed transfer system to the injection blow moulding machines. The pellets are fed
through a desiccating chamber to remove moisture. It is then fed from a storage silo into the
barrel of the extruder and heated to 280°C. The molten PET passes from the screw into a mould.
There are several moulds, mounted on a carousel, on the machine. These are located within a
safety enclosure. The moulds travel around the carousel where metal rods are inserted and the
final item is ‘blown’ into shape using compressed air. The moulded items are transferred onto a
conveyor belt, which takes them to a packing area. The moulded items cool rapidly, and by the
time they leave the safety enclosure around the carousel they are only slightly above room
temperature.
There are a large number of roof fans (extracting) and air handling units (blowing inward) in the
roof space, providing a high degree of air movement in the workroom. No LEV is applied to the
injection blow moulding process. RPE is not worn in the PET injection blow moulding area
during routine operation.
4.5.3 Main findings
• Very low levels of formaldehyde and other aldehydes (<0.1 µg/m3) were found.
• Very low levels of VOCs were found (all < 32 ppb).
least 3 orders of magnitude lower than any respective WEL . Naphthalene (IARC 2B)
and a range of non-carcinogenic PAHs were also detected at very low levels (all
<1ng/m3).
13
The background levels of all analytes were exceedingly low at this site demonstrating the low
levels of emissions generated from this process and effective temperature control of the
extrusion and blow moulding activities.
4.6 SITE 6 – ABS VACUUM FORMING OF SHEET
The site manufactures various items such as car roof boxes, caravan panels etc, primarily from
ABS and HDPE using vacuum forming techniques. The visit focussed on processes involving
ABS as sufficient information on PE had already been gathered. The acrylic capped (removable
thin coat) ABS sheets used to form a caravan panel was manually loaded onto a large carousel.
This is then rotated round to the heating oven position. The temperature and duration of heating
period is dependent on the type of product being produced. The typical processing temperature
was 160 –180 oC. From the oven the softened sheet is rotated to the heated mould onto which it
is lowered and vacuum applied. After approximately 30 seconds an array of cooling fans
situated around the mould are switched on for 3 minutes. The cast is finally rotated around to
the loading/unloading area and transferred by two operators to the trimming area where air
tools, or band saw are used. From here the moulded sheets are transferred to the CNC cutting
area.
There is an extensive general ventilation system to aid cooling within the production area given
that large amounts of heat are generated. No LEV is installed on the vacuum forming machines.
RPE is not worn during normal operation.
4.6.3 Main findings
• Very low levels of formaldehyde and other aldehydes (<0.1 µg/m3) were found.
least 3 orders of magnitude lower than their respective WEL. Analytes of particular
interest such as butadiene, acrylonitrile and styrene that would clearly demonstrate
polymer degradation were absent from the air samples. Naphthalene (IARC 2B) and a
range of non-carcinogenic PAHs were detected at very low levels (all <1ng/m3).
The background levels of all analytes were exceedingly low which demonstrates the low
emissions generated and effective temperature control of the vacuum forming process. The
monitoring data suggests a very low risk from carcinogens, respiratory sensitisers and irritants.
14
4.7 SITE 7 – PVC EXTRUSION
The company manufacture pipes for use in various applications such as gas and water mains.
This is made using a continuous extrusion processes. The majority of the pipe is manufactured
from polyethylene and a smaller proportion from PVC. The visit focussed on the processes
involving PVC as sufficient information on PE had already been gathered.
The bulk PVC pellet is stored in external silos and is hard piped to the mixing area. The
additives (pigments etc.) are stored within the main building. These are added in a separate area,
located on a mezzanine floor, away from the main extrusion hall. Additives are weighed in a
ventilated cabinet then mixed into the PVC in an automated mixer. From here, the raw materials
(PVC plus additives) are hard piped to the extrusion line, where they are fed into the extruder
via a continuous, automated sealed transfer system. Within the extruder the raw ingredients pass
through a heated screw that is maintained between 180°C and 200oC and through a die which
forms the profile of the pipe. The pipe then passes through a vacuum oven, approximately 6
metres long then into two sequential enclosed cooling baths, each around 6 metres long.
Between the vacuum oven and the cooling baths, a section of the pipe, which is still warm after
leaving the cooling oven, is open to the workroom atmosphere as it moves along the line. After
leaving the cooling baths, the pipe is cut to length using an automated saw then stacked
automatically. Under normal operating conditions the line requires very little manual operator
intervention.
On the day of the visit the PVC extrusion line was experiencing technical problems. This
resulted in a section of the enclosure adjacent to the extruder dye being removed and hot
product, visibly fuming as it left the extruder, being open to the workroom atmosphere. This
was manually cut from the line using a hand held knife and discarded onto the floor adjacent to
the extruder where it was left to cool. The cooled material was collected and sent for rework.
The line was operated in this manner for around 90 minutes at the beginning of the sampling
period. Airborne emissions to the workroom atmosphere from the process would have been
significantly higher during this period than during normal operation. Discussion with the line
operators indicated that such breakdowns were infrequent.
The transfer of material to the extruder, the heated screw, extrusion dye and vacuum oven are
totally enclosed under normal operation. The vacuum oven is maintained under negative
pressure by a vacuum pump. It was not clear where the exhaust of this pump vented, but it
appeared likely that it could have been venting within the workroom. The cooling baths are
totally enclosed. No RPE is worn for normal operations on the PVC extrusion area.
4.7.3 Main findings
• Low levels of formaldehyde and other aldehydes were found (<0.1 µg/m3).
• Very low levels of HCl (0.0011 – 0.0023 mg/m3) and VCM (<0.01 ppb) were consistent
with low levels of polymer degradation.
15
least 3 orders of magnitude lower than any respective WELs. VCM and HCl levels were
consistent with a lack of polymer degradation. Naphthalene at 100 ng/m3 (IARC 2B)
and a range of non-carcinogenic PAHs were also detected at low concentrations (all
<10ng/m3).
The background levels of all analytes were exceedingly low indicating the low emissions
generated and effective temperature control of the extrusion processes. The monitoring data
suggests a very low risk from carcinogens, respiratory sensitisers and irritants.
4.8 SITE 8 – EPS BLOW MOULDING AND HOT WIRE CUTTING
The site manufactures insulation products for the construction industry, using expanded
polystyrene.
Large polystyrene blocks (approximately 7.4 m x 1.5m x 1.5 m) are produced on site at
different densities, depending on the application of the final product, by the expansion of
polystyrene beads using pentane as a blowing agent under gentle heating. The block
manufacture takes place adjacent to the cutting lines, but in a dedicated area. Once blown the
blocks are stored on site in dedicated warehousing facilities. The blocks are taken from the
warehouse into the cutting hall where they are lowered onto one of two automated cutting lines.
As the block moves down the line it undergoes a series of cuts in both horizontal and vertical
planes by oscillating hot wires heated to around 200 oC. A final cut to produce the required
length is made by hot wires mounted in a movable frame. Off-cuts are recovered under suction
and returned to the block production area for recycling.
Forced mechanical dilution ventilation is installed in the main workroom. No LEV is used, RPE
is not worn for normal production activity.
4.8.3 Main findings
• No evidence of exposure to toxic metals was found (all <0. 01 mg/m3).
• Low levels of formaldehyde (5 – 9 µg/m3) and other aldehydes including benzaldehyde

