Chemical Hazards: Health Risk Assessment

and Exposure Evaluation

The companies belonging to the Royal Dutch/Shell Group of companies are separate and distinct entities, but in this
document the collective expressions "Shell" and "Group" are sometimes used for convenience in contexts where reference
is made to the companies of the Royal Dutch/Shell Group in general. These expressions are also used where no useful
purpose is served by identifying the particular company or companies.
This document is prepared by Shell Internationale Petroleum Maatschappij B.V. (SIPM) as a service under arrangements in
existence with companies of the Royal Dutch/Shell Group; it is issued for the guidance of these companies and they may
wish to consider using it in their operations. Other interested parties may receive a copy of this document for their
information. SIPM is not aware of any inaccuracy or omission from this document and no responsibility is accepted by SIPM
or by any person or company concerned with furnishing information or data used in this document for the accuracy of any
information or advice given in the document or for any omission from the document or for any consequences whatsoever
resulting directly or indirectly from compliance with or adoption of guidance controlled in the document even if caused by a
failure to exercise reasonable care.

September 1995
SHELL HEALTH, SAFETY AND ENVIRONMENT COMMITTEE

The copyright of this document is vested in Shell Internationale Petroleum Maatschappij B.V., The Hague, The Netherlands.
All rights reserved.

AMENDMENT RECORD SHEET

Chapter
No.

Section
No.

Description

All

All

Original paper issue

All

All

Conversion to CD-ROM

Correction/
Update

Date

Initials

Reference
Indicator

DM

EPO/61

Sep 95
Conversion

Oct 95

TABLE OF CONTENTS
INTRODUCTION

HEALTH RISK ASSESSMENT

1.1

GATHERING INFORMATION ON CHEMICAL AGENTS (HRA Step 3)

1.1.1
1.1.2
1.1.3
1.1.4

4
4
7
9

Identification of chemical agents

Information on hazard
Nature and degree of exposure
Screening (compliance) and performance criteria

1.2

EVALUATING THE RISK TO HEALTH (HRA STEP 4)

11

1.3

DECIDING ON REMEDIAL (CORRECTIVE) ACTION (HRA Step 5)

13

1.3.1
1.3.2
1.3.3
1.3.4

13
14
14
15

Types of control measures

Examples of inadequate control
Examples of control improvements
Factors to consider in the selection of control measures

1.4

FURTHER READING

16

MONITORING OF CONTROLS

17

2.1

DEVISING A MONITORING STRATEGY

17

2.2

HAZARDOUS SUBSTANCES

17

2.3

MONITORING METHODS

18

2.4

TRIGGER POINTS

19

2.5

MANAGEMENT OF EXPOSURE MEASUREMENT

21

2.6

SUPPLEMENTARY MONITORING METHODS

21

EXPOSURE MEASUREMENT

23

3.1

AIR MEASUREMENT

23

3.1.1
3.1.2
3.1.3
3.1.4
3.1.5
3.1.6

23
23
23
23
24
25

Selection of an appropriate sampling and analytical methodology

Validation of sampling and analytical methods
Records
Types of exposure measurement survey
Personal exposure protocols
Interpretation of results (checking compliance)

3.2

BIOLOGICAL MONITORING

26

3.3

QUALITY ASSURANCE

26

3.3.1
3.3.2

26
27

Good practice
Managing critical quality control points

3.4

COMPETENCE

27

3.5

FURTHER READING

27

3.5.1

27

HSE 071
September 1995

Air measurement

3.5.2
3.5.3
3.6

Biological monitoring
Quality assurance

ACRONYMS

28

APPENDIX 1

INTRODUCING TOXICOLOGY - AN OUTLINE

29

APPENDIX 2

COMMON TOXICITY TERMS

31

APPENDIX 3

OVERVIEW OF EXPOSURE MEASUREMENT STRATEGY

34

APPENDIX 4

CALCULATION FOR COMBINING FRACTIONAL

EXPOSURE MEASUREMENTS TO ALLOW COMPARISON
WITH A SPECIFIED REFERENCE PERIOD

35

UNITS OF MEASUREMENT

35

CALCULATIONS

35

APPENDIX 5

ii

28
28

ADDRESS LIST

37

HSE 071
September 1995

INTRODUCTION
The Shell HSE Committee publication on 'Health Risk Assessment' issued in September
1994, provides general advice on carrying out Health Risk Assessment (HRA) of chemical,
physical, biological and ergonomic health hazards found in the workplace, in a structured
manner. HRA is the tool for implementing the Hazard and Effects Management Process
(HEMP) as it relates to health hazards.
The Health Risk Assessment guide is referred to as the 'General Guide' throughout this
document and Health Risk Assessment as HRA.
This publication on 'Chemical Hazards: Health Risk Assessment and Exposure Evaluation'
supplements the General Guide by providing advice on assessing risks to health arising
from chemical agents in the workplace. The information is advisory and is intended for the
use of Assessment Teams.
The guide is divided into three parts as follows:Part 1: Health Risk Assessment:
Part 1 expands on the following HRA Steps introduced in the General Guide
focusing on chemical hazards:Step 3:

Gathering Information on chemical agents, personal exposures and

screening and performance criteria. (HEMP: Identify)

Step 4:

Evaluating the risk to health. (HEMP: Assess)

Step 5:

Deciding on remedial action (control measures) to reduce exposures to 'as

low as reasonably practicable' (ALARP). (HEMP: Control and Recover)

In addition to these Steps, the assessment should be recorded (Step 6) and reviewed
for continuing validity (Step 7).
Part 2: Monitoring of Controls (HEMP: Monitoring and corrective action)
Monitoring of controls to check on their continuing effectiveness is necessary to
prompt corrective action and thereby ensure that exposures continue to be
controlled to ALARP. Part 2 recommends monitoring methods, together with
identifying triggers for when and how often they should be implemented.
Part 3: Exposure Measurement
Collection of quantitative exposure data may be necessary as part of the HRA itself
or as part of the monitoring of controls. Part 3 provides an overview of what is
involved in data collection and its subsequent interpretation under the headings air
measurement, biological monitoring, quality assurance and competence.

HSE 071
September 1995

HEALTH RISK ASSESSMENT

The implementation of HRA involves the following steps:-

Details on the process of HRA are given in the Shell HSE Committee publication on
Health Risk Assessment, September 1994, which is referred to as the 'General Guide'
throughout this document.

HSE 071
September 1995

In order to assist in the HRA of chemical hazards additional guidance is given in Section 1
specific to chemical agents, focusing on HRA Step 3, gathering information, Step 4,
evaluating the risk to health, and Step 5, deciding on remedial action.
This document deals with workplace risk assessment of chemical hazards.
Risk assessment terminology associated with chemical agents is also defined by the
European Union in the Regulation on Risk Assessment of Existing Substances. For
completeness and comparison purposes, the definitions associated with this Regulation are
given as a footnote to Appendix 1.

HSE 071
September 1995

1.1

GATHERING INFORMATION ON CHEMICAL AGENTS (HRA Step

3)
HRA begins by gathering the following information:-

agents in the workplace and their harmful effects;

the nature and degree of exposure to the agents;

screening and performance criteria against which to evaluate the risk to health.

The guidance applies to toxic, corrosive, irritant and sensitising aspects. Hazards resulting
from flammability, explosivity or oxidising (as it relates to fire propagation) characteristics
need to be addressed separately.

