Prepared by the Health and Safety Laboratory for the Health and Safety Executive 2013

Health and Safety Executive

Assessment of exposure to carcinogens and asthmagens in the contract import, processing and repackaging industries

RR983Research Report

Joan Cooke Health and Safety LaboratoryHarpur HillBuxtonDerbyshire SK17 9JN

The aim of this research was to assess the effectiveness of exposure controls at small and medium-sized enterprises (SMEs) carrying out the import, reprocessing and repackaging of chemical carcinogens and asthmagens.

Visits were made to 10 companies which decant and repack chemicals including carcinogens and asthmagens. The visits examined handling practices and exposure controls, and included, where possible, a quantitative exposure assessment, either by biological monitoring or air sampling.

Although there were some examples of good practice, overall, this survey found that control of exposure was variable in its effectiveness. Deficiencies in COSHH assessments (Control of Substances Hazardous to Health) and/or inadequacies in engineering controls (LEV - Local Exhaust Ventilation) and/or PPE (Personal Protective Equipment) were found at all but one site visited.

Recommendations for improvements to management systems and/or exposure control were made for all but one site. Recommendations included the need to improve LEV systems; to introduce health surveillance programmes; and to improve PPE programmes, including ensuring the introduction of fit testing for Respiratory Protective Equipment (RPE), undertaking routine RPE maintenance and ensuring correct glove selection.

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.

Assessment of exposure to carcinogens and asthmagens in the contract import, processing and repackaging industries

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Health and Safety Executive

© Crown copyright 2013

First published 2013

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Acknowledgements

HSL wish to thank the Chemical Business Association (CBA) for their assistance in the early stages of this work, the ten companies that provided access to their premises and all the individuals who participated in the sampling exercises. Thanks are also given to HSL’s Analytical Sciences Unit who analysed all the samples collected.

ii

iii

KEY MESSAGES

The Chemical Business Association (CBA) provided a listing of some 15 companies actively

involved in the import and supply of chemical carcinogens and asthmagens. When contacted

three of companies advised that although they imported such chemicals, they did not in fact

break open any containers. They advised that the chemicals were sold on to end users in the

manufacturers’ containers without decanting and repackaging.

In total, ten companies were visited as part of this survey. Exposure control standards were

highest at the only top tier COMAH site visited. Poor management systems and / or control at

source were observed at the other sites. These were a mixture of lower tier, sub, and non

COMAH sites. This supports a conclusion drawn from a previous survey JS2002998 (‘A

workplace survey on the control of task specific exposures to carcinogens, mutagens and

reprotoxins in the UK chemical industry’), that in general, standards of exposure control were

higher at top tier COMAH sites than at lower tier sites, which in turn were higher than the few

sub-COMAH sites visited.

The potential for liquid dyes containing the azo compounds CI Solvent Red 164 and 24 to

metabolise within the body to ortho-toluidine or aniline was investigated also. Aniline only was

detected, and then, in only 3 of 47 samples at levels significantly below the relevant guidance

value.

iv

EXECUTIVE SUMMARY

Introduction

The chemical industry in the UK comprises businesses of a range of sizes. The larger

organisations are members of the Chemical Industries Association (CIA) and they handle

approximately 80% of the UK chemical business but employ only 20% of UK chemical workers

(these figures came from an informal discussion with the Chemical Business Association -

CBA). This industry sub sector was surveyed in 2005 (JS2002998 ‘A workplace survey on the

control of task specific exposures to carcinogens, mutagens and reprotoxins in the UK chemical

industry’) and the findings reported in HSL report HSL/2005/35[1]

.

The purpose of this project was to survey small and medium sized enterprises (SMEs), many of

who are members of the CBA. This industry sub sector handles 20% of UK chemical business

but employs 80% of UK chemical workers (again these figures came from an informal

discussion with the CBA). The aim was to assess the effectiveness of exposure controls at those

SMEs carrying out the import, reprocessing and repackaging of chemical carcinogens and

asthmagens. The objectives of the work were:

i) To engage with relevant internal and external stakeholders and assemble a schedule

of workplaces, representative of this industry sector, to be visited. Stakeholders

included HSE’s Hazardous Installations Directorate (HID) and the CBA. The CBA

provided valuable assistance by liaising with members to secure agreement to

support this project.

ii) To visit up to 30 workplaces and assess handling practices and exposure controls

for carcinogens and/or asthmagens. The assessment methodology included (where

possible) a quantitative exposure assessment, either by biological monitoring or air

sampling.

iii) To analyse the findings and compile a final report to compare and contrast with the

findings from JS2002998. If appropriate, the report findings may also be used to

inform possible future work by HSE or industry relating to exposure control at the

import, reprocessing and repackaging of chemical carcinogens and asthmagens.

Methodology

A listing of some 15 companies was provided by the CBA and a further seven companies were

sourced from other surveys (the earlier task specific exposure survey mentioned above and one

looking at exposures in the surface engineering industry). Four formulators of the azo dye CI

Solvent Red 164 were approached following concerns that this substance can metabolise within

the body to ortho toluidine and aniline. A programme of cold calling was also undertaken.

Of those contacted, ten businesses, described below and identified as sites A - J, indicated they

decant and repack and agreed to assist this survey.

Sites A, B, C and D are formulators of dye penetrant solution reported as containing the azo dye

CI Solvent Red 164. Site C also supply a diesel marker concentrate containing the azo dye CI

Solvent Red 24.

Site E take delivery of a concentrated solution of hydrazine hydrate (hydrazine is a carcinogen)

and dilute it before selling on to end users.

v

Site F manufacture potassium chromate solution using chromic acid flake. This and the

resulting potassium chromate solution contain chromium in its hexavalent state (a known

carcinogen and respiratory sensitiser).

Sites G and H manufacture nickel solutions for the electroplating industry using solid nickel

sulphate. Nickel sulphate is a carcinogen and also a respiratory sensitiser.

Site I uses azodicarbonamide (ADC) in the production of blowing agents for flooring material.

ADC is a respiratory sensitiser.

Site J receive bulk deliveries of trichloroethylene (a carcinogen), transfer to bulk storage and

then utilise an automated closed loop filling system to decant and repackage chlorinated

solvents, to be sold on for use as vapour cleaning/degreasing agents.

A HSL occupational hygienist visited all the sites (accompanied at some by a HSE inspector)

and assessed work practices and exposure controls. Quantitative exposure measurements were

carried out using (where applicable) either air sampling and/or biological monitoring. A full

occupational hygiene report was then written and fed back to the company via the site inspector.