and acetophenone were found (<5 - 9 µg/m3).
• Very low levels of aromatic compounds such as benzene (0.3 – 0.7 ppb, R45, IARC 1),
styrene (23 – 84 ppb), toluene (0.8 – 1.6 ppb) and ethylbenzene (9 – 20 ppb) were
found.
• N-Pentane (3–5.2 ppm) and methylbutane (1.2 – 2.6 ppm) were the predominant VOCs
that originated from the blowing agent.
• The concentrations of aldehydes, styrene, benzene, VOCs and other organic compounds
were typically at least 3 orders of magnitude lower than their respective WEL.
16
Naphthalene (< 50 ng/m3, IARC 2B) and a range of non-carcinogenic PAHs were also
detected at very low levels. (<10 ng/m3).
Apart from the blowing agent, n-pentane and methyl butane, background concentrations of
aldehydes, aromatic hydrocarbons and VOCs were very low. It is possible that these compounds
originate from the blow moulding and/or the hot wire cutting. The temperature of the hot wires
was well controlled to reduce the fume emitted although some fume was still visible and was
dispersed by the general ventilation. Slightly higher levels of aromatic compounds and PAHs
were found compared to most of the other sites which may reflect the type of material in use
however other than naphthalene none of the PAHs were classified as carcinogenic. Overall the
4.9 SITE 9 - PVC/CHLORINATED PVC ALLOY THERMOFORMING
The site manufactures a range of products by vacuum thermoforming of PVC sheet. Single
sheets of the PVC alloy were loaded into the vacuum thermoforming machine where it was
heated to approximately 180 oC. The mould is raised up such that it comes into contact with the
sheet and a vacuum is then applied to complete the forming process. The heat and vacuum are
applied for a predetermined length of time usually a few minutes. The moulded product is then
cooled by fans and removed from the machine manually and transferred to the trimming and
finishing area.
Forced mechanical dilution ventilation is present. Together with cooling fans on the
thermoforming machines this provided good air movement. No LEV was used, RPE was not
worn for normal production activity.
4.9.3 Main findings
• Total inhalable particulate results were all <0.1 mg/m3.
• Low levels of formaldehyde (<0.1–2 µg/m3) and other aldehydes (all <0.1 µg/m3) were
found.
• HCl (<0.001 mg/m3) and VCM (<0.01 ppb) were consistent with low levels of polymer
degradation.
• Very low levels of VOCs (all < 190 ppb) were found.
least 3 orders of magnitude lower than any respective WEL. VCM and HCl levels were
evidence of the lack of significant polymer degradation. A range of PAHs including
naphthalene (20 ng/m3, IARC 2B) and a range of non-carcinogenic PAHs (all <20
ng/m3) were detected.
17
emissions generated and effective temperature control of the thermoforming processes. The
4.10 SITE 10 – PVC WELDING
The company manufactures a range of u-PVC plastic products, primarily door frames. The u-
PVC profiled components are manually loaded into a welding machine. With the exception of
the unloading stage, the rest of the welding process is automated although the operator will stay
in close proximity. Heated plates are lowered onto the faces of the u-PVC components that are
to be welded together for about 45 seconds. The plate temperature is controlled to 245 oC. The
plates are then retracted and the two components are automatically mated to allow the two parts
to weld. The time period allowed for the welding of the two components to take place is 35
seconds. The welded component can then be unloaded. Each machine can perform two welds
simultaneously so the manufacture of a complete door- frame from the four individual
components will require two weld cycles. Once complete the four welds on each door- frame
are machined automatically which improves the appearance of the weld.
No forced mechanical dilution ventilation is installed. No LEV was in use, RPE was not worn
for normal production activity.
4.10.3 Main findings
• Total inhalable particulate levels were in the range < 0.02 – 0.17 mg/m3.
• Low levels of formaldehyde were found (<0.1 µg/m3) and an absence of other
aldehydes.
• HCl (0.0046 – 0.0054 mg/m3) and VCM (<0.01 ppb) were consistent with low levels of
polymer degradation.
• Other than dichloromethane (2.3–3.7 ppm, WEL 100 ppm) low levels of VOCs (all <
340 ppb) were found.
• The concentrations of aldehydes, VOCs, solvents and other organic compounds were
typically at least 1- 3 orders of magnitude lower than their respective WEL . VCM and
HCl levels were evidence of the lack of significant polymer degradation. A range of
PAHs was also detected. Other than naphthalene,(60 ng/m3, IARC 2B) all others
compounds (all < 20 ng/m3) are considered to be non-carcinogenic.
emissions generated and effective temperature control of the welding processes.
Dichloromethane (R40) was the most predominant VOC that originated from a lamination
18
process adjacent to the welding operation. The monitoring data suggests a very low risk from
carcinogens, respiratory sensitisers and irritants.
19
5 DISCUSSION
5.1 MATERIALS AND PROCESSES INVESTIGATED
The majority of the thermo-polymers and thermoforming processes initially identified by

the stakeholders were studied during the scope of this project. Several of the sites processed
other polymers in addition to the one studied during the site visit. PP and high and low
density PE were the most commonly encountered polymers.
Amongst the sites visited, the perception was that the fume generated from thermal
processing of plastics was, under normal operating conditions, of relatively low toxicity.
None of the sites perceived significant potential for exposure to carcinogens or respiratory
sensitisers from their operations.
The only widely used polymer not encountered in the survey was PMMA. PMMA is known
to thermally degrade to its monomer when treated at excessive temperatures (Gao Z et al.,
2004). There is also a lack of evidence in the literature to support concerns over the release
of carcinogens or respiratory sensitisers from this material when processed. Evidence from
laser cutting of PMMA (Sims et al., 1993) also suggests that thermal breakdown products
are of low toxicity.
Evidence in the literature (Sims et al., 1993) suggested that laser cutting would be a process
that had the greatest potential to generate substantial quantities of harmful substances,
particularly from PVC. The view of the Association of Industrial Laser Users (AILU), with
regard to best practice to safely laser cut plastics is clear, and recommends a high level of
control or containment (Roberts, 2005). AILU promote in their guidance to their association
that because of the high standard of controls required and the potential health risks from the
fume, laser cutting has limited use for plastics. It also advises against cutting PVC because
it has the greatest potential to release harmful substances (Green M and Powell J, 1999).
AILU confirmed that small job shops avoid laser cutting of plastics because of high level of
controls required compared to the cutting of steel but suggested that PMMA was the most
likely material to be cut because of the low risk associated with the fume.
5.2 AIR MONITORING RESULTS
At the majority of sites it was not possible to clearly separate background environmental
levels of contaminants, those generated from other procedures carried out at the site and
those generated from the thermoforming activity of interest due to the low concentrations
found.
The carcinogens detected during the site visits are summarised in Table 4. Respiratory
sensitisers are not included in Table 4 since none were detected at any site.
20
Table 4. Summary of carcinogens detected.
Site reference Process studied Carcinogens detected