1.1.1 Identification of chemical agents

Create an inventory of all chemical agents stored/used/produced in each work area and
obtain health hazard information on each. Maintain a register of manufacturer's/suppliers
health and safety data sheets.
To ensure that the list is comprehensive, consider:-

feedstocks and additives;

intermediates and by-products;

final products;

ancillary chemicals used in the process, e.g. catalysts, vessel flushing agents, solvents,
acids and alkalis used for pH adjustment, drilling mud chemicals, biocides,
surfactants;

waste products, e.g. residues, gaseous emissions, dirty rags, empty contaminated
containers;

proprietary products e.g. cleaning agents, oils and greases, paints, degreasing agents,
glues;

building, plant and equipment construction materials e.g. insulation and fire retarding
materials, paints, gaskets and packing materials;

chemical agents produced as a result of tasks or processes, e.g. welding fumes and
gases, oil mist, vehicle exhausts.

1.1.2 Information on hazard

By way of background information on the hazards of chemical agents, an introduction to
toxicology and a list common toxicity terms are given Appendix 1 and 2 respectively.
Advice on where to obtain information on the harmful effects of chemical agents is given
below. In addition, guidance on the routes of in-take and key physico-chemical properties
of interest when assessing exposures is provided.
a)

Sources of information

Information may be obtained from, for example:-

manufacturer's and supplier's health and safety data sheets, labels or manuals on
products;

databases or published texts;

Operating Company and Service Company guidance material;

or advice may be obtained from:4

HSE 071
September 1995

occupational health advisers such as occupational hygienists, toxicologists,

occupational health physicians;

organisations with knowledge and experience of the activity or operation, e.g. industry
associations, government health and safety advisory bodies.

b)

Routes of exposure

Exposure can occur via three routes:-

Inhalation (via the lungs);

Skin contact, either directly or from contaminated surfaces or clothing. Some

chemicals are able to enter the body through intact skin, e.g. xylene, toluene, phenol,
hydrofluoric acid. In addition, tasks involving high pressure equipment may result in
injection of chemicals through the skin, e.g. paint spraying, grease injection, or by
contact with sharp objects which are themselves contaminated;

Ingestion (via the mouth), either directly or by consuming contaminated food or drink.
Smokers are vulnerable to transferring chemical agents on their hands to their mouth if
they have not ensured their hands are clean before smoking a cigarette, as are nail
biters.

c)

Physical and chemical properties

Both the physical and chemical properties of a chemical agent may affect its intrinsic
hazard or the potential for an increase in the exposure level.
General considerations are:-

different physical forms of the same chemical agent may present different hazards,
e.g. a granule or flake may present negligible hazard but, when ground into dust of a
respirable size, it may be very hazardous;

many chemicals contain impurities which could present a greater hazard than the
substance they contaminate, e.g. crystalline silica is often present in mineral-based
materials which would otherwise be of low toxicity;

fibres which are toxic because of their length and diameter (see Particulates below);

some chemical processes may be known to cause ill health but the causative agent(s)
may not have been identified, e.g. isopropyl alcohol production using the strong acid
process which causes lung cancer;

additive or synergistic effects (see Appendix 2) of mixtures, e.g. the Special Boiling
Point Solvents (SBPs) contain n-hexane in concentrations ranging from <1 to 50%
where n-hexane is known to cause effects on the nervous system;

the toxicity of a solvent carrier may enhance skin penetration of the 'active' chemical.

Some specific items are:-

Gases/vapours
-

Relative vapour density

The weight of a specific volume of a gaseous chemical agent compared to the
weight of the same volume of air.
If the relative vapour density of a gas is greater than 1, the gas will sink and tend
to collect at floor level or in depressions. Such collection can result in unexpected
high exposures as well as a potential fire and explosion hazard for those which
are flammable. In some circumstances, the gas may completely replace air,
including the oxygen which is essential for life, leading to asphyxiation
(suffocation).

HSE 071
September 1995

For low concentrations of gases or vapours usually involved in occupational

exposures, unless the result of an incidental release, such separation does not
occur.

Liquids/solids
-

Vapour pressure
The pressure of a vapour produced by a liquid or solid at a specified temperature
and is usually expressed in Pascals (Pa) or millibar (mb) at 20C. Chemicals with
a high vapour pressure are described as volatile.
The higher the vapour pressure the higher the potential concentration in air. The
vapour pressure of a chemical increases with temperature.
The boiling point of a chemical agent is a useful indicator of its volatility. One
that boils at or below the reference temperature and pressure of 20C and 101.3
kPa means it is usually present in gaseous form. Thus the closer the boiling point
of a liquid is to these reference levels the greater its vapour pressure and hence its
tendency to vaporise.

Solubility and molecular weight

The solubility of a chemical in the surface layer of the skin is the major
determinant of the potential for a substance to be absorbed into the body via this
route. Fat soluble compounds are generally well absorbed by the skin whilst
water soluble substances are not. In addition, the size of the molecule is also an
important factor in skin absorption. Molecular weight or, more accurately,
molecular volume, will affect absorption, although to a much lesser degree than
solubility. Large molecules (molecular weight > 500) will only be absorbed very
slowly, if at all.
Those chemicals easily absorbed via the skin are usually given a 'skin' notation in
the references listing occupational exposure limits (see 1.1.4.).

Mixtures
Volatile mixtures present special problems in terms of the concentration of individual
components in air and the possibility of additive and synergistic effects. It is important
to know the different components so that the health effect can be assessed for the
relevant ones. See Appendix 2 for a definition of 'Additive effect' and 'Synergistic
effect'. In addition, the different components may have differing vapour pressures.

Particulates
These are divided into:-

dust: solid particles in air which may be amorphous, crystalline or fibrous

fume: condensed solids in air

mist: liquid droplets in air

smoke: small gas borne particles derived from incomplete combustion

Aerosol is a general term for solid or liquid airborne particulate matter.

-

Particle size and shape

In respect of inhalation, the particle size and shape play a significant role in the
ability of a particulate to become and remain airborne, as well as their ability to
enter and penetrate into the respiratory system. In simplified terms the following
applies:o

particulates that have Stokes diameter of less than 100 micrometres can enter
the respiratory tract and are termed the 'Total Inhalable Fraction'*

HSE 071
September 1995

< 7 micrometres diameter can be inhaled deep into the lungs and are referred
to as the 'Respirable Fraction'*. This size range is of particular relevance to
substances which cause pneumoconiosis or related effects.

* CEN 481: Workplace atmospheres - Size fraction definitions for measurement of airborne
particles.

fine fibrous dusts with an aspect ratio (length to breadth) of at least 3:1
become easily aligned with the airstream of inhaled air and are regarded as
respirable;

particles of irregular shape are more easily trapped in the mucous lining of
the upper respiratory tract.

1.1.3 Nature and degree of exposure

Information on exposure should include:-

who is exposed;

exposure level; and

related circumstances (work practices, existing controls).

For the chemical agents to which people are exposed see 1.1.1.;
Prior to commencing a review of exposure to each chemical agent identified within an
Assessment Unit*, it may be possible to simplify the process by grouping chemicals
on the basis of their hazardous properties and the way they are being handled.

An Assessment Unit may comprise for example a small complete operational site, a self-contained
segment of a large or complex site, or a group supporting a single business process, so defined as to assist
in the management of HRA within an organisation.

Be alert to individual chemicals in mixtures which pose specific hazards. Examples of

these are:-

Liquefied Petroleum Gas (LPG) normally comprises a mixture of C3 to C5 saturated

hydrocarbons. However, LPG derived from 'cracking processes' may contain 1,3butadiene which is classified by IARC (International Agency for Research on Cancer)
as Category 2B probably carcinogenic to humans (IARC monograph no 54, 1992).