Main findings

Local exhaust ventilation (LEV) systems were present at all four sites, however improvements

were required. Personal Protective Equipment (PPE) consisted of protective gloves (worn at all

sites), coveralls worn at sites A and C, and Respiratory Protective Equipment (RPE) worn at

sites B and C. At sites B and D the workers were not provided with coveralls but instead wore

their own normal clothing.

Improvements had been made to the process at site E since a previous visit made to the site (not

as part of this project) by HSE. At the time of the previous visit, the company relied on PPE to

control exposure to the chemical handled (hydrazine). By the time of this project visit, the

hydrazine was handled remotely using a sealed transfer system and a computer controlled filling

station, thus achieving almost total containment.

At site F chromic acid flake was manually added to a caustic solution. The resulting solution

was then manually decanted by gravity feed through a flexible hose into containers for onward

despatch. Biological monitoring and air sampling was carried out to assess exposure to

chromium. Inhalation exposures to total chromium and hexavalent chromium were less than the

UK Workplace Exposure Limit (WEL) of 0.5 mg/m3 and 0.05 mg/m

3 respectively. One

worker’s urinary chromium concentration exceeded the UK Biological Monitoring Guidance

Value (BMGV). Control measures included LEV and PPE. The PPE worn consisted of chemical

protective suit, gloves and RPE.

Sites G and H mixed nickel sulphate crystals with other substances to make an electroplating

solution. At site G, the nickel sulphate was placed into a grinder to break down any large lumps

prior to mixing. Once mixed the solution was dispensed into containers for delivery. Biological

monitoring and air sampling were carried out to assess exposure to nickel. Air sampling for

exposure to TID was also carried out. Inhalation exposures to TID at both sites were less than

the COSHH exposure limit of 10 mg/m3. Exposures to nickel were also less than the WEL of

0.1 mg/m3. Inhalation exposures to TID and Ni at site H were all in fact less than the limits of

detection for the analytical methods (<0.02 mg/m3 and <0.001 mg/m

3 respectively) as 8-hr time

weighted averages. Urinary concentrations of nickel at site G were all within the range for those

with no occupational exposure (<10 µmol/mol creatinine). At site H, one urinary nickel

exceeded the standard that HSL adopted for this survey, but was lower than the German value.

vi

Control measures at both sites G and H consisted of LEV and PPE. The LEV was located at the

mixing vessels at both sites. PPE consisted of overalls and disposable gloves. RPE was worn at

site H.

At site I, bags of powdered ADC were manually emptied into a mixing vessel. Air sampling

was carried out for exposure to TID and ADC. The 8-hr TWA inhalation exposures were 4.6

mg/m3 and 2.8 mg/m

3 respectively. The exposure to ADC exceeded the WEL of 1 mg/m

3 by

almost three times. LEV was provided but deficiencies in its design meant that control was not

achieved at source. Battery powered RPE was worn by the operator carrying out the work.

At site J, trichloroethylene was handled in a closed loop system, with minimal worker contact.

Both air sampling and biological monitoring were carried out. Inhalation exposures were

significantly less than the UK WEL of 100 ppm. Urinary concentrations of trichloroacetic acid

(the urinary marker for trichloroethylene) were significantly less than the UK BMGV of 35

mmol/mol creatinine.

Urine samples were received from sites A through to D after work was carried out with liquid

dyes containing the azo compound CI Solvent Red 164. The samples were analysed for ortho

toluidine and aniline in response to concerns regarding the potential metabolisation to these

substances within the body. The majority of the results for ortho toluidine were at the non-

detected level (<0.4 µmol/mol creatinine). Measurable concentrations ranged from 0.4 to 2

µmol/mol creatinine, all of which were within the range for those with no occupational exposure

(up to 5µmol/mol creatinine). The majority of the aniline concentrations were within the range

for those with no occupational exposure (up to 10µmol/mol creatinine). One result was at this

value and two exceeded it, however the latter two should be treated with caution as they were

analysed after significant dilution due to low sample volume. However all results were

significantly less than the German Guidance Value [2]

. These findings were reported to the HSE

Working Group on Action to Control Chemicals (WATCH) in October 2011[3]

.

Urine samples were also received from site C after work with CI Solvent Red 24. All urinary

concentrations of ortho toluidine were at the non-detected level and none of the aniline

concentrations exceeded the reference range for those with no occupational exposure. This dye

is used in powder form, thus there is the potential for inhalation exposure. Air sampling for total

inhalable dust (TID) was carried out. The 8-hr time weighted average (8-hr TWA) exposure was

3.3 mg/m3 with the task based exposure being 21.5 mg/m

3 (over a sampling period of 73

minutes).

Recommendations

Recommendations for improvements to management systems and / or exposure control were

made to all sites apart from site E where none were required. These are summarised below:

o Improvements / reviews of COSHH assessments

o Carry out improvements to LEV systems; this included re-designing systems to offer better

control at source

o Compare future LEV through examination and test (TExT) reports to HSE guidance in

order to ascertain whether the report is comprehensive enough

o Introduce, where applicable, a programme of health surveillance when using asthmagens

o Improvements to PPE programmes including face fit testing, RPE maintenance and correct

glove selections.

CONTENTS PAGE

1. INTRODUCTION ....................................................................... 1

1.1 Project background 1

1.2 Overview of use of each substance 2

1.3 UK Regulatory position for each substance 3

2. METHODOLOGY ...................................................................... 5

2.1 The design of the study 5

2.2 Analysis details 5

3. RESULTS ................................................................................. 7

3.1 Formulators of CI Solvent Red 164 (A – D) and 24 (c) – as reported 7

3.2 Hydrazine Supplier – Site E 9

3.3 Potassium chromate producer – Site F 10

3.4 Nickel plating salts producer – Sites G and H 11

3.5 Producer of blowing agent for flooring material containing ADC – Site I 12

3.6 Repackaging of trichloroethylene into closed loop systems – Site J 13

4. DISCUSSION .......................................................................... 15

4.1 CI Solvent Red 164 and 24 15

4.2 Hydrazine 15

4.3 Potassium chromate 15

4.4 Nickel plating salts 16

4.5 ADC 16

4.6 Trichloroethylene 16

4.7 Common themes 16

5. CONCLUSIONS ...................................................................... 18

6. RECOMMENDATIONS ........................................................... 19

7. REFERENCES ........................................................................ 20

1

1. INTRODUCTION

1.1 PROJECT BACKGROUND

The chemical industry in the UK comprises businesses of a range of sizes. Most larger

organisations are members of the Chemical Industries Association (CIA) and they handle

approximately 80% of the UK chemical business but employ only 20% of UK chemical workers

(these figures came from an informal discussion with the Chemical Business Association

(CBA)). This industry sub sector was surveyed in 2005 (JS2002998 ‘A workplace survey on the

control of task specific exposures to carcinogens, mutagens and reprotoxins in the UK chemical

industry’) and the findings reported in HSL report HSL/2005/35[1]

.