1 PVC Vinyl chloride monomer (max concentration 20 ppb,
compounding UK WEL 3 ppm)
PAH at typical environmental concentrations
2 PE/PP extrusion Formaldehyde (max concentration 3.4 µg/m3, UK WEL
2.5 mg/m3)
3 PE and recycled Formaldehyde (max concentration 1.7 µg/m3, UK WEL
PE extrusion, 2.5 mg/m3)
blown film, PAH at typical environmental concentrations
welding
4 PE, PP, PS Formaldehyde (max concentration 7.2 µg/m3, UK WEL
recycling and 2.5 mg/m3)
extrusion PAH at typical environmental concentrations
5 PET extrusion PAH at typical environmental concentrations
and injection
blow moulding
6 ABS vacuum PAH at typical environmental concentrations
forming
7 PVC extrusion PAH at typical environmental concentrations
8 EPS blow Formaldehyde (max concentration 9 µg/m3, UK WEL
moulding and 2.5 mg/m3)
hot wire cutting PAH at typical environmental concentrations
9 PVC Formaldehyde (max concentration 2 µg/m3, UK WEL
thermoforming 2.5 mg/m3)
10 PVC welding PAH at typical environmental concentrations
5.3 EXPOSURE CONTROL STRATEGIES
The principal exposure control employed by most sites was careful temperature control of
the thermoforming process. Although the main drivers for effective temperature control are
process considerations, i.e overheating plastics during thermoforming will result in
scorching, which is not acceptable in the finished product. However there are clear benefits
in terms of exposure control. The results of this project strongly suggest that temperature
control is sufficient to prevent the generation of highly toxic thermal decomposition
products.
Most sites did have forced mechanical ventilation (dilution) in the areas where
thermoforming was performed. This appeared effective in controlling the low levels of fume
that were generated from the thermoforming processes. At almost all sites the processes
were largely automated, with very little operator intervention required under normal
conditions. This provides an additional level of exposure control.
21
The application of LEV to plastics thermoforming operations was not common at the sites
visited. None of the sites used RPE as an exposure control during normal production
activities.
It is clear that the existing guidance within Controlling fume during plastics processing,
Plastics processing sheet no 13 (HSE, 2002) is valid and that well maintained plant and
following the recommended processing parameters such as temperature and residence or
dwell time will deliver adequate control of process fume. As the processes investigated in
this work are equally prevalent in SME’s, as well as larger businesses, then this guidance
equally applied to them.
22
6 CONCLUSIONS
6.1 MAIN FINDINGS FROM THE MEASUREMENT SURVEY
6.1.1 Carcinogens
• The levels of carcinogens detected in the process fume at the sites investigated were
found to be either low or not detected.
• Where low levels of carcinogens or potential respiratory sensitisers were found these
were at concentrations 2 – 3 orders of magnitude below the respective WEL where one
exists.
• The maximum concentrations of carcinogens found at the sites visited were: Benzene
(R45) 11 ppb; formaldehyde (R40) 9 µg/m3; naphthalene (IARC 2B) < 100 ng/m3; and,
other carcinogenic polycyclic aromatic hydrocarbons (IARC 1, 2A and 2B) all < 10
ng/m3
• All substances detected in this study were measured at levels below 10% of their
respective WEL, demonstrating the low level of process fume encountered.
• The low levels of total inhalable particulate measured (values from all sites were below
1.15 mg/m3) and the low concentration of all other substances measured, further
demonstrates the low levels of fume generated and the effective temperature control of
the respective thermal processing operations.
• A notable absence of monomers was found in the process fume, which is often a
predictor of polymer degradation, and supports the evidence for good temperature
control and minimal generation of process fume at the sites investigated.
• At the majority of sites it was not always possible to clearly separate background
environmental levels of contaminants from those generated from other procedures
carried out at the site and those generated from the thermal processing activity of
interest due to the low concentrations found.
6.1.2 Respiratory Sensitisers and Irritants
• No known respiratory sensitisers (R42) were found at any of the sites investigated.
• Where low levels of respiratory irritants such as aldehydes, ketones and hydrochloric
acid and were found these were at concentrations 2 – 3 orders of magnitude below
respective WELs where one exists.
6.1.3 Adequacy of Control Measures
• The principal exposure controls employed at the sites investigated were a combination
of process temperature control and forced mechanical dilution ventilation.
• Most processes at the sites investigated required very little operator intervention, which
in itself reduced exposure risk.
• The use of LEV and RPE to control exposures to airborne contaminants generated by
thermoforming processes was not commonplace at the sites visited.
23
• The measurement results indicate that no carcinogens, respiratory sensitisers or
respiratory irritants were detected at levels of concern at any of the sites visited. This
indicates that the strategies employed are adequate to control the risks associated with
exposure to these agents.
24
7 REFERENCES
1. HSE (2006). Disease Reduction Programme: Cancer Project. The nature and extent of use of,
and occupational exposure to, chemical carcinogens in the UK workplaces. Available from:
http://www.hse.gov.uk/aboutus/meetings/iacs/acts/watch/091106/p7annex2.pdf. Accessed
26/11/08.
2. Office of Population Censuses and Surveys (1995). Occupational health decennial

supplement the Registrar General’s decennial supplement for England and Wales (1995). Edited
by Dever F., p. 80, HMSO.
Office for National Statistics. Occupational Mortality in England and Wales, 1991 – 2000.
ISBN 978-1-85774-696-9.
3. Brown et al., (2007). The burden of occupational cancer in Britain. Results for bladder
cancer, leukaemia, cancer of the lung, mesothelioma, non-melanoma skin cancer and sinonasal
cancer. Available from: http://www.hse.gov.uk/research/rrpdf/rr595main.pdf. Accessed
20/01/09.
4. HSE (2002). Controlling fume during plastics processing. Plastics processing sheet no 13.
HSE Books.
5. Sims J et al., (1993). Pollutants from laser cutting and hot gas welding of plastics, Ann.
occup. Hyg., Vol. 39, No 1, pp. 35-53.
6. Forrest M et al., (1995). Emissions from processing thermoplastics, Ann. occup. Hyg., Vol.
37, No 6, pp. 665-672.
3. HSE (2005). Approved supply list. Information approved for the classification and labelling
of substances and preparations dangerous for supply. Chemicals (Hazard Information and
Packaging for Supply) Regulations 2002. Approved list L142 (8th edition), HSE Books, ISBN
07 17661385.
3. Meijster et al. (2004). Evaluating Exposures to complex mixtures of chemicals during a new
production process in the plastics industry. Ann. occup. Hyg., Vol. 48, No 6, pp. 499-507.
6. UK Air Quality Archive. Available from:

http://www.airquality.co.uk/archive/data/pah/PAH_Quarterly_Andersen_Data_to_2007_Q4_fin
al_v2.xls. Accessed 21/11/08.
7. Unwin J (1999). Measurement of polycyclic aromatic hydrocarbons in mineral quench oils.

HSL report No OMS/99/14.
8. Gao Z et al., (2004). Kinetics of thermal degradation of poly(methylmethacrylate) studied

with the assistance of the fractional conversion at the maximum reaction rate. Polymer
degradation and stability, Vol. 84, 3, pp 399-403.
9. Roberts D (2005), Laser fume and UK law. The Industrial Laser User, Issue 38, pp 6-7.
10. Green M and Powell J (1999). Dealing with plastics fume during laser cutting. The
Industrial Laser User, Issue 15, p 12.
25
11. The Nordic Expert Group for Criteria Documentation of health Risks from Chemicals
(1998). Thermal degradation products of polyethylene, polypropylene, polystyrene,
polyvinylchloride, polytertrafluoroethylene, in the processing of plastics. Available from:
http://www.inchem.org/documents/kemi/kemi/ah1998_12.pdf. Accessed 14/01/09.
12. IARC (2009). Overall Evaluations of Carcinogenity to Humans. Lists of all agents, mixtures
and exposures evaluated to date. Available from:
http://monographs.iarc.fr/ENG/Classification/crthalllist.php. Accessed 15/01/09.
13 McElvenny (2007). Burden of Occupational Cancer in Great Britain. HSL Report No

HSL/2007/32.
10. OH2008/LET/14. HSL Occupational Hygiene Section Site Visit Report
26
8 APPENDIX 1 – ADDITIVES AND DEGRADATION
PRODUCTS
Table 1A. Some Additives used in Polyethylenes

Class of additive Example
Fillers Carbon black
Pigments Titanium dioxide, chromic acid
Flame retardants Antimony trioxide, chlorinated compounds
Slip agents Fatty acid amines
Blowing agents Azodicarbonamide,
4,4-oxybisbenzenesulphonohydrazide
Rubbers Polyisobutylene, butyl rubber
cross-linking agents Peroxides
antioxidants Phenols
antistatics Polyethylene glycol alkyl esters
Table 2A. Compounds Identified in Thermo-oxidation of Polyethylene at 264 – 289 oC

Carbon dioxide Hexene Tetrahydrofuran Methylvinyl Butyric acid.
ketone
Water. Hexane10 Formaldehyde 2, 9, Methylethylketone. Isovaleric acid.
11
Ethene. Heptene. Acetaldehyde 3, 9 2-Pentanone. Hydroxyvaleric acid

Propene. Heptane. Propanol. 2-Hexanone. Crotonic acid.
Propane. Octene. Acrolein4 2-Heptanone. Caproic acid.
Cyclopropane. Octane. Butanal. Formic acid. Butyrolactone.
Butene. Methanol. Isobutanal. Acetic acid. Valerolactone.
Butane. Ethanol. Pentenal. Propionic acid. Hydroperoxides.
Pentene. Furan. Acetone. Acrylic acid. Alkoxy radicals.
Table 3A. Compounds Identified in Thermo-oxidation of Polypropylene at Processing Temperatures