Chemical solvents can be grouped and assessed on the basis of their functional
composition, e.g. alcohols, ketones, aromatic solvents, paraffinic solvents. However,
the solvents may contain components with the potential for causing serious ill-health
effects, e.g. benzene (a carcinogen) or n-hexane (a nervous system toxin).

a)

Who is exposed

Employees and other workers should be assigned to Job Types based on similar tasks and
thus having similar potential for exposure. Job Types may represent one or more jobs,
reflecting likely exposure patterns (See General Guide Steps 2.4 Job Types and 2.5 Tasks
and Hazardous Agents). Job Types which involve similar tasks can be combined.
Ensure that all potential exposures to hazardous chemical agents have been identified for
assessment by reviewing:-

the individual operations which are carried out, e.g. manufacturing, processing,
blending, storage, distribution, transport, disposal;

the specific activities/tasks, e.g. sampling, filter changing, pump maintenance;

the personnel involved either directly or indirectly, e.g. process operators,

maintenance technicians, cleaners, laboratory technicians, office workers, supervisors;

HSE 071
September 1995

all others including contractors, temporary staff including students and trainees,
visitors or persons working in the vicinity of an activity, community or site
neighbours;

all the potential points of release of the chemical agents in question, e.g. vents and
exhausts, leaking pumps, valves, in addition to those tasks involving potential
exposure.

Some persons may be at increased risk for whom special consideration is required and
include:-

pregnant women and nursing mothers;

untrained or inexperienced persons (e.g. new recruits, temporary workers);

persons working in confined or poorly ventilated spaces;

persons with pre-existing conditions (e.g. bronchitis, sensitised to the chemical

concerned, asthmatics);

persons receiving medications which might increase their susceptibility to toxic

effects;

persons suffering from malnutrition or a chronic infection;

smokers, who may be at increased risk due to additive or synergistic effects.

All such persons should be identified and appropriate action taken.

b)

Exposure Level

The personal exposure level to a particular chemical agent is established by estimating:-

the magnitude of exposure (e.g. breathing zone concentration of the agent or

opportunity for skin contact)

the frequency of exposure (times per day, week, month, year);

the duration of exposure (minutes or hours per day);

taking into account the likelihood of an increased level of exposure during normal
operations or resulting from abnormal conditions or foreseeable emergencies.
Exposure levels may be estimated by direct measurement or from relevant data and
experience. Refer to Part 3 'Exposure Measurement' for an outline on measurement
strategies.
For both direct measurement and qualitative assessment, observation of the tasks involving
potential exposure is essential. This should also include discussion with supervisors and
staff doing the work to ensure a clear understanding of what is involved and any potential
for loss of control, thereby increasing the potential for exposure.
In addition to routine work, also consider activities such as one-off maintenance jobs, plant
start-up, shutdowns, commissioning, turn-arounds, etc.

Magnitude of exposure
Refer to Section 1.1.2. for those chemical and physical properties which affect the
potential concentration of a chemical agent in air or its ability to be absorbed via the
skin. For those chemical agents which cause an effect by direct contact, e.g. irritants,
corrosives and sensitisers, consider the potential for contact with the skin, eyes or
respiratory tract.
Where there is a combination of exposures to different chemical agents, the combined
health effect should be considered (see Appendix 2 Additive and Synergistic Effects).

Frequency and duration of exposure

HSE 071
September 1995

The pattern and total time of exposure during the entire work period can be
determined by observing the task(s)/process, by asking relevant supervisors and the
people actually doing the work.
Remember that certain Job Types, e.g. maintenance technicians, may carry out many
tasks in any one work period and also across more than one Assessment Unit,
particularly in a large chemical plant or refinery. Exposures may be to the same,
similar or totally different chemical agents. Exposure times in such circumstances will
also vary considerably.

Likelihood of an increase in exposure

Many changes in process or equipment could result in increases in potential exposure,
typical examples being:-

c)

change in physical form of the agent as a result of the task (e.g. a liquid changed
to an aerosol by spraying, a solid changed to a respirable dust by grinding);

an increase in the exposure period as a result of a greater workload;

pump/flange/equipment leakage;

faulty high level sensor leading to vessel overflow;

reduced airflow into local exhaust ventilation system owing to, e.g. a blocked
filter, faulty fan operation, system leakages or mal-adjustment of ventilation
ducting dampers;

higher in-take during heavy physical labour.

Related circumstances (work practices, existing controls)

The level of exposure is influenced by the effectiveness of existing control measures and
their usage by staff.
See the General Guide item 3.2.3. for general advice on reviewing existing control
measures and judging their adequacy. Additional information in respect of control
measures for chemical agents is given under Sections 1.1.4. and 1.3. below.

1.1.4 Screening (compliance) and performance criteria

Exposure should be controlled to a level 'as low as reasonably practicable' (ALARP) and
should, in any case, be less than the occupational exposure limit (OEL) for the agent in
question. In addition, the recommended measures to achieve a level ALARP for that agent
should be specified. The OEL and specifications for control are known as screening
(compliance) and performance criteria. These criteria may be in place prior to the HRA
commencing, or may be introduced as a result of an unsatisfactory level of control
identified during the HRA.
Definitions of OELs for chemical agents are given below. For reference to specifications
for control measures see the General Guide item 3.3.; further examples of controls are
given in Section 1.3. below.
a)

OEL: Personal exposure - air measurement

Many countries have identified Occupational Exposure Limits (OELs) for various chemical
agents - units are in parts per million (for gases and vapours), milligrams per cubic metre
(for all except fibrous dusts) or fibres per millilitre of air (for fibrous dusts). In general, the
limits comprise:-

a Time-Weighted Average (TWA) exposure: the TWA concentration for a normal 8hour workday and a 40-hour workweek, to which nearly all workers may be
repeatedly exposed, day after day, without adverse effect;

HSE 071
September 1995

a Short Term Exposure Limit (STEL): this is applied to chemicals with acute effects
and, in general, is a maximum allowable exposure over a 15 minute period; and, in
some cases,

a Ceiling Limit: the concentration that should not be exceeded during any part of the
working exposure.

Where a country has no OEL for a substance, Shell Companies are recommended to refer
to the documentation and Threshold Limit Values (TLV) list published annually by the
American Conference of Governmental Industrial Hygienists (ACGIH). Other reference
sources are the European Union Indicative Limit Values (ILVs - these are currently draft
limits), individual country's limits such as the United Kingdom's Occupational Exposure
Standards (OESs) and Maximum Exposure Limits (MELs), the Netherland's MAC
waarden, the German Maximale Arbeitsplatzkonzentrationen (MAKs) and Technical
Exposure Limits (TRKs).
If no OEL exists for a particular substance its supplier should be requested to provide a
working limit, together with evidence to support that limit. Alternatively, a request for an
advised limit may be made to Occupational Health Advisers in the Service Companies.
By exception, Shell Occupational Health Advisers may recommend an OEL lower (i.e.
more stringent) than other published limits for a substance where the lower limit is readily
achievable, or evidence exists to justify it.
b)

OEL: Personal Exposure - Biological Monitoring

Biological Limit Values (BLVs) have been set for a number of chemical agents. A BLV is
the maximum allowable concentration in body fluids of workers of a chemical or its
metabolite* which does not cause adverse effects. Shell Service Company recommended
BLVs are given in Report HSE 94.014 Laboratory Tests for Biological Monitoring and
Biochemical Effect Monitoring available from SIPM-HSE/50.
*

10

A metabolite of a substance is either a breakdown product or modified (more soluble)

form suitable for excretion by the kidney in the urine or by the liver into the intestine.