The purpose of this project was to survey small and medium sized enterprises (SMEs), many of

who are members of the Chemical Business Association (CBA). This industry sub sector

handles 20% of UK chemical business but employs 80% of UK chemical workers (again these

figures came from an informal discussion with the CBA). The aim was to assess the

effectiveness of exposure controls at those SMEs carrying out the import, reprocessing and

repackaging of chemical carcinogens and asthmagens. The objectives of the work were:

i) To engage with relevant internal and external stakeholders and assemble a schedule

of workplaces, representative of this industry sector, to be visited. Stakeholders

included HSE’s Hazardous Installations Directorate (HID) and the CBA. The CBA

provided valuable assistance by liaising with members to secure agreement to

support this project.

ii) To visit up to 30 workplaces and assess handling practices and exposure controls

for carcinogens and/or asthmagens. The assessment methodology included (where

possible) a quantitative exposure assessment, either by biological monitoring or air

sampling.

iii) To analyse the findings and compile a final report to compare and contrast with the

findings from JS2002998. If appropriate, the report findings may also be used to

inform possible future work by HSE or industry relating to exposure control at the

import, reprocessing and repackaging of chemical carcinogens and asthmagens.

A listing of some 15 companies was provided by the CBA and a further five companies were

sourced from internal HSE sources. Four of this five were formulators of the azo dye CI Solvent

Red 164 following concerns that this substance can metabolise within the body to ortho

toluidine and aniline. The Surface Engineering Association (SEA) identified two companies as

suppliers of nickel solutions to the industry. A programme of cold calling was also undertaken.

Of those contacted, ten businesses, described below and identified as sites A - J, indicated they

decant and repack and agreed to assist this survey.

Sites A, B, C and D are formulators of dye penetrant solution reported as containing the azo dye

CI Solvent Red 164. Site C also supply a diesel marker concentrate containing the azo dye CI

Solvent Red 24.

Site E take delivery of a concentrated solution of hydrazine hydrate (hydrazine is a carcinogen)

and dilute it before selling on to end users.

2

Site F manufacture potassium chromate solution using chromic acid flake. This and the

resulting potassium chromate solution contain chromium in its hexavalent state (a known

carcinogen and respiratory sensitiser).

Sites G and H manufacture nickel solutions for the electroplating industry using solid nickel

sulphate. Nickel sulphate is a carcinogen and also a respiratory sensitiser.

Site I uses azodicarbonamide (ADC) in the production of blowing agents for flooring material.

ADC is a respiratory sensitiser.

Site J receive bulk deliveries of trichloroethylene (a carcinogen), transfer to bulk storage and

then utilise an automated closed loop filling system to decant and repackage chlorinated

solvents, to be sold on for use as vapour cleaning/degreasing agents.

A HSL occupational hygienist visited all the above sites (accompanied at some by a HSE

inspector) and assessed work practices and exposure controls. Quantitative exposure

measurements were carried out using (where applicable) either air sampling and/or biological

monitoring. A full occupational hygiene report was then written and fed back to the company

via the site inspector.

1.2 OVERVIEW OF USE OF EACH SUBSTANCE

1.2.1 CI Solvent Red 164 (as reported) and CI Solvent Red 24

Site A receive (from site D) a pre-blended dye penetrant kerosene based solution containing CI

Solvent Red 164, which they then put into aerosol cans for supply to the non-destructive testing

(NDT) industry.

Site B receives CI Solvent Red 164 in a xylene-based solution. This is then blended with other

materials and then packed into metal aerosols or tins for supply to the NDT industry.

Site C receives CI Solvent Red 164 as a 70% solution in xylene. This solution is then used to

formulate dyes for gasoline and petrochemical products. This site also uses CI Solvent Red 24

to manufacture gas oil marker concentrate (the substance added to diesel to form ‘red diesel’).

CI Solvent Red 24 is considered to have similar toxicological properties as CI Solvent Red 164.

It is delivered to site as a powered solid and blended with other ingredients to make a solution

that is 0.5% CI Solvent Red 24.

Site D receives CI Solvent Red 164 in a 40-60% solution in a petroleum solvent. This is then

blended with kerosene and a plasticiser before being dispatched to site A.

1.2.2 Hydrazine

Site E receives an aqueous solution of hydrazine hydrate (80% hydrazine hydrate, 51%

hydrazine), which they then dilute down to various strengths (in an aqueous solution) to be sold

on to end users. A small proportion is retained by the site and used to manufacture hydrazine

mono nitrate.

1.2.3 Potassium chromate

Site F adds chromic acid flake to a mixture of water and potash liquor to make potassium

chromate solution.

3

1.2.4 Nickel sulphate

Both sites G and H use nickel sulphate in the production of nickel solutions for the

electroplating industry. At both sites solid nickel sulphate is added to water along with other

ingredients, allowed to mix and then transferred to containers to be sold on to the end user.

1.2.5 Azodicarbonamide (ADC)

Site I blends powdered ADC with a plasticiser. The resulting substance is then sold on as a

blowing agent for flooring material.

1.2.6 Trichloroethylene

At Site J, trichloroethylene is pumped into specialist chlorinated solvent closed loop system

containers. These are then dispatched for cleaning/degreasing purposes.

A more detailed summary of the processes above can be found in the results section of this

report.

1.3 UK REGULATORY POSITION FOR EACH SUBSTANCE

All exposure limits, UK BMGV’s and risk phrases except for CI Solvent Red 164 and CI

Solvent Red 24 have been taken from EH40/2005 amended 2011 and the European Chemical

Substances Information System – ESIS (http://esis.jrc.ec.europa.eu/home.php).

1.3.1 CI Solvent Red 164

Some azo dyes are known to metabolise in the body to o-toluidine (classified as a Category 2

carcinogen in the EU) and/or aniline (a Category 3 carcinogen). Concerns have been raised with

HSE regarding health risks from the use of one of these dyes (CI Solvent Red 164). As a result

of this, in 2008 the Working group on Action to control Chemicals (WATCH) advised that

users of Solvent Red 164 should regard the substance as a suspect (Category 3) carcinogen [4]

and asked HSE to investigate exposure and potential for carcinogenic substances to form.