Ethene. Methylpentene Methacrolein . Methylhexanal. Acetone.
Propene. Methylheptene Butanal. Nonanal. Butanone.
Isobutene. Methanol Methylpentanal. Ethenone. Cyclopropylethanone
Pentadiene. Methylpropen-ol Octanal. 3-Buten-2-one. 3-Penten-2-one
Dimethylpentene. Ethanol Decanal. 1-Hydroxy-2- 2, 3-Butanedione
propenone.
Dimethylbenzene Methylfuran Acetaldehyde 3, 9 Methyl-3-buten-2-one. 2,4-Pentanedione.
Ethane. Dimethylfuran Propanal. Pentanone. Methylheptanone
Propane. Formaldehyde2 Methylpropanal. Cyclopropyl-2- Formic & Acetic acid
propanone.
Butane. Acrolein4 Vinylcrotonaldehyde Methylpentanone. Propionic acid.
Data in tables 1A-3A from The Nordic Expert Group for Criteria Documentation of health Risks from Chemicals (1998).
27
Table 4A. Emissions Resulting from the Laser Cutting of Plastics *
Cut assist gas
Plastic Argon Air
1, 5, 11
Polycarbonate Benzene Benzene 1, 5, 11
Hexane10
Toluene8 Toluene8
Xylenes8 Xylenes8
8
Styrene Styrene8
Phenol8 Phenol8
p-Cresol. m-Cresol.
Naphthalene6 Benzo-furan derivative.
Benzo-furan derivative. Benzo(a)fluorine.
2-Ethyl-1,4-dimethylbenzene. Fluorene.
Alkanes. Fluoranthene.
Dibenzo(a,h)anthracene5
Benzo(b)fluoranthene6
Benzo(e)pyrene.
Polyvinylchloride 2-Chloro-1,3-butadiene 6 2-Chloro-1,3-butadiene 6
1,4-Pentadiene. Benzene 1, 5, 11
Z-3-Pentenene-1-yne.
1,5-Hexadiene. Toluene8
Benzene 1, 5 Styrene8
Methylmethacrylate7 1-Propynylbenzene.
Methylcyclohexane. 1,3-Butadienylbenzene.
Toluene8 Naphthalene6
Chlorobenzene8 Alkanes.
Styrene8 Pyrene.
Benzaldehyde. Benzo(a)fluorine.
1,2-Propadienylbenzene.
4-Ethylstyrene.
Naphthalene6
Alkanes.
Fluorene.
Polyethylene terephthalate Benzene 1, 5, 11 Phenylacetylene.
Benzaldehyde.
8
Toluene Methylphenyl ketone.
Xylene 8 Phenol 8
Styrene8 Alkanes.
Phenylacetylene. Fluorene.
Benzaldehyde. Pyrene.
Methylphenyl ketone. Chrysene6
Alkanes. Benzo(a)anthracene6
Phenanthrene. Dibenz(a,h)anthracene5
Anthanthrene.
Polymethyl methacrylate Methylmethacrylate7 Methylmethacrylate7

Toluene8 Toluene8
Xylene 8 Xylene 8
Trimethylbenzene. Trimethylbenzene.
Alkanes. Alkanes.
Epoxide-glass Toluene8 Xylenes8
Z-2-Heptenal. Tridecanols.
Xylenes8 Trimethylbenzene.
4-Methylcycloheptanone. Alkanes.
Tridecanol. Anthanthrene.
Trimethylbenzene.
Alkanes.
Anthanthrene.
* Data from Sims et al., (1993).
28
Table 5A. Emissions Resulting from the Hot Gas Welding of Plastics (+ 15 o C from optimum
processing temperature) *
Plastic
Polycarbonate Toluene8 Acetone.
Isobutyl acetate. Chlorobenzene8
Butyl acetate. Phenol8
Chlorobenzene8 Alkanes.
Ethylbenzene8 Methylcyclohexane.
Xylenes8
Alkanes.
Polyvinylchloride Acetone. Methylcyclohexane.
Toluene8 2-Ethoxyethylacetate.
3-methy-2-butanone. 6-Methyl-1-heptanol.
8
Xylene Alkanes.
Polymethy methacrylate Acetone. Xylene 8

Hexane10 1,3-Dichlorobenzene.
Methylmethacrylate7 Alkanes.
Ethylbenzene 8
Nylon Acetone. Xylene 8

Toluene8 6-Aminohexanoic acid.
Ethylbenzene8
Polypropylene Acetone Hexenol.

Toluene8 4-Methyl-2-heptanone.
Ethylbenzene8 Alkanes.
Xylene 8
* Data from Sims et al., 1993.
Key to tables 2-5.

1
R45 (may cause cancer)
2
R43 (may cause sensitisation by skin contact)
3
R36/37 (irritating to eyes and respiratory system),
4
R26 (very toxic by inhalation)
5
IARC 2A (Carcinogenic to humans (IARC, 2009))
6
IARC 2B (Probably carcinogenic to humans (IARC, 2009))
7
R37/38 (irritating to the respiratory system and skin)
8
R20 (harmful by inhalation)
9
R40 (limited evidence of carcinogenic effect)
10
R48/20 (Harmful: danger of serious damage to health by prolonged exposure through inhalation
11
IARC 1 (carcinogenic to humans, (IARC), 2009))
29
9 APPENDIX 2 - AIR MONITORING RESULTS
Site 1- PVC Compounding and extrusion