HSE 071
September 1995

1.2

EVALUATING THE RISK TO HEALTH (HRA STEP 4)

Using the information obtained in Step 3, the risk to health is evaluated by making a
judgement on:-

the 'severity' of the possible ill-health effect form over-exposure to the agent to give a
Hazard Rating;

the 'chance of over-exposure' to give an Exposure Rating;

The 'Hazard' and 'Exposure' Ratings are then evaluated in a Risk Matrix. Guidance on this
process is given in the General Guide.
The Exposure Rating indicates whether or not exposures to a particular agent are
adequately controlled when compared against the relevant screening and performance
criteria. Its purpose is to assist in deciding when additional control measures should be
implemented to reduce exposures. When combined with the Hazard Rating in the Risk
Matrix, priorities for action can be determined.
For ease of reference the Hazard Ratings, Exposure Ratings and Risk Matrix are
reproduced below.
Table 1: Hazard Ratings
HAZARD
RATING

DEFINITION(1) in terms of potential to cause 'Harm to People'(2)

NO INJURY OR DAMAGE TO HEALTH

SLIGHT INJURY/ILLNESS: Commonly causing nuisance not

affecting work performance or causing disability.
-

e.g. low toxicity dusts.

MINOR INJURY/ILLNESS: Affecting work performance, such as

restriction of activities (Restricted Work Case), or a need to take a few
days to fully recover (Lost Workday Case).

Agents which have limited health effects which are reversible, e.g.
alcohols, many hydrocarbons

MAJOR INJURY/ILLNESS: Resulting in a Permanent Partial

Disability or affecting work performance in the longer term, such as a
prolonged absence from work.

Agents which are capable of irreversible damage without serious

disability, e.g. amine skin sensitisers.

PERMANENT TOTAL DISABILITY OR FATALITY:

Agents which are capable of irreversible damage with serious
disability or death, e.g. hydrochloric acid, sodium hydroxide (caustic
soda), hydrogen sulphide, asbestos, benzene.

MULTIPLE FATALITIES
Agents as in 4.

(1)

Refer to the SHC Guide on Health Performance Reporting, 1993, Appendix 1 for the definition of Work
Injury, Occupational Illness, Restricted Work Case, Lost Workday Case, Permanent Partial Disability,
Permanent Total Disability and Fatality

(2)

Refer to the SHC Guide Incident Potential Matrix, 1991, Appendix 2, Table 2a.

Table 2: Exposure Ratings

EXPOSURE
RATING

HSE 071
September 1995

DEFINITION

11

A. Very Low

Negligible exposures

B. Low

Exposures below the OEL are controlled and likely to remain so in

accordance with screening and performance criteria.

C. Medium

Exposures approaching the OEL, currently controlled to meet screening

and performance criteria, but control cannot be assured.

D. High

Exposures at or above the OEL, not adequately controlled to meet

screening and performance criteria and continuously/regularly exceed
OELs.

E. Very High

Exposures well above the OEL likely to result in health damage to

persons exposed.

Table 3: Risk Matrix

Potential consequence of exposure to
the hazardous agent as determined by
the agent's HAZARD RATING
RATING

HARM TO PEOPLE

Slight
injury/illness

Minor
injury/illness

Major
injury/illness

Permanent total
disability/fatality

Multiple fatalities

Measure of exposure as determined by the

EXPOSURE RATING
VERY
LOW
(A)

LOW

MED

HIGH

(B)

(C)

(D)

VERY
HIGH
(E)

In respect of chemical agents the Exposure Rating may be further defined as Category I or
Category II exposures:-

Category I :

Category II: > 0.1 x OEL

< 0.1 x OEL

Category I applies to the Exposure Rating 'A: Very Low'. Category II applies to the
remaining Exposure Ratings. Where exposures fall within the range 0.1-1 x OEL, i.e.
Exposure Ratings 'B: Low' and 'C: Medium', judgement can be exercised in the selection of
methods to monitor controls to ensure their continuing integrity - see Part 2, Table 4
'Monitoring of controls : what method versus when to carry out'.

12

HSE 071
September 1995

1.3

DECIDING ON REMEDIAL (CORRECTIVE) ACTION (HRA Step 5)

Where the need for additional control measures is identified to reduce the risk, a systematic
review of all control options should be made with a view to controlling exposures to
ALARP. 'Controls' equate to the term 'barriers' in HEMP.
Part 2 'Monitoring of Controls' provides guidance on the need for measures to monitor the
continuing integrity of the control options in use.
The following provides examples of exposure control measures by way of illustration of:-

types of controls (item 1.3.1.);

what are considered inadequate controls (item 1.3.2.);

recommended control improvements (item 1.3.3.); and

factors to consider in the selection of control measures, including examples of

recovery measure for the mitigation of effects should controls fail (item 1.3.4.).

1.3.1 Types of control measures

The hierarchy of controls comprises:-

elimination of the hazard

substitution of the hazard

engineering measures

procedural measures

personal protective equipment

personal hygiene

Examples are:-

Substitution of the hazard, for example:replace with a less hazardous substance, introduce a non-dusting powder for one that
is friable.

Engineering (plant and equipment), for example:-

totally enclosed process and handling systems. Examples of equipment used to

contain products are mechanical seals, Dopak sampling systems;

plant or processes which minimise generation of, or suppress or contain, the

hazardous dust, fume, etc. and which limit the area of contamination in the event
of spills and leaks. Examples are temperature controllers, pv valves, bunding and
enclosed draining systems;

enclosure with local exhaust ventilation, examples are fume cupboards, tipping
cabinets, with filters or scrubbers;

general ventilation.

Procedural, for example:-

provision of information, instruction and training;

the use of Permits to Work for controlling hazardous operations;

systems of work which minimise generation of, or suppress, the emission to

atmosphere of the hazardous chemical, e.g. damping down dusts, controlling
temperatures and pressures;

minimising the number of employees exposed and exclude non-essential access;

HSE 071
September 1995

13

minimising the period of exposure;

decontamination of walls, surfaces;

safe storage and disposal of hazardous chemicals;

prohibition of eating, drinking, smoking, in the work room;

facilities for washing, changing and separate storage of personal and work
clothing, including arrangements for laundering contaminated clothing;

Personal Protective Equipment (PPE)

Examples of situations where the use of suitable PPE may be appropriate include:-

where it is presently not technically feasible to achieve adequate control of

exposure by engineering or procedural measures alone;

where a new or revised assessment indicates that PPE is necessary to safeguard

health until such time as adequate control is achieved by other means;

where entry into high concentrations is unavoidable, e.g. because of plant failure,
the only practicable solution in the time available may be the provision and use of
PPE;

where exposure occurs for short periods involving a small number of people and
where further process control measures are not reasonably practicable.

In each of these cases the use of PPE would be considered as a reasonably practicable
option.

Personal hygiene, facilities for:-

washing and changing personal and work clothing;

separate storage of clothing;

arrangements for laundering contaminated clothing.

1.3.2 Examples of inadequate control

The following situations are examples of where exposures are likely to present a risk to
health:-

collection of samples of hazardous substances or process streams from open systems;

failure to decontaminate systems before opening for maintenance;

open bench cutting/shaping gaskets containing asbestos by sawing or grinding;

filling drums with volatile hydrocarbons without delivery and ventilation controls;

dumping drilling mud chemicals into a mixing hopper which is not fitted with
effective local exhaust ventilation;

loading volatile products into road tankers without vapour recovery systems.

dumping of catalysts from reactors without controlling dust emissions;

poorly maintained and non operational engineering controls.

In each of these cases it would be reasonably practicable to introduce additional control

measures to reduce exposures to Category I.