Both aniline and o-toluidine can be measured in urine. There are currently no UK biological

monitoring guidance values (BMGV) for either substance. As a guideline the German BAT

value of ~900µmol/mol creatinine [2]

is used for aniline, there is no corresponding value to use

for o-toluidine so the reference range for those with no occupational exposure (NOE) have been

used as a guide.

1.3.2 CI Solvent Red 24

CI Solvent Red 24 is considered to have similar toxicological properties as CI Solvent Red 164.

The WATCH Committee concluded in 2008 that this material (CI Solvent Red 164) be treated

as a suspect carcinogen due to the potential of metabolisation in the body to ortho toluidine (o-

toluidine) and/or aniline.

1.3.3 Hydrazine

Hydrazine is classified as a carcinogen (R45) and also has the risk phrases, R10 (flammable),

R23/24/25 (toxic by inhalation, in contact with skin and if swallowed), R34 (causes burns) and

R43 (may cause sensitisation by skin contact). It can also be absorbed through the skin. There is

a UK WEL of 0.02ppm (as an 8-hr TWA).

4

1.3.4 Potassium chromate

Potassium chromate is a hexavalent chromium compound. Hexavalent chromium (CrVI

) is

classed as both a carcinogen and respiratory sensitiser. Due to these classifications there is a

requirement under Regulation 7 of the COSHH Regulations 2002 as amended (‘Prevention or

control of exposure to substances hazardous to health’) ACoP to ‘reduce exposure so far as is

reasonably practicable’. Potassium chromate the compound has also been assigned the risk

phrases R49 (may cause cancer by inhalation), R46 (may cause heritable genetic damage),

R36/37/38 (irritating to eyes, respiratory system and skin) and R43 (may cause sensitisation by

skin contact).

The UK workplace exposure limit for chromium is 0.5mg/m3 and for hexavalent chromium is

0.05mg/m3. There is also a UK biological monitoring guidance value (BMGV) set for urinary

chromium at 10µmol/mol creatinine in a post shift sample.

1.3.5 Nickel sulphate

Many nickel compounds are known respiratory sensitisers. Nickel sulphate had been assigned

the risk phrases R49 (may cause cancer by inhalation), R38 (irritating to skin), R61 (may cause

harm to the unborn child), R20/22 (harmful by inhalation and if swallowed), R42/43 (may cause

sensitisation by inhalation and skin contact), R48/23 (toxic: danger of serious damage to health

by prolonged exposure through inhalation) and R68 (possible risk of irreversible effects).

Soluble nickel compounds (such as nickel sulphate) are assigned an 8 hour TWA WEL of 0.1

mg/m3 (as Ni).

There is no UK Biological Monitoring Value (BMGV) for nickel. At the time the site visits

were carried out, the HSL biological monitoring database contained approximately 2000 results

for urinary nickel, from a wide range of industries. The 90th percentile of the urinary nickel data

in this database was approximately 24µmol/mol creatinine and this was adopted as a guidance

value for the purpose of this project.

1.3.6 Azodicarbonamide

Azodicarbonamide is classed as a respiratory sensitiser (capable of causing occupational

asthma). ADC also has the following health based risk phrase: R42 (may cause sensitisation by

inhalation). In the UK there is an assigned workplace exposure limit (WEL) of 1mg/m3 to ADC

(based on an 8-hr time weighted average reference period).

1.3.7 Trichloroethylene

Trichloroethylene is classified as a carcinogen (R45) and has also been assigned the following

health based risk phrases: R36/38 (irritating to eyes and skin) and R67 (vapours may cause

drowsiness and dizziness). The substance can also be absorbed through the skin. The current

UK WEL is 100ppm (as an 8-hr TWA). There is a UK BMGV of 35mmol/mol creatinine for

urinary levels of trichloroethylene in a post shift sample.

5

2. METHODOLOGY

2.1 THE DESIGN OF THE STUDY

Initially a list of 15 companies was drawn up in consultation with the CBA. Three of these

stated that they no longer decanted / repackaged or split carcinogens / asthmagens. One of the

companies (site I) used azodicarbonamide in the manufacture of a flooring material and as such

was visited.

Internal HSE sources provided the contact details of a further five companies. One of which

(site E) had earlier been visited as part of another project [1]

. When visited the company had

placed a heavy reliance on PPE when handling hydrazine. HSL decided that a re visit to assess

improvements could be included in this study.

Survey work carried out on worker exposures in the surface engineering industry generated two

companies that manufactured nickel plating solutions using nickel sulphate for the

electroplating industry (sites G and H).

In 2008 WATCH requested HSE to investigate the potential for CI Solvent Red 164 to

metabolise to o-toluidine and aniline, therefore the names of four reported formulators of CI

Solvent Red 164 (sites A through to D) were identified as part of this work. This included one

formulator of gas oil marker concentrate containing CI Solvent Red 24.

Cold calling produced two sites (Sites F and J). Site F manufactured potassium chromate and

Site J distributed trichloroethylene in closed loop systems.

For sites A through to D, F and J, workers were asked to volunteer in a biological monitoring

programme. Informed consent was obtained in accordance with HSG167 “Biological

monitoring in the workplace”, a practical guide to its application to chemical exposure’ (HSE,

1997).

This programme involved submitting pre and post shift urine samples for analysis. Samples

were requested to be given over five days that exposure would occur.

At sites C, F, G, H, I and J, air sampling was also carried out for the substance handled.

2.2 ANALYSIS DETAILS

A list of the substances measured and the corresponding methods are presented in Table 1,

overleaf.

6

Table 1 – List of the substances measured per site and analysis methods used

Site Substance(s) Sampling and analysis method

A, B, C, D Aniline (in urine) Gas chromatography with mass spectrometry

(GC-MS).

Ortho toluidine (in urine) GC-MS

Total inhalable dust (Site C

only)

MDHS14/3 ‘General methods for sampling and

analysis of respirable and inhalable dust’.

F Chromium (total) (airborne) MDHS91 ‘Metals and metalloids in workplace

air by X-ray fluorescence spectrometry’.

Chromium (hexavalent)

(airborne)

BS ISO 16740 – utilising Ion chromatography

(IC).

Chromium (in urine) Inductively coupled plasma mass spectrometry

(ICP-MS) with collision cell technology.

G & H Total inhalable dust (airborne) MDHS14/3 ‘General methods for sampling and

analysis of respirable and inhalable dust’.

Nickel (airborne) MDHS91 ‘Metals and metalloids in workplace

air by X-ray fluorescence spectrometry’.

Nickel (in urine) ICP-MS

I Total inhalable dust (airborne) MDHS14/3 ‘General methods for sampling and

analysis of respirable and inhalable dust’.