Method Measured airborne concentration
Analyte 8-hr WEL
reference Sampler A1 Sampler A2 Sampler B1 Sampler B2
Formaldehyde 1/2 2.5 mg/m3 <0.08 µg/m3 <0.08 µg/m3
Butanal 1/2 - <0.01 µg/m3 <0.01 µg/m3
Glyoxal 1/2 - <0.01 µg/m 3
<0.01 µg/m3
Benzaldehyde 1/2 - <0.01 µg/m 3
<0.01 µg/m3
Hexanal 1/2 - <0.01 µg/m 3
<0.01 µg/m3
Pentanal 1/2 - <0.01 µg/m3 <0.01 µg/m3
Pyruvaldehyde 1/2 - <0.01 µg/m 3
<0.01 µg/m3
3 3 3
HCl 3 2 mg/m 0.0036 mg/m 0.0038 mg/m 0.0043 mg/m3 <0.002 mg/m3
3 3 3 3
TIP** 4 10 mg/m 0.39 mg/m 0.46 mg/m 0.55 mg/m 0.64 mg/m3
3 3 3 3
Azodicarbonamide 4 1.0 mg/m <0.04 mg/m <0.04 mg/m <0.04 mg/m <0.04 mg/m3
3 3 3 3
Total Chromium 5 0.5 mg/m <0.01 mg/m <0.01 mg/m <0.01 mg/m <0.01 mg/m3
3 3 3 3
Cadmium 5 0.025 mg/m <0.01 mg/m <0.01 mg/m <0.01 mg/m <0.01 mg/m3
3 3 3 3
Lead 5 0.15 mg/m <0.01 mg/m <0.01 mg/m <0.01 mg/m <0.01 mg/m3
1,2-ethanediol 6/7 - <0.5 ppm <0.5 ppm <0.5 ppm <0.5 ppm
nC8-nC14
6/7 - <0.5 ppm <0.5 ppm <0.5 ppm <0.5 ppm
hydrocarbons
Ethylhexanol 6/7 - <0.5 ppm <0.5 ppm <0.5 ppm <0.5 ppm
2,4-pentadione 6/7 - <0.5 ppm <0.5 ppm <0.5 ppm <0.5 ppm
1,3 –butadiene 8 10 ppm <0.5 ppb <0.5 ppb <0.5 ppb <0.5 ppb
Vinyl chloride
9/10 3 ppm 6 ppb 20 ppb 10 ppb 3 ppb
monomer
Acrylonitrile 11 2 ppm <0.01 ppb <0.01 ppb <0.01 ppb <0.01 ppb
2,4 bis(1,1- 3 3
12 - <1 ng/m <1 ng/m
dimethyl) phenol
Butylated hydroxy
12 10 mg/m3 <1 ng/m3 <1 ng/m3
toluene
Drometrizole 12 - <1 ng/m3 <1 ng/m3
Napthalene 12 - <1 ng/m3 <1 ng/m3
Fluorene 12 - <1 ng/m3 <1 ng/m3
Fluoranthene 12 - <1 ng/m3 <1 ng/m3
Phenanthrene 12 - <1 ng/m3 <1 ng/m3
Pyrene 12 - <1 ng/m3 <1 ng/m3
**Total Inhalable Particulate
30
Site 2- PE and PP Extrusion and blown film
Measured airborne concentration
Method
Analyte 8-hr WEL
Formaldehyde 1/2 2.5 mg/m3 3.4 µg/m 3
2.3 µg/m3
Glyoxal 1/2 - <0.01 µg/m3 <0.01 µg/m3
Pyruvaldehyde 1/2 - <0.01 µg/m3 <0.01 µg/m3
HCl 3 2 mg/m3 0.0028 mg/m3 0.0040 mg/m3 0.0036 mg/m3 0.0028 mg/m3
TIP 4 10 mg/m3 <0.27 mg/m 3
<0.27 mg/m3 <0.27 mg/m 3
0.43 mg/m3
Azodicarbonamide 4 1 mg/m3 <0.03 mg/m 3
<0.03 mg/m3 <0.03 mg/m 3
<0.03 mg/m3
Total Chromium 5 0.5 mg/m3 <0.01 mg/m 3
<0.01 mg/m3 <0.01 mg/m 3
<0.01 mg/m3
Cadmium 5 0.025 mg/m3 <0.01 mg/m 3
<0.01 mg/m3 <0.01 mg/m 3
<0.01 mg/m3
Lead 5 0.15 mg/m3 <0.01 mg/m 3
<0.01 mg/m3 <0.01 mg/m 3
<0.01 mg/m3
Ethanol 6/7 1000 ppm <1.0 ppm <1.0 ppm <1.0 ppm <1.0 ppm
nC10-nC14
6/7 - <1.0 ppm <1.0 ppm <1.0 ppm <1.0 ppm
hydrocarbons
Ethyl acetate 6/7 200 ppm <1.0 ppm <1.0 ppm <1.0 ppm <1.0 ppm
Propyl acetate 6/7 200 ppm <1.0 ppm <1.0 ppm <1.0 ppm <1.0 ppm
Propylene glycol 6/7 150 ppm <1.0 ppm <1.0 ppm <1.0 ppm <1.0 ppm
Methylether 6/7 400 ppm <1.0 ppm <1.0 ppm <1.0 ppm <1.0 ppm
n-propanol 6/7 200 ppm <1.0 ppm <1.0 ppm <1.0 ppm <1.0 ppm
Iso-propanol 6/7 400 ppm <1.0 ppm <1.0 ppm <1.0 ppm <1.0 ppm
1,3 –butadiene 8 10 ppm <0.5 ppb <0.5 ppb <0.5 ppb <0.5 ppb
Vinyl chloride
9/10 3 ppm <0.01 ppb <0.01 ppb <0.01 ppb <0.01 ppb
monomer
2,4 bis(1,1- 3 3 3
12 - <1 ng/m <1 ng/m <1 ng/m <1 ng/m3
dimethyl) phenol
nC16-nC20
12 - <1 ng/m3 <1 ng/m3 <1 ng/m3 <1 ng/m3
hydrocarbons
Tetradecanoic acid 12 - <1 ng/m3 <1 ng/m3 <1 ng/m3 <1 ng/m3
3
n-hexadecanoic acid 12 - <1 ng/m <1 ng/m3 <1 ng/m 3
<1 ng/m3
3
Hexadecene 12 - <1 ng/m <1 ng/m3 <1 ng/m 3
<1 ng/m3
3
Octadecene 12 - <1 ng/m <1 ng/m3 <1 ng/m 3
<1 ng/m3
3 3
Naphthalene 12 - <1 ng/m <1 ng/m
Pyrene 12 - <1 ng/m3 <1 ng/m3
31
Site 3- PE and recycled PE Extrusion, blown film and welding
Analyte 8-hr WEL
Formaldehyde 1/2 2.5 mg/m3 1.7 µg/m3 0.2 µg/m3
Acetaldehyde 1/2 - < 0.01 µg/m3 < 0.01 µg/m3
Glyoxal 1/2 - < 0.01 µg/m 3
< 0.01 µg/m3
Benzaldehyde 1/2 - < 0.01 µg/m3 < 0.01 µg/m3
Pyruvaldehyde 1/2 - < 0.01 µg/m3 < 0.01 µg/m3
3
HCl 3 2 mg/m 0.0034 mg/m 0.0030 mg/m 0.0034 mg/m3 <0.0016 mg/m3
3 3
3
TIP 4 10 mg/m 0.08 mg/m3 0.10 mg/m3 <0.05 mg/m3 0.15 mg/m3
3 3
Azodicarbonamide 4 1 mg/m3 <0.03 mg/m3 <0.03 mg/m <0.03 mg/m <0.03 mg/m3
Total Chromium 5 0.5 mg/m3 <0.01 mg/m3 <0.01 mg/m3 <0.01 mg/m3 <0.01 mg/m3
3 3 3 3
Cadmium 5 0.025 mg/m <0.01 mg/m <0.01 mg/m <0.01 mg/m <0.01 mg/m3
Lead 5 0.15 mg/m3 <0.01 mg/m3 <0.01 mg/m3 <0.01 mg/m3 <0.01 mg/m3
nC10-nC14 hydrocarbons 6/7 - <0.5 ppm <0.5 ppm <0.5 ppm <0.5 ppm
Toluene 6/7 50 ppm <0.5 ppm <0.5 ppm <0.5 ppm <0.5 ppm
Limonene 6/7 - <0.5 ppm <0.5 ppm <0.5 ppm <0.5 ppm
1, 3-Dichlorobenzene 6/7 - <0.5 ppm <0.5 ppm <0.5 ppm <0.5 ppm
Iso-propanol 6/7 400 ppm <0.5 ppm <0.5 ppm <0.5 ppm <0.5 ppm
50 ppm
n-Butanol 6/7 <0.5 ppm <0.5 ppm <0.5 ppm <0.5 ppm
(STEL)
Methylethyl ketone 6/7 - <0.5 ppm <0.5 ppm <0.5 ppm <0.5 ppm
Propylene glycol
6/7 100 ppm <0.5 ppm <0.5 ppm <0.5 ppm <0.5 ppm
methylether
1,3-butadiene 8 10 ppm <0.5 ppb <0.5 ppb <0.5 ppb <0.5 ppb
Vinyl chloride monomer 9/10 3 ppm <0.01 ppb <0.01 ppb <0.01 ppb <0.01 ppb
2,4 bis(1,1-dimethylethyl)
12 - < 1 ng/m3 < 1 ng/m3
phenol
nC16-nC22 Hydrocarbons 12 - < 1 ng/m3 < 1 ng/m3
Nonylphenol 12 - < 1 ng/m3 < 1 ng/m3
Naphthalene 12 - < 1 ng/m3 < 1 ng/m3
Acenapthalene 12 - < 1 ng/m3 < 1 ng/m3
Phenanthrene 12 - < 1 ng/m3 < 1 ng/m3
Pyrene 12 - < 1 ng/m3 < 1 ng/m3
Anthracene 12 - < 1 ng/m3 < 1 ng/m3
Chrysene 12 - < 1 ng/m3 < 1 ng/m3
Benzo(b,k)fluoranthene 12 - < 1 ng/m3 < 1 ng/m3