1.3.3 Examples of control improvements

The following are examples of current good practice from Shell operations:-

14

HSE 071
September 1995

the replacement of hydrazine solutions used as an oxygen scavenger in boiler water

treatment by alternative less hazardous proprietary chemicals, due to the potential
carcinogenicity of hydrazine;

the replacement of chlorinated hydrocarbon degreasing agents with water soluble

alternatives;

installation of contained sampling systems e.g. Dopak-type;

use of double-mechanical seals on pumps or the use of canned pumps;

modification of batch processes to 'closed reactor' technology;

the removal of harmful gases, vapours, fumes or dusts at the point of generation by the
use of local exhaust ventilation, wherever practicable, e.g. dust collection systems for
catalyst loading/dumping operations, welding fumes;

the formalisation by procedure of the provision of information on the health hazards of

chemical agents used by staff and the measures to be taken to avoid exposure;

the prevention of eating, drinking or smoking where chemical agents are stored,
handled or used.

1.3.4 Factors to consider in the selection of control measures

Future maintenance needs, for example:-

easy access to engineering control systems which require routine inspection;

availability of competent persons for checking and maintaining ventilation

systems, e.g. laboratory fume cupboards, dumping cabinets, welding fume
extractors, mixing vessel extractors;

personal protective equipment, particularly respiratory protective equipment,

require considerable back-up in terms of training, supervision and maintenance, if
it is to provide the intended level of protection. Incorrect selection, fitting and
insufficient use all contribute to over-exposure.

Measures for ensuring that the controls are used and maintained, for example:-

adequate and competent supervision to ensure that appropriate control measures

are correctly used;

periodic checks and procedures to ensure that any defects in control measures are
quickly identified, immediately reported and corrections made promptly;

arrangements for maintenance to include schedules for inspection and testing of

control equipment and associated records.

Recovery measures to mitigate effects of loss of control, for example:-

trained people and availability of equipment to minimise materials release and to

contain/recover that which has been released;

written emergency procedures in place and staff trained to cope with any
foreseeable incident;

sufficient and suitable personal protective equipment;

provision for the prompt decontamination of personnel and personal protective

equipment, e.g. eye wash baths, emergency showers, wash rooms, spare clothing;

prior consideration to safe methods for disposal of the chemical agent(s) and any
contaminated personal protective equipment.

HSE 071
September 1995

15

1.4

FURTHER READING
The following are ADDITIONAL references to those listed in Appendix 8 of the General
Guide; the latter should also be consulted. For details of the acronyms and contact
addresses refer to Section 3.6. and Appendix 5 respectively.

16

UK-HSC Control of Substances Hazardous to Health (COSHH) - General Approved

Code of Practice. Fourth edition 1993. ISBN 0-11-882085-0.

UK-HSE HS(G)97 - A Step by Step Guide to COSHH Assessment. 1993. ISBN 0-11886379-7.

UK-HSE HS(G)37 - An Introduction to Local Exhaust Ventilation. 1993. ISBN 0-11882134-2.

UK-HSE HS(G)54 - The Maintenance, Examination and Testing of Local Exhaust

Ventilation. 1990. ISBN 0-11-885438-0.

ACGIH Industrial Ventilation - A Manual of Recommended Practice. 21st Edition.

UK-HSE HS(G)53 - Respiratory Protective Equipment - a Practical Guide for Users.

1990. ISBN 0-11-885522-0.

SIPM Design and Engineering Practices (DEPs) publications

HSE 071
September 1995

MONITORING OF CONTROLS
This Section proposes a strategy for checking that measures in place for controlling risk are
adequate and remain effective. This forms part of HRA Step 5 - Decide on remedial action,
and equates to the monitoring and corrective action steps in HEMP. In addition, the role
and application of exposure measurement is explained as one of several monitoring
methods. Advice on how to carry out exposure measurement is given in Section 3.
The strategy is applicable to all workplace situations and is based on an action level below
which only minimum actions are required.
There are a number of trigger points which lead to specified actions for direct and indirect
evaluation of control.

2.1

DEVISING A MONITORING STRATEGY

The important issues which have a bearing on the strategy are:-

2.2

the need for reliable estimates of exposure for the HRA;

the need to identify and apply controls which keep exposure to ALARP and, in any
event, below the Occupational Exposure Limit (OEL). The terminology for OELs is
explained in 1.1.4.a.;

the need to show that exposure is unlikely to exceed the OEL;

the need to recognise failure of controls and take prompt remedial action.

HAZARDOUS SUBSTANCES
Chemical agents of particular strategic concern are those which:-

cause irreversible harmful effects e.g. carcinogens;

are absorbed through the lungs or skin;

have an exposure response relationship which is ill defined;

have stringent OELs;

have poor warning properties;

are volatile.

Benzene, as an example, is found widely in the oil and petrochemical industry. It may be
present in streams at low concentrations and may exist as a feedstock or product. It may be
used in dedicated or general purpose plant, sometimes by the drum. Transfer can be by
pipeline, road, rail or by ship.

HSE 071
September 1995

17

2.3

MONITORING METHODS
Exposure measurement is one of nine procedural and technical methods for monitoring
exposure.
As a general rule, as exposures move away from the OEL there is less need for
measurement. At the extremes, exposure is either insignificant or clearly unacceptable.
The following monitoring methods apply to all situations:1.

Health risk assessment, which specifies the controls, plus any need for exposure
measurement and health surveillance. The HRA should identify whether exposures are
Category I (less than 0.1 x OEL) or Category II (more than 0.1 x OEL). Refer to
section 1.2. above.

2.

Baseline exposure evaluation, which provides the data on which the assessment of
risk is based.

3.

Visual inspection, which provides daily checks on obvious control measures.

4.

Examination and test, which provides a thorough regular check on the performance
of plant and equipment used to control exposures, e.g. ventilation performance and
reusable respiratory protective equipment.

5.

Process audit, which provides an in-depth evaluation of plant control and operational
performance relative to company technical standards.

The following are used when required:6.

Routine exposure measurement, in the form of personal sampling and checks of

compliance with the OEL (see 3.1.4.c.).

7.

Investigation, to determine the causes of failure to control exposure.

8.

Biological monitoring, to give an index of individual intake.

9.

Health surveillance, to detect, trace and quantify harmful effects.

If any of the above monitoring methods indicate that exposures are not controlled to a level
ALARP, then appropriate remedial action to regain control should be identified and
implemented.

18

HSE 071
September 1995

2.4

TRIGGER POINTS
In this strategy, the following triggers are recommended for implementing the various
monitoring methods (see also Table 4):-

a minimum yearly reassessment for carcinogens and others agents posing long term
irreversible hazards;

a minimum 5-yearly reassessment;

a minimum annual examination and test;

a change in situation, e.g. a new work process, new pattern of work, revised
appreciation of hazard and risk;

unknown exposure;

Category II exposures;

Category II exposures that have a probability of 5% or more of systematically

exceeding the OEL (refer to 3.1.6. Air measurement: interpretation of results);

adverse health surveillance findings.

Corrective action may be triggered by:-

exposures not ALARP;

failure identified by examination and test;

failure identified by visual inspection;

failure identified by audit;

HSE 071
September 1995

19

Table 4: Monitoring of controls: what method versus when to carry out

Monitoring Method
Methods 1-5 apply to all situations
Methods 6-9 apply when required

When to carry out

1.

Health risk assessment

Category I, every 5 years

a change in situation
Category II, consider more frequently*

2.

Baseline exposure evaluation

unable to categorise exposure

3.

Visual inspection

all situations, daily

4.

Examination and test

all situations, at least annually* (respiratory

protective equipment at least quarterly)
plant start-up

5.

Process audit

Category I, every 5 years

Category II, consider more frequently*

6.

Routine exposure measurement

(see 3.1.4.c.)

consider* for Category II

7.