ADC (airborne) MDHS92 ‘Azodicarbonamide in air’.

J Trichloroethylene (airborne) MDHS80 ‘Volatile organic compounds in air’.

Trichloroethylene (in urine) Trichloroacetic acid in urine by Liquid

chromatography – mass Spectrometry – mass

spectrometry (LC-MS-MS).

7

3. RESULTS

3.1 FORMULATORS OF CI SOLVENT RED 164 (A – D) AND 24 (C) – AS REPORTED

The findings of this and similar work on end users of the dye was presented to WATCH in

October 2011[3]

.

Site A

Dye penetrant solution supplied from site D in 1000L IBCs was used to fill up aerosol cans. The

solution was transferred from the IBC to an aerosol supply tank by pneumatic pump and lance.

The empty aerosol cans arrived on a conveyor belt and were filled automatically in a closed

transparent chamber. They were then crimped and gassed remotely in a separate unoccupied

building. At the time of the visit the local exhaust ventilation (LEV) was being renewed.

Personal protective equipment (PPE) consisted of poly cotton overalls (with disposable Tyvek

also being available), reusable and disposable nitrile gloves.

There were up to 20 workers potentially exposed to CI Solvent Red 164.

Site B

Dye penetrant solution was delivered to site in 100L drums. These were fitted with taps which

were used to release the drum contents into an open tub. This tub was then poured into a mixing

vessel and other ingredients were added. The vessel was then lidded and the contents allowed to

mix. The resulting solution was then transferred to either aerosols (in a semi enclosed system)

or either 5 or 25L tins in an open workroom. Workers wore their own clothing along with

disposable gloves, either PVC, neoprene or nitrile. Respiratory protective equipment (RPE) was

worn when loading the mixer. LEV was fitted to the lidded mixing vessel and also to the aerosol

filling station.

Up to five workers were potentially exposed to CI Solvent Red 164.

Site C

CI Solvent Red 164 was delivered to site in either 1 tonne IBCs or 200L steel drums. The

contents of the IBC/drum were loaded into a sealed mixing vessel by vacuum transfer using a

flexible hose and lance, with the operator in close proximity to the drum. There was a moveable

captor hood available for use. The other ingredients were added to the vessel in the same

manner. Whilst still sealed, the vessel contents were allowed to mix. The final product was

gravity dropped to either 1 tonne IBC or 200L drum. PPE worn consisted of RPE, chemical

resistant clothing and gloves.

CI Solvent Red 24 was supplied in powder form in polythene lined cardboard boxes. The boxes

were placed in an extracted booth that had been constructed ‘in house’. The dye was

pneumatically transferred using a hand held lance to a mixing vessel where it was dissolved in a

hydrocarbon solvent along with other ingredients. This vessel had a moveable captor hood at its

opening. When mixed the vessel contents were piped to heated storage tanks and held there

overnight prior to dispatch. PPE worn consisted of a positive pressure full body suit with

integrated visor, two pairs of latex gloves and safety footwear.

There were 37 employees at the company with around ten exposed to both dyes.

8

Site D

About 18kg of dye penetrant concentrate was transferred from a 100kg drum to an empty drum

using a flexible hose and lance. Other ingredients were added to the drum manually. A flexible

captor hood was available for this part of the process but was not always used. This drum was

then moved by forklift truck to a closed vat. Using an electronic pump, the drum contents were

transferred to the vat with kerosene then pumped in from a remote storage tank. Two more

drums of dye penetrant were then added to the vat using the electric pump. The vat was then

closed and its contents stirred until mixed. The solution was then pumped to a 1000L IBC where

it was stored until ready to be delivered to site A. PPE worn consisted of safety shoes, poly

cotton top (workers’ own jeans), natural rubber gloves and safety glasses.

Three people were potentially exposed to CI Solvent Red 164.

Poor local exhaust ventilation (LEV) design was observed at Sites A, C (for handling CI

Solvent Red 164) and D. The location of the discharge point for the LEV system at Site B was

also found to be inappropriate.

At site B workers own clothing was worn, advice was given on the day that this was

unacceptable. Respiratory protective equipment (RPE) was worn at Sites B and C (when

handling CI Solvent Red 24). Face fit testing was not carried out at Site B, not applicable for the

RPE worn at Site C.

For all sites urinary levels of both o-toluidine and aniline were within the range for those with

no occupational exposure (up to 5µmol/mol creatinine and 10µmol/mol creatinine respectively)

with the exception of 3 aniline results. Two of these 3 should be treated with caution, as the

sample volumes were very low, resulting in significant sample dilution. The remaining sample

had a ‘low creatinine’ concentration (see foot note below Table 2).

CI Solvent Red 24 is used by site C in powder form. The total inhalable dust exposure (8-hr

TWA) was 3.3mg/m3 (below the COSHH exposure limit of 10mg/m

3) and the task based

exposure during the addition of the dye to a mixing vessel was 21.5mg/m3 (over a sampling

period of 73 minutes). Static sample measured concentrations were in the range <0.08 to

2.6mg/m3. Urinary aniline concentrations were within the range for those with no occupational

exposure with o-toluidine ‘not detected’ in any of the samples. During the visit the company

stated that they were looking to switch to a liquid form of the dye. Contact was made with the

company during the writing of this report and they stated,

‘In the last 6 months or so we have completed the process development for making red 24 in

liquid form and production is going well …… we do have some stocks of red 24 in powder and

will use these up slowly over the next 6 months or so, although we will predominantly using red

24 liquid’.

Urinary o-toluidine and aniline results for Solvent Red 164 and 24 are summarised in Table 2.

9

Table 2 Urinary ortho-toluidine and aniline results (CI Solvent Red 164 & 24)

Substance Total µmol/mol creatinine

<LOD LOD - NOE >BMGV Min Max

Ortho-toluidine 69 55 14 N/A <LOD 2

Aniline 47 1 43 0 <LOD 61#

Note - The concentration of analytes in urine can vary depending on the state of hydration of the

worker. To compensate for this it is common practice to adjust an analyte concentration by

dividing its concentration by the concentration of creatinine. This assumes the analyte is

excreted in the same way as creatinine and for aniline and o-toluidine this is not certain.

However, creatinine adjustment is unlikely to introduce significant errors except at the extremes

of the concentration range so adjustments with 'low' (<3 µmol/l) and 'high' (>30 µmol/l)

creatinine concentrations are flagged as 'low' or 'high'. In such cases the result should be

interpreted with caution.