Benzo(a)pyrene 12 - < 1 ng/m3 < 1 ng/m3
Dibenze(a,h)anthracene 12 - < 1 ng/m3 < 1 ng/m3
Benzo(g,h,i) perylene 12 - < 1 ng/m3 < 1 ng/m3
32
Site 4- PE, PP, PS Recycling and extrusion
Analyte 8-hr WEL
Formaldehyde 1/2 2.5 mg/m3 3.1 µg/m3 7.2 µg/m3
Acetaldehyde 1/2 - <0.01 µg/m3 <0.01 µg/m3
Crotonaldehyde 1/2 - <0.01 µg/m 3
<0.01 µg/m3
Benzaldehyde 1/2 - <0.01 µg/m3 <0.01 µg/m3
Pyruvaldehyde 1/2 - <0.01 µg/m 3
<0.01 µg/m3
HCl 3 2 mg/m3 0.0057 mg/m3 0.0056 mg/m3 0.0015 mg/m3 0.0040 mg/m3
3
TIP 4 10 mg/m 0.44 mg/m3 0.61 mg/m3 1.03 mg/m3 0.66 mg/m3
Azodicarbonamide 4 1 mg/m3 <0.03 mg/m3 <0.03 mg/m3 <0.03 mg/m3 <0.03 mg/m3
3 3 3 3
Total Chromium 5 0.5 mg/m <0.01 mg/m <0.01 mg/m <0.01 mg/m <0.01 mg/m3
Cadmium 5 0.025 mg/m3 <0.01 mg/m3 <0.01 mg/m3 <0.01 mg/m3 <0.01 mg/m3
3 3 3 3
Lead 5 0.15 mg/m <0.01 mg/m <0.01 mg/m <0.01 mg/m <0.01 mg/m3
nC10-nC14 hydrocarbons 6/7 - <0.5 ppm <0.5 ppm <0.5 ppm <0.5 ppm
C5-C10 branched
6/7 - <0.5 ppm <0.5 ppm <0.5 ppm <0.5 ppm
hydrocarbons
Cyclohexane 6/7 100 ppm <0.5 ppm <0.5 ppm <0.5 ppm <0.5 ppm
Styrene 6/7 100 ppm <0.5 ppm <0.5 ppm <0.5 ppm <0.5 ppm
Methyl cyclohexane 6/7 - <0.5 ppm <0.5 ppm <0.5 ppm <0.5 ppm
Xylene 6/7 50 ppm <0.5 ppm <0.5 ppm <0.5 ppm <0.5 ppm
Limonene 6/7 - <0.5 ppm <0.5 ppm <0.5 ppm <0.5 ppm
Trimethylbenzenes 6/7 25 ppm <0.5 ppm <0.5 ppm <0.5 ppm <0.5 ppm
1,1 bis(1,2-
12 - <1 ng/m3 <1 ng/m3
cyclobutanediyl) benzene
nC16-nC22 Hydrocarbons 12 - <1 ng/m3 <1 ng/m3
n-hexanoic acid 12 - <1 ng/m3 <1 ng/m3
Napthalene 12 - <1 ng/m3 <1 ng/m3
Acenapthalene 12 - <1 ng/m3 <1 ng/m3
Chrysene 12 - <1 ng/m3 <1 ng/m3
Benzo(b,k) fluoranthene 12 - <1 ng/m3 <1 ng/m3
Benzo (a)pyrene 12 - <1 ng/m3 <1 ng/m3
Benzo(a)anthracene 12 - <1 ng/m3 <1 ng/m3
Benzo(b,k) fluoranthene 12 - <1 ng/m3 <1 ng/m3
33
Site 5- PET Extrusion and injection blow moulding
Analyte Method 8-hr Measured airborne concentration
reference WEL Sampler Sampler Sampler Sampler
A1 A2 B1 B2
Formaldehyde 1/2 2.5 <0.1 µg/m3 <0.1 µg/m3
mg/m3
Glyoxal 1/2 - <0.1 µg/m3 <0.1 µg/m3
HCl 3 2 mg/m3 0.0007 0.0008 0.0012 0.0010
mg/m3 mg/m3 mg/m3 mg/m3
TIP 4 10 mg/m3 0.16 0.19 0.08 0.32
Azodicarbonamide 4 1 mg/m3 <0.07 <0.07 <0.07 <0.07
Total Chromium 5 0.5 <0.01 <0.01 <0.01 <0.01
mg/m3 mg/m3 mg/m3 mg/m3 mg/m3
Cadmium 5 0.025 <0.01 <0.01 <0.01 <0.01
g/m3 mg/m3 mg/m3 mg/m3 mg/m3
Lead 5 0.15 g/m3 <0.01 <0.01 <0.01 <0.01
Ethanol 6/7 1000 ppm 11 ppb 6.5 ppb 1 ppb 1 ppb
Isopropyl alcohol 6/7 - 32 ppb 29 ppb 3 ppb 3 ppb
Limonene 6/7 - 1 ppb 2 ppb 1 ppb 1 ppb
Methyl pentane 6/7 - 32 ppb 23 ppb 5 ppb 7 ppb
1-methoxy 2-propanol 6/7 100 9 ppb 21 ppb 2 ppb 9 ppb
1-methoxy 2-propyl 6/7 50 ppm 0.3 ppb 0.8 ppb 0.6 ppb 0.5 ppb
acetate
Methylcyclohexane 6/7 - 21 ppb 8 ppb 3 ppb 5 ppb
nC7 6/7 - 9 ppb 6 ppb 1 ppb 2 ppb
nC9 6/7 - 0.1 ppb 0.3 ppb <0.1 ppb <0.1 ppb
nC10 6/7 - 0.4 ppb 0.4 ppb 0.1 ppb 0.1 ppb
Toluene 6/7 50 0.6 ppb 0.6 ppb 0.4 ppb 0.4 ppb
Xylene 6/7 50 1.4 ppb 0.7 ppb 1.5 ppb 0.4 ppb
2,4-bis-(1,1- 12 - <1 ng/ m3 <1 ng/ m3
dimethylethyl)phenol
Naphthalene 12 - <1 ng/ m3 <1 ng/ m3
Fluorene 12 - <1 ng/ m3 <1 ng/ m3
Phenanthrene 12 - <1 ng/ m3 <1 ng/ m3
Fluoranthene 12 - <1 ng/ m3 <1 ng/ m3
Pyrene 12 - <1 ng/ m3 <1 ng/ m3
34
Site 6 – Vacuum forming of acrylic capped (coated) ABS
reference WEL Sampler Sampler Sampler Sampler
A1 A2 B1 B2
Formaldehyde 1/2 2.5 1.3 µg/m3 2.2 µg/m3
mg/m3
Butanone 1/2 600 <0.1 µg/m3 <0.1 µg/m3
mg/m3
HCl 3 2 mg/m3 0.0011 0.001 0.0006 0.0006
TIP 4 10 0.08 0.09 0.07 0.11
Total Chromium 5 0.5 <0.01 <0.01 <0.01 <0.01
Cadmium 5 0.025 <0.01 <0.01 <0.01 <0.01
Lead 5 0.15 <0.01 <0.01 <0.01 <0.01
Methyl pentane 6/7 - 10.9 ppb 0.2 ppb 1.5 ppb 0.31 ppb
Methylmethacrylate 6/7 50 ppm 2 ppb 1 ppb 4 ppb 4 ppb
Alpha-Pinene 6/7 - 0.2 ppb 0.1 ppb 0.04 ppb 0.08 ppb
nC7 6/7 - 1.4 ppb 0.1 ppb 0.2 ppb 0.1 ppb
nC10 6/7 - 0.5 ppb 0.2 ppb 0.2 ppb 0.2 ppb
Toluene 6/7 50 0.4 ppb 0.3 ppb 0.4 ppb 0.2 ppb
Xylene 6/7 50 2.2 ppb 0.3 ppb 1.3 ppb 0.3 ppb
2,4-bis-(1,1- 12 - <1 ng/ m3 <1 ng/ m3
Pyrene 12 - <1 ng/ m3 <1 ng/ m3
35
Site 7 – Extrusion of PVC
Reference WEL Sampler Sampler Sampler Sampler
A1 A2 B1 B2
mg/m3
Butanone 1/2 600 <0.1 µg/m3 <0.1 µg/m3
mg/m3
Glyoxal 1/2 - <0.1 µg/m3 <0.1 µg/m3
HCl 3 2 mg/m3 0.0011 0.0018 0.0023 0.0023
TIP 4 10 0.23 0.23 1.15 0.58
Total Chromium 5 0.5 <0.01 <0.01 <0.01 <0.01
Cadmium 5 0.025 <0.01 <0.01 <0.01 <0.01
Lead 5 0.15 <0.01 <0.01 <0.01 <0.01
Methyl pentane 6/7 - 38 ppb 12 ppb 25 ppb 2 ppb
Methylethylketone 6/7 - 307 ppb 168 ppb 201 ppb 118 ppb
Ethylene glycol 6/7 - 2 ppb 2 ppb 16 ppb 9 ppb
nC10 6/7 - 1 ppb <0.01 ppb 2 ppb 2 ppb
nC11 6/7 - < 0.01 ppb <0.01 ppb 2 ppb 2 ppb
nC12 6/7 - 1 ppb <0.01 ppb 2 ppb 2 ppb
2,4-bis-(1,1- 12 - <1 ng/ m3 <1 ng/ m3
Acenaphthalene 12 <10 ng/ m3 <10 ng/ m3
Acenaphthene 12 <10 ng/ m3 <10 ng/ m3
Pyrene 12 - <10 ng/ m3 <10 ng/ m3
36
Site 8 – EPS Blow moulding and hot wire cutting
A1 A2 B1 B2
Formaldehyde 1/2 2.5 9µg/m3 5µg/m3
mg/m3
Benzaldehyde 1/2 - <9µg/m3 <5 µg/m3
Acetophenone 1/2 - <9µg/m3 <5µg/m3
Glyoxal 1/2 - <9µg/m3 <5µg/m3
Pyruvaldehyde 1/2 - <9µg/m3 <5µg/m3
HCl 3 2 mg/m3 <0.001mg/m3 <0.001 <0.001 <0.001mg/m3
mg/m3 mg/m 3
TIP 4 10 mg/m3 0.21 mg/m 3