Investigation

exposure data shows a probability that 5% of

samples or more systematically exceed the OEL
biological data shows a probability that 5% of
samples or more systematically exceed the OEL
recognition of adverse health effects

8.

Biological monitoring

consider* for Category II

exposure is unknown

9.

Health Surveillance

pre-employment
Category I, basic occupational health record
Category II, comprehensive health record
record of known or suspected high exposure
incidents following loss of controls

exposure is not ALARP

fails visual inspection
fails examination and test
fails technical audit

Results of monitoring of controls

which will trigger corrective action

20

The terms 'at least', 'consider' and 'consider more frequently' indicate the need for a local decision on the need for linking
monitoring to risk (see item 1.2. Evaluating the risk to health).

HSE 071
September 1995

From Table 4 it can be seen that there are only three occasions when exposure
measurement, for company purposes, is appropriate, i.e.:-

2.5

when baseline data are required (monitoring method 3);

for routine measurement, when exposures are Category II, if considered necessary
(monitoring method 6);

when investigation is required, and then only if measurement is appropriate

(monitoring method 7).

MANAGEMENT OF EXPOSURE MEASUREMENT

Implementation of exposure measurement to obtain quantitative data needs to be managed
in order to achieve the maximum benefit from the effort expended. The main features are:-

the requirement for measurement is determined as part of the HRA;

if exposure is not known it may be determined by analogy with previous

measurements in similar situations, or it should be measured as the baseline;

the exposure should be ALARP. If not, this should first be achieved by modification
of the control measures before measurement is undertaken;

when exposure is ALARP and Category I the only action is to ensure that the HRA
remains valid;

when exposure is Category II there may be a requirement for routine exposure

measurement (see 3.1.4.c.);

if the exposure data obtained from routine measurement show Category II exposures
with stability within the range 0.1 - 1 x OEL at the 95% probability level (see 3.1.6.)
and exposures are controlled to ALARP, repeated measurement is discontinued. The
need for future measurement is determined by HRA;

if routine exposure measurement data show less than 95% compliance, the situation
needs to be investigated;

if investigation shows that the deficiency is systematic the situation should be

reassessed and the controls reviewed.

Refer also to Section 3, which provides an overview of what is involved in the collection of
quantitative exposure data.

2.6

SUPPLEMENTARY MONITORING METHODS

The use of supplementary methods is encouraged because they are low cost, easily carried
out and directly applicable.
Generally, the resources required for such measurements for routine use is modest and can
be incorporated into a 'common sense monitoring programme' to indicate how effective a
control regime is. In addition, they can be used to give rapid feedback on the performance
of controls, thus facilitating prompt remedial action.
They are:-

spot measurement of workplace levels, e.g. by indicator tubes;

measurement of releases ('sniffing') from specific items of plant, e.g. flanges, pump
seals;

measurement of or indicators of airflow, e.g. in local extract and general ventilation

systems;

HSE 071
September 1995

21

detectors and alarms, e.g. in selected areas where releases are likely to occur.

These methods are particularly effective for checking plant performance. For this reason
they should be included in any monitoring programme whenever technically possible.

22

HSE 071
September 1995

EXPOSURE MEASUREMENT
Section 2 introduced exposure measurement as one of several methods for monitoring the
adequacy and continuing effectiveness of exposure control measures. In this Section the
focus turns to how exposure measurement is carried out and considers air measurement,
biological monitoring, quality assurance and competence.
Acronyms used are explained in 3.6.

3.1

AIR MEASUREMENT

3.1.1 Selection of an appropriate sampling and analytical methodology

Appropriate validated methods to meet the requirements of the overall exposure
measurement strategy, and their subsequent analysis, should be selected.
Methods for individual chemical substances are published by OSHA, NIOSH and the UKHSE, i.e. the MDHS series (refer to Section 3.6 for an explanation of the acronyms).
It should be noted that publication of a method does not necessarily mean that it has been
validated. The analysing laboratory must be satisfied on the validity before samples are
collected.

3.1.2 Validation of sampling and analytical methods

Critical steps in the validation of a method and guidance can be found in MDHS 27 & 54
as well as a number of NIOSH and OSHA documents.
More recently, CEN, the European Standard setting body, has issued a standard EN482
General Requirements for the Performance of Procedures for Workplace Measurements.
This standard applies to all methods of measurement including direct reading devices. It
will act as the basis of forthcoming European Standards for specific procedures and devices
for workplace measurement, e.g. diffusive samplers, charcoal tubes, indicating tubes.

3.1.3 Records
Records of exposure measurement details must be complete, traceable and stand up to close
legal scrutiny. The record should consist of the survey report plus sampling and analytical
results which is incorporated in the HRA process and associated record.

3.1.4 Types of exposure measurement survey

A simplified overview of exposure measurement strategy is given in Appendix 3 which
links the main measurement survey types in a flow chart and is applicable to measuring
exposures to all agents hazardous to health. With regard to chemical agents, relevant action
levels are given under item 2.5. Management of exposure measurement.
Further details on the three types of survey identified are outlined below. An overview of
techniques used to obtain air measurement data is given in 3.1.5.
a)

Preliminary Survey

The aim of the Preliminary Survey is to obtain quantitative exposure data of an acceptable
quality and at reasonable cost to support the HRA decision-making process. It should be
considered when:-

there is doubt about compliance with a recognised OEL (see 1.1.4. above);

to determine Category I or Category II exposures (see 1.2.);

particularly serious effects could result from excessive exposure;

HSE 071
September 1995

23

justification is required for the implementation of control measures to meet acceptance

criteria;

the choice of control measures is dependent on concentration of exposure;

the efficiency of control measures needs to be evaluated;

to alleviate employee concerns;

legal requirements.

It is appropriate to focus on workers who are expected to carry out tasks with the highest
potential exposures, known as 'worst case' exposures. In this way possibly unnecessary
measurement will be avoided, thereby enabling resources to be concentrated on improving
exposure control measures.
b)

Detailed Survey

If the degree and pattern of exposure cannot be reliably determined by the Preliminary
Survey, a more thorough study will be necessary. The objective of the Detailed Survey is to
obtain more accurate and reliable information about the exposures.
Results from the Detailed Survey would be expected to show if:-

exposure is variable;

numbers of people are at risk from excessive exposure, e.g. operators and maintenance
personnel engaged in a plant turn-around;

personal sampling results are close to the relevant OEL.

c)

Routine Monitoring/Exposure Measurement

Routine exposure measurement may be required for the following reasons:-

to comply with national legislation for particular agents/tasks/processes;

to verify compliance with OELs where exposure measurements are in Category II;

to confirm the continuing effectiveness of control measures and to give early warning
of changes in patterns of exposure before excessive exposures occur;

to obtain exposure data as part of an epidemiological study.

3.1.5 Personal exposure protocols

Protocols may include:a)

Personal Sampling

Sampling for personal exposures is designed to collect the air contaminant from the
employee's breathing zone, normally over a full shift, for comparison with the relevant
OEL. It may also be carried out for the duration of a particular task in order to identify the
short term exposure peaks. The calculation for combining fractional exposures obtained
over a shift for comparison with the time-weighted average OEL is given in Appendix 4.
There are two types of personal air sampling:-

Dynamic (also known as active) sampling, in which the contaminant is collected by

actively drawing the air through an absorbent or adsorbent material at a known flow
rate by means of a small battery powered pump unit*.
*

If used in potentially flammable atmospheres, the pump unit should be certified as intrinsically safe.

Diffusive (also known as passive) sampling. Diffusive samplers are compact devices
(badge or tube) in which the contaminant diffuses through a membrane and is
collected on a sorbent. They are most usually used to collect full shift samples.