NOE = Reference range for those with no occupational exposure (5µmol/mol creatinine for o-

toluidine and 10µmol/mol creatinine for aniline)

LOD = ~ 0.4µmol/mol creatinine for both substances

BMGV = ~900µmol/mol creatinine for aniline [2]

. There is no value for o-toluidine

# = Result should be treated with caution due to significant sample dilution

3.2 HYDRAZINE SUPPLIER – SITE E

A previous visit to the site (as part of another project) found that there was open handling of

hydrazine on a daily basis. The conclusions from this visit were that the exposure controls relied

heavily upon PPE. At the time of that visit the company had plans to make significant

improvements. By the time of the visit for this project these improvements had been carried out

and were in operation.

Hydrazine hydrate was delivered to the site by road tanker and off loaded into dedicated storage

tanks within bunded areas. When required the solution was pumped to the mixing vessel

through welded fixed steel pipe work. Water was then added to dilute the hydrazine down to

varying strengths. Using a sealed transfer system operated by a computer controlled filling

station, the solution was loaded into various sized containers. There were approximately five

workers potentially exposed to hydrazine. PPE worn (to protect the worker if there is a break in

containment) consisted of chemical protective suit, gloves and footwear.

Upon inspection the handling, dilution and repackaging of the hydrazine was carried out in

almost total containment, therefore controlling exposure to as low as is reasonably practicable

(ALARP). Experimental BM was attempted but this failed to produce valid and meaningful

results.

10

3.3 POTASSIUM CHROMATE PRODUCER – SITE F

Chromic acid flake was added to a vessel containing potassium hydroxide manually using a

scoop. The vessel contents were left to settle overnight. The following morning the supernatant

liquid was pumped through pipe work containing in line filters to a holding vessel and the

sediment at the bottom of the tank washed out into a waste pit. The pipe work was then used to

connect the holding vessel to the original vessel and the liquid pumped back over and stored

until required. The final product was pumped into 5L containers using a hose. The hose was

placed in the container and the contents pumped in. When the container was full the hose was

taken out and placed in the next container. The headspace of the mixing vessel was extracted

and there was LEV present at the drumming off point in the form of a moveable captor hood.

PPE worn consisted of safety wellingtons, chemical protective suit (during flake addition), poly

cotton overalls, apron, hard hat, safety glasses, a half mask respirator and a battery powered

RPE system.

There were ten employees in total with five of these potentially exposed.

The company’s COSHH assessments were not considered suitable and sufficient. These were

re-written with only minor improvements required. The company’s most recent 14 monthly

thorough examination and test report of LEV (carried out by an external contractor) was not

adequate with the issue being raised with the relevant HSE personnel. One worker wore a half

facemask which face fit testing had not been carried out on.

Inhalation exposures to chromium and hexavalent chromium were substantially less than the

relevant WELs. One worker had urinary concentrations of chromium above the reference value

for those with no occupational exposure with one sample exceeding the UK BMGV of

10µmol/mol creatinine by 1.5 times. Tables 3 and 4 present summaries of the air sampling and

the biological monitoring respectively

Table 3 Results of the air sampling for total and hexavalent chromium

Sample type No

Substance (mg/m3)

Total chromium range Hexavalent chromium range

Task based 8-hour TWA Task based 8-hour TWA

Personal 4 <0.01 – 0.05 <0.001 – 0.008 0.003 – 0.017 0.0004 – 0.003

Static 2 <0.01 – 0.38 - 0.002 – 0.174 -

Exposure limit (8-hr TWA) 0.5 0.05

Sampling durations ranged from 53 – 76 minutes for the personal samples and were 72 minutes

for the static samples.

11

Table 4 Results of BM for chromium (in µmol/mol creatinine)

Total <LOD LOD - NOE >BMGV Range

6 0 2 1 1.14 to 15.13

NOE = 3µmol/mol creatinine

LOD = <0.08µmol/mol creatinine

BMGV = 10µmol/mol creatinine

3.4 NICKEL PLATING SALTS PRODUCER – SITES G AND H

Site G

Nickel sulphate was placed into a grinder to break down large lumps. Once ground it exited the

grinder via a discharge point and entered a bucket. This bucket was then tipped into a 1200L

IBC containing water. Other ingredients were in bags and were manually emptied into the IBC.

The contents were mixed by agitation and then left to settle. After ~24 hrs the solution was

drummed off into 25L containers. The container was placed onto scales and filled with a lance

connected to the IBC. When the required weight had been delivered, the lance was raised, the

container removed, a fresh one put on and the process repeated. There were two people

potentially exposed. There was a portable fan and filter unit at the discharge point of the grinder

and a moveable captor hood above the grinder, which was then moved to the IBC when that was

in use. PPE worn consisted of polypropylene overalls, safety shoes, safety glasses, disposable

latex gloves and a FFP1 mask.

Site H

The operator stood on a platform of stacked wooden pallets and manually emptied nickel

sulphate from 25kg sacks into a mixing vessel containing water. Other ingredients were added

and the vessels’ agitator turned on to allow the contents to mix for 15minutes. The solution was

then dispensed into 25L drums. The drums were placed in a wooden crate located on the top of

scales. There were 16 drums in one crate. A hose was connected via cam lock to the mixing

vessel and the solution then pumped into the drums using the weight as a guide. There were

three captor hoods, one over the mixing vessel, one over the drumming off area and another

over a storage area. When not in use these hoods were blanked off. PPE worn consisted of poly

cotton overalls, safety boots, visor and rigger type gloves; disposable nitrile gloves were

sometimes used.

Two workers were potentially exposed to nickel sulphate.

The COSHH assessments at both sites required some improvements. The LEV hood over the

mixing vessel at Site H was blocked when the hatch was raised.

None of the exposures to inhalable dust and nickel exceeded relevant exposure limits. Inhalation

exposures at site H were less than the detection limits of the method.

12

For site G, none of the urine results exceeded the reference range for those with no occupational

exposure (up to 10µmol/mol creatinine). For site H three results exceeded this value with one

result exceeding the standard adopted for this project (24µmol/mol creatinine). For this site the

urine samples were not supplied on the date of the air sampling therefore they cannot be directly

compared.

Tables 5 and 6 present the summaries of the air sampling and biological monitoring

respectively.