0.21 0.16 0.11 mg/m3
mg/m3 mg/m 3
Azodicarbonamide 4 1 mg/m3 <0.04 mg/m3 <0.04 <0.04 <0.04 mg/m3

mg/m3 mg/m 3
Total Chromium 5 0.5 <0.01 mg/m3 <0.01 <0.01 <0.01 mg/m3

mg/m3 mg/m3 mg/m 3
Cadmium 5 0.025 <0.01 mg/m3 <0.01 <0.01 <0.01 mg/m3

mg/m3 mg/m3 mg/m 3
Lead 5 0.15 <0.01 mg/m3 <0.01 <0.01 <0.01 mg/m3

mg/m3 mg/m3 mg/m 3
Methyl butane 6/7 - 2609 ppb 2285 ppb 1242 ppb 1785 ppb
n-Pentane 6/7 - 5244 ppb 4821 ppb 3013 ppb 3514 ppb
Cyclopentane 6/7 - 99 ppb 68 ppb 56 ppb 60 ppb
Benzene 6/7 1 ppm 0.7 ppb 0.5 ppb 0.3 ppb 0.4 ppb
Toluene 6/7 50 ppm 1.6 ppb 1.3 ppb 0.8 ppb 0.8 ppb
Methylformamide 6/7 - 1.9 ppb 3.5 ppb <0.01 1.4 ppb
ppb
Ethyl Benzene 6/7 100 ppm 20 ppb 25 ppb 9 ppb 17 ppb
Styrene 6/7 100 ppm 84 ppb 76 ppb 23 ppb 42 ppb
Alpha-pinene 6/7 - 1.1 ppb 0.6 ppb 0.7 ppb 0.4 ppb
Acetophenone 6/7 - 3.5 ppb 2.3 ppb 3.5 ppb 2.8 ppb
Benzene 6/7 - 11 ppb 10 ppb 5 ppb 7 ppb
Benzoic acid 6/7 - 21 ppb 56 ppb <0.01 7 ppb
ppb
Vinyl chloride 9/10 3 ppm <0.01 ppb <0.01 <0.01 <0.01 ppb
monomer ppb ppb
Acrylonitrile 11 2 ppm <0.01 ppb <0.01 <0.01 <0.01 ppb
ppb ppb
Naphthalene 12 - <50 ng/m3 <50 ng/m3
Acenaphthalene 12 - <10 ng/m3 <10 ng/m3
Acenaphthene 12 - <10 ng/m3 <10 ng/m3
Pyrene 12 - <10 ng/m3 <10 ng/m3
37
Site 9 – PVC/chlorinated PVC alloy Vacuum thermoforming
A1 A2 B1 B2
Formaldehyde 1/2 2.5 2 µg/m3 <0.1 µg/m3
mg/m3
Glyoxal 1/2 - <0.1 µg/m3 <0.1 µg/m3
Acetaldehyde 1/2 - <0.1 µg/m3 <0.1 µg/m3
HCl 3 2 mg/m3 <0.001 <0.001 <0.001 <0.001
TIP 4 10 < 0.1 < 0.1 < 0.1 < 0.1
Total Chromium 5 0.5 <0.01 <0.01 <0.01 <0.01
Cadmium 5 0.025 <0.01 <0.01 <0.01 <0.01
Lead 5 0.15 <0.01 <0.01 <0.01 <0.01
Isopropyl alcohol 6/7 - 50 ppb 111 ppb 49 ppb 110 ppb
Dichloromethane 6/7 100 ppm 45 ppb 149 ppb 48 ppb 143 ppb
Methylmethacrylate 6/7 50 ppm 38 ppb 190 ppb 57 ppb 163 ppb
Naphthalene 12 - 20 ng/m3 20 ng/m3
Pyrene 12 - <20 ng/m3 <20 ng/m3
38
Site 10 – Welding of PVC
A1 A2 B1 B2
mg/m3
HCl 3 2 mg/m3 0.0053 0.0046 0.0049 0.0054
TIP 4 10 <0.02 0.14 0.17 0.14
Total Chromium 5 0.5 <0.01 <0.01 <0.01 <0.01
Cadmium 5 0.025 <0.01 <0.01 <0.01 <0.01
Lead 5 0.15 <0.01 <0.01 <0.01 <0.01
nC5 6/7 - 19 ppb 282 ppb 47 ppb 299 ppb
Dichloromethane 6/7 100 ppm 3683 ppb 2876 ppb 3295 ppb 2294 ppb
Methylethylketone 6/7 200 ppm 32 ppb 53 ppb 24 ppb 62 ppb
nC7 6/7 - 17 ppb 278 ppb 15 ppb 340 ppb
Methylcyclohexane 6/7 - 6 ppb 112 ppb 5 ppb 146 ppb
Toluene 6/7 50 ppm 8 ppb 4 ppb 7 ppb 4 ppb
n-butylacetate 6/7 200 ppm 5 ppb 13 ppb 9 ppb 8 ppb
1-Methoxy-2-propyl 6/7 - 3 ppb 2 ppb 4 ppb 2 ppb
acetate
nC10 6/7 - 3 ppb 3 ppb 3 ppb 3 ppb
Butanedioic acid 6/7 - 12 ppb 6 ppb 10 ppb 6 ppb
dimethylester
Pentanedioic acid 6/7 - 20 ppb 11 ppb 17 ppb 11 ppb
dimethylester
Naphthalene 12 - 60 ng/m3 60 ng/m3
Pyrene 12 - <10 ng/m3 <10 ng/m3
39
10 APPENDIX 3 - SAMPLING AND ANALYTICAL
TECHNIQUES
10.1 INTRODUCTION
A summary of the sampling and analytical methodology is given in table 13. Static sampling at
2 positions in close proximity to the process was employed as the aim was to identify the
presence of carcinogens and respiratory sensitisers generated from the process rather than
personal exposure. This allowed a broad array of highly sensitive screening techniques to be
deployed at each position. A further, more detailed investigation could be carried out should
hazardous substances be detected from the static sampling exercises. A number of specific
analytes are listed in table 13 that includes vinyl chloride monomer, butadiene and acrylonitrile.
Such potential analytes were identified from the literature (4, 5) as possible components in fume
generated during thermal processing of the polymer.
10.2 LOW VOLUME SAMPLING
Samples were collected for approximately 2–6 hours depending on the type of analyte and
sampling flow-rate (0.05 to 2 L/min). Sorbent tubes samples (0.05 L/min) collected for analysis
by methods 6 – 11 were limited to approximately 2 hours collection time to avoid sample
breakthrough. This allowed a morning and afternoon sample of each type to be collected. A
sorbent tube (0.05 L/min) and also a treated filter sampler (1 L/min) were collected at each
position for the aldehyde screen for robustness. The data for the filter sampler was reported here
due to the greater sensitivity afforded by this sampling technique.
10.3 HIGH VOLUME SAMPLING
The high volume sampling system has been described elsewhere (7). The sampling train
consists of a quartz filter (100 mm diameter) and a sorbent cartridge containing two
polyurethane foam plugs retaining 25g of XAD2 resin. The sampling rate of 200 l/min ensures a
low limit of detection (sub-ppb) for any particulate and semi-volatile materials such as
polycyclic aromatic hydrocarbons (PAHs). The filter and cartridge are analysed separately to
identify non-volatile and semi-volatile fractions of the air sample. The filter retains only
particulate material whilst the cartridge will retain any semi-volatile material draw through the
filter. This is the case for PAHs where a wide range of vapour pressures exists for the target
compounds (EPA16).
10.4 ASSIGNMENT OF MEASUREMENT VALUES
The results of the analytical measurements in tables X – Y are frequently assigned less than
values (<) in the table where concentrations either fell below the limit of detection of the
analytical procedure or below the lowest calibration point of the method . Exhaustive calibration
of analytical procedures down to the very low concentrations observed in many cases would
have been technically difficult and time consuming and would not have benefited the
interpretation of the data since demonstration of the low concentrations present was fit for
purpose.
40
Table 13. Summary of sampling and analysis methodology
A
Method
Analyte(s) Sampling medium Sample flow rate B Analytical method Other information
reference
37 mm GF/A filter treated with 2,4
1 Aldehydes 1 litre/minute (1) HPLC/UV MDHS 93
dinitrophenylhydrazine (DNPH)
As above, tube is SKC
2 Aldehydes DNPH treated silica gel tube 50 ml/minute (1) As above
part number 226-119
Ion chromatography. In-
3 HCl Sodium carbonate treated 25 mm filter 2 litres/minute (2) house method IM OP IOM sampler
411
TIP – gravimetric.
Azodicarbonamide/Total Inhalable
4 25 mm GF/A filter, pre-conditioned 2 litres/minute (2) Azodicarbonamide – IOM sampler
Particulate (TIP)
HPLC/UV
MDHS 91.
5 Metals 25 mm GLA 5000 membrane filter 2 litres/minute (2) XRF
IOM sampler
General volatile organic compound Automated thermal desorption (ATD) tube In-house method OMS-
6 50 ml/minute (1*) ATD-GC/MS
41
(VOC) screen – tube 1 containing Tenax sorbent 001
In-house method OMS-
7 General VOC screen – tube 2 ATD tube containing chromosorb 106 sorbent 50 ml/minute (1*) ATD-GC/MS
001
8 Butadiene ATD tube containing Carbopack X sorbent 50 ml/minute (1*) ATD-GC/FID
001
Vinyl chloride monomer (VCM) and In-house method OMS-
9 ATD tube containing PFC sorbent 50 ml/minute (1*) ATD-GC/MS
low molecular weight hydrocarbons 001
10 VCM tube 2 ATD tube containing air toxics sorbent 50 ml/minute (1*) ATD-GC/MS
001
In-house method
11 Acrylonitrile ATD tube containing TAUC sorbent 50 ml/minute (1*) ATD-GC/FID
OMS-001
Semi volatiles to include 100 mm quartz filter backed up with 2 x Anderson Instruments
12 polycyclic aromatic hydrocarbons Polyurethane Foam (PUF) samplers with 200 litres/minute (1*) GC/MS PS-1 high volume
(PAHs) C XAD sorbent bed in between. PUF sampler
A
Reference number for sampling and analysis method employed. B Values in brackets = number of sample replicates at each position, * sampler
replaced after approximately 2 hours (morning and afternoon samples collected). CUS EPA list of 16 polycyclic aromatic hydrocarbons compounds.
Published by the Health and Safety Executive 05/10
Health and Safety
Executive