Personal samplers also include direct readers for certain toxic gases such as H2S, CO and
SO2.

24

HSE 071
September 1995

An important requirement of personal sampling is to ensure that a representative number of

samples is obtained for groups of 10 or more individuals carrying out a similar work
activity. The advice of an Occupational Hygienist should be sought when deciding on a
representative number. Provided that the group is homogeneous* exposure data will be
valid for the work activity.
*

A homogeneous group is a group of workers whose exposures are sufficiently similar that measuring the exposure of
any one worker in the group provides data which can be used to predict the exposures of the other workers in the same
group.

Sampling is carried out to determine exposures which are representative of the whole
process (particularly important in batch operations) and including 'normal' or 'worst case'
conditions.
Repeat exposure measurements for any one worker may differ widely in view of the
variable environmental factors at the workplace (e.g. air movement, position of operator in
relation to contaminant source, fugitive emissions) and the way in which operations are
carried out.
Part of the variation in exposure concentration is caused by sampling and analytical errors
which can be estimated and minimised by method validation (see 3.1.2.).
b)

Area Monitoring

Samples for area monitoring are collected from designated points around the workplace.
The same sampling methods used for personal sampling may be applied to area monitoring
(see 3.1.5.a.). In addition, where toxic substances are present, e.g. hydrogen sulphide,
carbon monoxide, fixed multi-point sampling systems with direct reading instrumentation
may be used to alert staff immediately to increases in workplace concentrations.
Although results of area monitoring do not relate directly to personal exposure they may be
used to detect the pattern of emissions associated with process and workplace activities.
Area monitoring cannot be viewed as a substitute for personal sampling since actual
breathing zone concentrations are heavily influenced by the work method.
c)

Wipe samples

Although not a well developed technique, wipe samples may be used to estimate surface
contamination, including skin, of chemical agents which have a low vapour pressure.
Examples of contaminants for which wipe samples may be used are Pyrethroids and
Polycyclic Aromatic Hydrocarbons (PCAs).

3.1.6 Interpretation of results (checking compliance)

For practical purposes, a guide to compliance with an OEL or action level as per Category I
or II (see 1.2.) is that not more than 1 in 20 samples of a homogeneous group, i.e. 5%,
should exceed the prescribed limit. This equates with a 95% compliance level which is
normally confirmed by the analysis of the data by probability (or cumulative frequency)
plotting. This method depends on the data being log normally or near log-normally
distributed and being representative of the full range of exposures. Refer to CONCAWE
Report no. 87/57, see 3.5.1.
Alternatively, judgement on the need for additional measures to control exposures may be
based on worst case exposure measurements, which, by definition, indicate the highest
potential exposure.

3.2

BIOLOGICAL MONITORING
Biological monitoring involves the measurement and assessment of workplace agents or
their metabolites (transformation products) in body fluids (usually urine or blood), or
exhaled breath, to evaluate exposure and health risk compared to an appropriate reference.

HSE 071
September 1995

25

Biological monitoring may be particularly useful because it reflects uptake by all routes,
i.e. by skin absorption and ingestion as well as by inhalation where air measurement alone
may provide insufficient information on possible uptake of chemical substances.
Measurement of the 'internal dose' also provides information on personal hygienic
behaviour, and the effectiveness of personal protective equipment and respirators.
Examples of biological monitoring methods are:-

Lead in urine to evaluate exposure to Tetra Ethyl Lead and Tetra Methyl Lead (lead
additives used in gasoline);

S-Phenylmercapturic Acid (SPMA) in urine to evaluate exposure to benzene.

There is an increasing number of chemical agents or their metabolites for which guidelines
for maximum allowable concentrations in body fluids have been recommended by
authoritative bodies such as the American Conference of Governmental Industrial
Hygienists (ACGIH) and the German MAK Committee.
Specific guidance on biological monitoring methods, sampling strategies and collection of
samples in relation to a wide range of chemicals relevant to Shell is given in SIPM HSE
Report 94.014: Laboratory Tests for Biological Monitoring and Biochemical Effect
Monitoring.

3.3

QUALITY ASSURANCE

3.3.1 Good practice

To demonstrate that the required standards for air sampling and analysis have been
achieved an adequate quality assurance programme as outlined in, for example, MDHS 71
Analytical Quality in Workplace Air Monitoring should be followed. These elements are
also applicable to a laboratory carrying out biological monitoring. The main elements of
the programme are:a)

Management of the Analytical Laboratory

Accreditation by an acknowledged scheme (e.g. NAMAS in the UK) will demonstrate
that the laboratory's management and administration procedures are operating to a
specified standard.

b)

Internal quality control

This will indicate whether the analytical methodologies or techniques are routinely
standardised and used correctly.

c)

External quality control

This provides objective measurement of the analytical performance achieved by a
laboratory and can give both the performance against a standard and a comparison
against other laboratories. This can be achieved by participation in quality control
schemes such as WASP, AQUA, RICE and PAT.

3.3.2 Managing critical quality control points

Critical points exist in all measurement systems and must be identified and controlled for a
laboratory to produce reliable results. In respect of the preparation of sampling packages
and analysis of samples, the critical control points are:a)

Selection of methods
Liaison between persons collecting the samples in the field and analytical staff,
confirmation of methods and sampling and analytical limits.

b)
26

Preparation of Sampling Package

HSE 071
September 1995

Suitability of pumps, calibration, sampling media, certification of thermal desorption

tubes where used, contamination-free specimen containers.
c)

Transport and storage of samples

Specified conditions of storage to ensure integrity of samples.

d)

Sample Analysis
Use of validated reference methods including calibration over the range,
desorption or recovery efficiencies over the range, precision, accuracy, selectivity and
quantifiable limits.

e)

Inadvertent errors
Systems to minimise errors due to, for example, the improper identification of a
sample, failure to follow methods properly, data recording and transposing,
calculating.

f)

Analytical Instrumentation
Equipment properly maintained and calibrated.

g)

Analytical errors
Quality assurance proficiency checks as a measure of performance.

3.4

COMPETENCE
Certain aspects of health risk assessment and exposure evaluation require relevant
knowledge skills, experience and resources. Refer to the General Guide, Appendix 1,
'Competence', for an overview. Further advice can be obtained from Medical Advisers in
the Service Companies.

3.5

FURTHER READING
Addresses for the organisations listed below are given in Appendix 7.

3.5.1 Air measurement

CONCAWE, Report no. 87/57 - Review of Strategies for the Evaluation of Employee
Exposures to Substances Hazardous to Health. 1987.

CEN, PrEN137 - Assessment of Exposure to Chemical Agents in Air at the Workplace

for Comparison with Limit Values and Measurement Strategy.

BOHS, Technical Guide No. 11 - Sampling Strategies for Airborne Contaminants in

the Workplace. 1993. ISBN - 0-948237-14-7. Published by H and H Scientific
Consultants Ltd.

UK-HSE, Guidance Note EH 42 - Monitoring Strategies for Toxic Substances. 1989.

ISBN 0-11-885412-7.

Monitoring for Health Hazards at Work, Indira Ashton and Frank S Gill. 2nd edition
1992. Publisher: Blackwell Scientific Publications, UK - ISBN 0-632-02984-6

UK-HSE, MDHS 27: Protocol for Assessing the Performance of a Diffusive Sampler.
1987.

UK-HSE, MDHS 54: Protocol for Assessing the Performance of a Pumped Sampler
for Gases and Vapours. 1986.

HSE 071
September 1995

27

3.5.2 Biological monitoring

HSE Report 94.014: Laboratory Tests for Biological Monitoring and Biochemical
Effect Monitoring, available from SIPM-HSE/51

Industrial Chemical Exposure - Guidelines for Biological Monitoring. Robert R

Lauwerys and Perrine Hoet. 2nd edition, 1993. Lewis Publishers.