Table 5 Results of the air sampling for inhalable dust and nickel

Sample type No

Substance (mg/m3)

Total inhalable dust range Nickel range

Task based 8-hour TWA Task based 8-hour TWA

Personal 3 <0.24 to 1.75 <0.02 to 0.30 <0.02 to 0.17 <0.001 to 0.03

Static 7 <0.24 to 0.31 - <0.01 to 0.03 -

Exposure limit (8-hr TWA) 10 (COSHH 2002) 0.1 (WEL)

Sampling durations ranged from 31 to 82 minutes for the personal samples and 31 – 38 minutes

for the static samples

Table 6 Results of BM for nickel (in µmol/mol creatinine)

Total <LOD LOD - NOE >Guidance value Range

24 0 21 1 2.08 to 31.48

NOE = 10µmol/mol creatinine

LOD = ~<2µmol/mol creatinine

Guidance value (standard adopted) = 24µmol/mol creatinine (the 90th percentile in HSL’s

monitoring database)

3.5 PRODUCER OF BLOWING AGENT FOR FLOORING MATERIAL CONTAINING ADC – SITE I

ADC was received in 20kg bags, and manually added by the operator to a mixing vessel already

containing a plasticiser. The contents of this vessel were allowed to mix until blended. LEV was

present at the headspace of the vessel. The process itself was a one man job but there were ten

who are trained to do it. PPE worn consisted of a battery powered positive pressure hood, cotton

overalls, safety footwear, high visibility vest, hard hat and safety goggles. There were 36 people

employed on site.

During the visit airborne particulate was visibly generated during when the bags of ADC were

emptied into the mixing vessel. As the LEV was connected to the headspace of the vessel and

not at the point where the bags were emptied, it offered no enclosure of the source. The COSHH

assessment needed improvement.

13

The inhalation exposure measured was nearly three times the WEL, Table 7. As ADC is a

respiratory sensitiser, control can only be treated as adequate if exposure is reduced to as low a

level as is reasonably practicable (ALARP).

Table 7 Results of the air sampling for total inhalable dust and ADC

Sample type No

Substance (mg/m3)

Total inhalable dust range ADC range

Task based 8-hour TWA Task based 8-hour TWA

Personal 1 24.7 4.6 15.1 2.8

Static 5 0.84 to 5.8 - 0.64 to 3.0 -

Exposure limit (8-hr TWA) 10 (COSHH 2002) 1 (WEL)

The sampling period for the task based exposure was 45 minutes

There are no biological monitoring methods for ADC

Battery powered RPE was worn which would supply the worker with a protection factor of 20.

This would be adequate if the exposures obtained above were typical, however control of

exposure should be achieved by other means prior to the provision of protective equipment

(COSHH 2002 as amended) such as improvements to the LEV system.

3.6 REPACKAGING OF TRICHLOROETHYLENE INTO CLOSED LOOP SYSTEMS – SITE J

Trichloroethylene was delivered to site by road tanker, pumped to a bulk storage tank and stored

until needed. When required the solvent was pumped into specialist closed loop systems using a

hydraulic lance connected to a semi automated filling station. One person operated this filling

station while another puts the lids on the closed loop system. There was LEV at the end of the

lance at the point where the trichloroethylene was dispensed. PPE worn consisted of safety

footwear, high visibility jacket, reusable chemical protective gloves, safety glasses and poly

cotton overalls. There were 23 people employed at the company with up to five potentially

exposed to trichloroethylene.

The companies LEV report did not constitute a thorough examination and test and the COSHH

assessment needed improvement.

Measurements showed that exposures to trichloroethylene during transfer of solvent to the

closed loop system were low. Measurable concentrations were obtained at the source and also

from the top of the closed loop tanks in the storage area, possibly due to residue, however all

concentrations were significantly below the WEL. The BM results confirm this. Tables 8 and 9

present the summaries of the air sampling results and biological monitoring results respectively.

14

Table 8 Results of air sampling for trichloroethylene

Sample type No Trichloroethylene (ppm)

Task based 8-hour TWA

Personal 2 3.9 to 4.1 0.5

Static 7 0.6 to 20.0 -

Exposure limit (8-hr TWA) 100 (WEL)

Sampling durations for the personal samples were 56 and 60 minutes and for the static samples

ranged from 40 to 50 minutes

Table 9 Results of urine sampling for trichloroethylene (in mmol/mol creatinine)

Total <LOD LOD - NOE >BMGV Range

14 0 N/A 0 0.2 to 4.1

NOE = N/A – no value

LOD = ~0.08mmol/mol creatinine

BMGV = 35mmol/mol creatinine

15

4. DISCUSSION

4.1 CI SOLVENT RED 164 AND 24

At all the sites CI Solvent Red 164 was handled in solution, thus limiting the potential for

inhalation exposure. There was the potential for dermal exposure at all sites, however, this

appeared to be reasonably well controlled with a combination of measures. One measure was

enclosure of the process and was applicable to aerosol filling (sites A and B) and sealed / closed

mixing vessels (sites B, C and D).

LEV was present at sites B, C and D, however deficiencies were present at each. These included

incorrect locations of exhaust points (site B) and limited capture of the captor hoods at sites C

and D. The LEV systems at site A were in the process of being renewed at the time of the visit.

At site B workers wore their own clothing. It was pointed out at the time of the visit that this

was not acceptable. At site D workers wore their own trousers but a company issue polo shirt.

At the other two sites company issue overalls were worn (poly cotton – site A or chemical

resistant – site C).

The extraction booth at site C for handling CI Solvent Red 24 had been constructed ‘in-house’.

There was no commissioning report available. HSE Guidance HSG258 ‘Controlling airborne

contaminants at work A guide to local exhaust ventilation (LEV) recommends the use of a

commissioning report as a reference with which to compare future thorough examination and

tests. Further process improvements were planned by the company, which included using the

dye in liquid form once all the powdered dye had been used. The operator wore a full

compressed air fed positive pressure suit with integrated visor, which had an APF of 200.

Urinary levels of aniline for formulators of CI Solvent Red 164 and CI Solvent Red 24 (Sites A

to D) were within the reference range for those with no occupational exposure (up to

10µmol/mol creatinine) for all samples except three. These three results should be treated with

caution as two were significantly diluted prior to analysis and the third contained low creatinine

levels (the urine was dilute). However these three were significantly below the German

Guidance value of 900µmol/mol creatinine [2]

(there is no UK guidance value).

All urinary levels of o-toluidine were within the reference range for those with no occupational

exposure (up to 5µmol/mol creatinine).

Based on the measurements taken in this work it may be concluded that CI Solvent Red 164 is

not metabolised to ortho-toluidine. Only one formulator of products containing CI Solvent Red

24 was visited as such this report cannot make the same conclusion.

4.2 HYDRAZINE

Hydrazine was handled in almost total containment thus controlling exposure to hydrazine to

ALARP.