This work was carried out in support of HSE’s FIT3
Disease Reduction Programme Cancer Project’s
aim to develop a strategy to reduce the incidence
of occupational cancer in Great Britain. As part
of this strategy, HSE has initiated research that
aims to deliver evidence that will help to identify
carcinogens of concern, improve control of
exposure to carcinogens at work and provide a
baseline for evaluating strategies for intervention.
Earlier, in 2005-7, HSL characterised the exposure

profiles of a selected group of occupational
carcinogens and determined baseline exposures
with which to compare future levels. The project
identified the potential for exposure to carcinogens
in the thermoplastic processing and finishing
industries however there was a scarcity of published
quantitative exposure data. A number of laboratory
and other studies had shown that carcinogens could
be generated from the processing of thermoplastics
in some situations but further investigation was
required to establish the levels of exposure that may
originate in the industrial setting.
The report describes the results of sampling for

carcinogens and respiratory sensitisers at ten large
processing plants. The measurement strategy
used was sufficiently broad in scope to take into
account the presence of respiratory sensitisers
and respiratory irritants as well as carcinogens.
The findings demonstrate that compliance with
HSE guidance achieves adequate prevention and
control of exposure in the common thermoplastic
processes considered. This report will be helpful
to smaller plants operated by small and medium
enterprises who undertake the same processes
albeit on a smaller scale.
This report and the work it describes were funded

by the Health and Safety Executive (HSE). Its
contents, including any opinions and/or conclusions
expressed, are those of the author alone and do not
necessarily reflect HSE policy.
RR797
www.hse.gov.uk

Investigation of Potencial Exposure To Carcinogens and Respiratory Sensitisers During Thermal Processing of Plastics

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Investigation of Potencial Exposure To Carcinogens and Respiratory Sensitisers During Thermal Processing of Plastics

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Health and Safety

Investigation of potential exposure to

Investigation of potential exposure to

First published 2010

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2 ENGAGEMENT OF INDUSTRY STAKEHOLDERS .....................................5

3 SITE VISITS ......................................................................................................7

8 APPENDIX 1 – ADDITIVES AND DEGRADATION PRODUCTS.............27

9 APPENDIX 2 - AIR MONITORING RESULTS.............................................30

10 APPENDIX 2 - SAMPLING AND ANALYTICAL TECHNIQUES............40

• Carry out occupational hygiene assessments for each process investigated.

• The measurement results indicate that no carcinogens, respiratory sensitisers or

Thermoplastics are generally processed as pellets, granules or powders, sometimes containing

HSE considered that:

there was a need for the work described in this report.

The objectives of the work were:

• To carry out occupational hygiene assessments for each process investigated.

• Mr Trevor Oliver (Polymer Training Ltd);

• Dr Bryan Willoughby (Consultant, formerly employed by the Rubber and Plastics

• Materials in common use

• Potential to generate fume

• Representative range of manufacturing processes and recycling

• Number of workers exposed

Polyvinyl chloride (PVC)

Polymethyl methacrylate (PMMA)

Acrylonitrile butadiene styrene (ABS)

Polyethylene terephthalate (PET)

Potential fume generating process

Laser cutting: Polymer vaporisation during cutting.

Extrusion: Molten polymer forced by a screw through a temperature-controlled die.

Sheet, film and bag manufacture: Film blowing after extrusion

Injection moulding: Extruded molten polymer is forced into a cooled mould.

Welding: Heating of rigid polymer profiles before compression mating of joints

Recycling: Melting of recycled polymers and additives and extrusion to pellet.

3.1 RANGE OF SITES VISITED

Table 3. Description of Plastic Process Fume Sites

Site reference Polymer(s) processed Process OH Report

1 PVC compounding and OH2008/LET/14

2 PE and PP extrusion, blown film OH2008/LET/15

3 PE, recycled PE extrusion, blown film, OH2008/LET/16

4 Recycled PE, PP, PS recycling, extrusion OH2008/LET/17

5 PET extrusion, blow injection OH2008/LET/30

6 ABS vacuum forming of sheet OH2008/LET/44

7 PVC extrusion OH2008/LET/64

8 EPS blow moulding, hot wire OH2008/LET/45

9 PVC/chlorinated PVC alloy vacuum thermoforming OH2008/LET/70

10 PVC welding OH2008/LET/71

3.2 MEASUREMENT PROTOCOL

4.1 SITE 1 – PVC COMPOUNDING AND EXTRUSION

4.1.1 Overview of Process

4.1.2 Exposure controls

4.1.3 Main findings

• Vinyl chloride monomer was detected at concentrations of 3-20 ppb at values 2 to 3

• Several polycyclic aromatic hydrocarbons (PAHs) were detected at very low

4.1.4 General Conclusions

4.2 SITE 2 – PE AND PP EXTRUSION AND BLOWN FILM

4.2.1 Overview of process

4.2.2 Exposure controls

4.2.3 Main findings

4.2.4 General Conclusions

4.3 SITE 3 – PE AND RECYCLED PE EXTRUSION, BLOWN FILM AND

4.3.1 Overview of process