4.3 POTASSIUM CHROMATE

Chromic acid flake was handled in a slow and controlled manner. The resulting worker

inhalation exposures appeared to support this. However there was a high measured

concentration of hexavalent chromium for one of the static samples (0.174mg/m3) which

indicates the potential for generation of airborne particulate containing chromium.

16

Although inhalation exposures were low the biological monitoring results indicate exposure to

chromium. There was a high potential for dermal exposure to the potassium chromate solution

when removing filters from housings, drumming off and from splashes. Protective gloves were

worn when carrying out these tasks but good hygiene practices also need to be followed to

prevent exposure by other routes i.e. ingestion. Face fit testing of the negative pressure RPE

used by one of the workers had not been face fit tested, it was also observed that this mask was

dirty on the inside.

The companies COSHH assessments were not suitable and sufficient at the time of the visit.

Once they had been re-written only minor amendments were needed.

4.4 NICKEL PLATING SALTS

Inhalation exposure to nickel at both sites appeared to be well controlled by a combination of

controlled manual handling of the nickel sulphate and LEV. The low inhalation exposures

obtained support this. However the LEV hood at site H was blocked when the hatch of the

mixing vessel was raised.

At site G the urine results were all within the range for those with no occupational exposure,

indicating good control of nickel by all routes.

The biological monitoring results at site H exceeded the range for those with no occupational

exposure for three samples with one also exceeding the standard adopted for this work. These

samples were not from the same day as the air sampling and so could not be compared to

inhalation exposures obtained.

The COSHH assessments at both sites required improvements.

4.5 ADC

Exposure to ADC was not properly controlled at Site I; significant quantities of airborne

particulate were generated when adding ADC to the mixing vessel. The LEV system was fixed

to the headspace of the mixing vessel and therefore was not extracting at the source of the

exposure. The resulting 8-hr TWA inhalation exposure was nearly three times the WEL of

1mg/m3 (from a much higher task based exposure). ADC is a respiratory sensitiser and as such

control can only be considered adequate if exposure is reduced to as low a level as is reasonably

practicable (ALARP). LEV improvements and more controlled working practices would lower

exposures.

4.6 TRICHLOROETHYLENE

Worker exposure to the trichloroethylene occurred when the lance entered and exited the closed

loop system. There was LEV at the dispensing end of the lance i.e. at the source. As expected

with the closed loop type of system the air sampling and biological monitoring showed

exposure to be well controlled.

The LEV TExT report did not have all the required information to be considered a through

examination and test. The COSHH assessment also needed improvement.

4.7 COMMON THEMES

Deficiencies in the COSHH assessments at sites F, G, H, I and J were observed with the

individual site visit reports stating what was required by way of improvements.

17

A common denominator during the visits was poor LEV design. This was observed at Sites A

(however this was being renewed during the visit), B, C, D, H and I.

Inadequate LEV thorough examination and test reports were observed at Sites F and I. For site F

the issue was taken up with the relevant HSE inspector.

Face fit testing was not carried out, where applicable at Sites B and F. This is a requirement of

the COSHH Regulations 2002 as amended.

18

5. CONCLUSIONS

Based upon the results obtained in this work, the azo dyes CI Solvent Red 164 and CI Solvent

Red 24 are not metabolised to ortho toluidine.

At eight of the ten sites visited there was direct worker handling of the carcinogen / asthmagen.

Whereas the majority of these sites did this in a careful and controlled manner, one site did not

and thus elevated inhalation exposures were obtained.

There were flaws in LEV design as discussed earlier which resulted in the system not

controlling exposure at source i.e. incorrect positioning of hoods and the blocking of hoods by

vessel hatches.

Where applicable (sites F through to J) and with the exception of one site (I), all inhalation

exposures were low. There was, however evidence of a lack of control of exposure via other

routes (i.e. ingestion / dermal) from the biological monitoring results of sites F and H.

With the exception of site E further improvements could have been made at each site visited in

order to control exposure to carcinogens / asthmagens to ALARP.

19

6. RECOMMENDATIONS

Recommendations were made by HSE for improvements to management systems and / or

exposure control at all sites apart from site E where none were required.

The recommendations made are summarised below:

o Improvements / reviews of COSHH assessments

o Carry out improvements to LEV systems; this included re-designing systems to offer better

control at source

o Compare future LEV through examination and test (TExT) reports to HSE guidance in

order to ascertain whether the report is comprehensive enough

o Introduce where applicable a programme of health surveillance when using asthmagens

o Improvements to PPE programmes including face fit testing, RPE maintenance and correct

glove selections.

20

7. REFERENCES

[1] ‘A workplace survey on the control of task specific exposures to carcinogens, mutagens and

reprotoxins in the UK chemical industry’, C Keen 2005.

(http://www.hse.gov.uk/research/hsl_pdf/2005/hsl0535.pdf).

[2] ‘List of MAK and BAT Values 2012: Maximum Concentrations and Biological Tolerance

Values at the Workplace’.

http://onlinelibrary.wiley.com/book/10.1002/9783527666034

[3] ‘The supply and use of CI Solvent Red 164 as a penetrant dye in the detection of cracks in

metal components’, J Cooke, 2011

http://www.hse.gov.uk/aboutus/meetings/iacs/acts/watch/251011/watch-2011-4.pdf

[4] ‘The use of liquid dye penetrants containing the azo dye compound CI Solvent Red 164 in

the detection of flaws or cracks in metal components.

http://www.hse.gov.uk/foi/internalops/sectors/manuf/030810.htm

Published by the Health and Safety Executive 12/13

Assessment of exposure to carcinogens and asthmagens in the contract import, processing and repackaging industries

Health and Safety Executive

RR983

www.hse.gov.uk

The aim of this research was to assess the effectiveness of exposure controls at small and medium-sized enterprises (SMEs) carrying out the import, reprocessing and repackaging of chemical carcinogens and asthmagens.

Visits were made to 10 companies which decant and repack chemicals including carcinogens and asthmagens. The visits examined handling practices and exposure controls, and included, where possible, a quantitative exposure assessment, either by biological monitoring or air sampling.

Although there were some examples of good practice, overall, this survey found that control of exposure was variable in its effectiveness. Deficiencies in COSHH assessments (Control of Substances Hazardous to Health) and/or inadequacies in engineering controls (LEV - Local Exhaust Ventilation) and/or PPE (Personal Protective Equipment) were found at all but one site visited.

Recommendations for improvements to management systems and/or exposure control were made for all but one site. Recommendations included the need to improve LEV systems; to introduce health surveillance programmes; and to improve PPE programmes, including ensuring the introduction of fit testing for Respiratory Protective Equipment (RPE), undertaking routine RPE maintenance and ensuring correct glove selection.

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.