Biological Monitoring of Metals. C.-G. Elinder, L. Friber, T. Kjellstrm, G. Nordbery,

G. Oberdoerster. International Programme of Chemical Safety (IPCS), WHO 1994.

UK-HSE, EH 56 (January 1992) Biological Monitoring for Chemical Exposures in the

Workplace.

CEFIC Discussion paper on some practical aspects of the biological monitoring of

exposure to genotoxic substances, March 1995.

3.5.3 Quality assurance

3.6

CEN 482 Workplace atmospheres - general requirements for the performance of

procedures for the measurement of chemical agents 1994

UK-HSE MDHS 71: Analytical Quality in Workplace Air Monitoring. 1991.

ACRONYMS
ACGIH
AQUA
BOHS
CEN
CEFIC
CONCAWE
MDHS
NAMAS
NIOSH
OSHA
PAT
RICE
UK-HSE
WASP
WHO

28

American Conference of Governmental Industrial Hygienists

Analytical Quality Assurance Scheme (UK - HSE)
British Occupational Hygiene Society
Comit Europen de Normalisation (European Union)
Conseil Europen de L'Industrie Chimique (European Council of
Chemical Manufacturers' Federations)
The Oil Companies' European Organisation for Environmental and
Health Protection
Methods for the Determination of Hazardous Substances (UK-HSE)
National Measurement Accreditation Service (UK)
National Institute of Occupational Safety and Health (USA)
Occupational Safety and Health Administration (USA)
Proficiency Analytical Testing (NIOSH)
Regular Interlaboratory Counting Exchange (UK-HSE)
Health and Safety Executive (UK)
Workplace Analysis Scheme for Proficiency (UK-HSE)
World Health Organisation

HSE 071
September 1995

APPENDIX 1

INTRODUCING TOXICOLOGY - AN OUTLINE

Toxicology studies the adverse effects that chemical substances have on living organisms.
These adverse effects may occur as a result of local contact of the chemical with body
surfaces, such as the skin and eyes, the respiratory system or the digestive tract, or may
result from up-take into the body at sites remote from the place of up-take. The latter form
is called systemic toxicity.
The local interaction between the chemical substance and a body surface may result in
partial or complete disturbance of the physiological processes taking place in the cells of
the surface linings. The outcome may be anything between a very light irritation (some
swelling and redness) up to and including complete cell destruction as can be seen in
serious (heat) burns.
Chemicals which are strong acids or strongly basic can cause these local adverse reactions,
but lipophilic chemicals (such as solvents) may cause damage by dissolving the protective
fatty layer of the skin.
Another toxic reaction following local contact may be the induction of skin or respiratory
allergy. Fortunately, the number of chemicals which can cause allergic reactions (so called
sensitisers) is limited.
Systemic toxicity may result from uptake/absorption/injection of chemical substances into
the body. Usually the chemicals are transported in the blood and metabolised to make them
less toxic and better and more rapidly excretable.
Sometimes, the metabolite(s) are more toxic than the parent compounds, whilst some
chemicals are, even after being transformed in the metabolic process, only very slowly
excreted, resulting in accumulation.
The systemic toxicity may be categorised in terms of the target organ(s) which is/(are)
predominantly affected (kidneys: nephrotoxic; liver: hepatotoxic; bone marrow:
myelotoxic, etc.), or in terms of the specific nature of adverse effects caused, such as
carcinogenicity (the induction of tumours), mutagenicity (the induction of mutations) or
teratogenicity (the induction of congenital malformations/dysfunctions).
The nature of the mechanistic processes which cause the adverse effects is usually very
complex, but always based on interference with normal processes at the cellular level.
There are various defence and repair mechanisms which can deal with the invading
chemicals. As these defensive mechanisms have limitations, they may be overcome.
Chemicals of high toxicity require a lower dose to overcome the defence systems and cause
adverse effects than chemicals of low toxicity, reflecting the differences in potency.
Central in toxicology is the relationship between the dose and the resulting effect
(dose/effect relationship) and the relationship between the number of affected individuals
which react with a specific effect in response to the dose (dose-response relationship).
Experimental toxicology seeks to clarify these dose-effect and dose-response relationships,
in particular the NOAEL (No Observed Adverse Effect Level).
For risk characterisation it is necessary to identify the adverse effect of most concern, i.e.
the Critical Effect, as this will be used to arrive at safe levels of exposure.
Experimental toxicology tests are standardised by OECD guidelines and range from a very
simple determination of the lethal dose for 50% of the animals (LD 50) to very
sophisticated long term investigations of all possible adverse effects and the underlying
causative mechanisms.
new and existing substances and how the results are 'translated' into Materials Safety Data
Sheets and Labels.
Footnote

HSE 071
September 1995

29

EU Commission Regulation 1488/94 on Risk Assessment of Existing Substances: Terminology of Risk

30

Risk Assessment

A generic term describing an administrative and technical process which entails

some or all of he elements below.

Effects Assessment: i)
Hazard identification

Identification of the adverse effects which a substance has an inherent capacity

to cause; and, where possible and/or appropriate, the assessment of a particular
effect.

ii)

Estimation of the relationship between dose (or level of exposure) and the
incidence and severity of an effect.

Dose-response assessment

Exposure Assessment

Determination of the pathways and rates of movement of a substance, its

transformation or degradation and its concentration. when possible, at critical
points in order to estimate the doses to which defined populations,
environmental compartments or specific ecosystems are actually exposed.

Risk Characterisation

Estimation of the incidence and severity of the adverse effects likely to occur in
a population, environmental compartment or ecosystem exposed to a substance
and may include: -

Risk Estimation

Quantification of the likelihood of the incidence and severity of the adverse

effects.

Risk Reduction

The taking of measures to reduce the likelihood of adverse effects occurring.

HSE 071
September 1995

APPENDIX 2

COMMON TOXICITY TERMS

Toxicity

This is defined as 'the ability of a chemical compound to

produce injury once it reaches a susceptible site in or on
the body'.

Toxic substance

An agent which if inhaled, ingested or absorbed through

the skin, may result in/produce/involve serious, acute or
chronic health effects and even death.

Acute health effect

This effect occurs suddenly and in a short time (seconds to

hours) following exposure, generally to higher levels or
concentrations of a health hazard. An acute exposure runs
a comparatively short course. Examples are:-

inhalation of hydrogen sulphide gas leading to

respiratory paralysis;

inhalation of cadmium fume from silver solder

leading to pulmonary oedema (fluid on the lungs);

inhalation of solvents leading to narcotic effects and

coma.

Chronic health effect

This effect occurs gradually over a long period of time

following repeated exposure to relatively low levels or
concentrations of a hazardous agent, e.g. carcinogenic
agents. In certain cases, short term exposure may result in
a delayed effect which may remain for a long time.

Acute and chronic

Some chemical agents may have both acute and chronic

health effects, e.g. exposure to short term high levels of
benzene will result in acute narcotic effects, whilst
exposure to repeated relatively low levels may result in
damage to the red blood cells and potentially lead to the
development of myeloid leukaemia, cancer of the blood.

Additive effect

This applies to mixtures which contain chemical agents

that act on the same body organ(s), or by similar
mechanisms, so that the effects support each other and the
agents are additive in their effect. (See also 'synergistic
effect')

Asphyxiant (simple)

A chemically inert gas which can replace the oxygen

content in air in confined spaces thereby causing
suffocation, e.g. nitrogen, argon, propane, butane, carbon
dioxide.

Asphyxiant (chemical)

A chemical that interferes with the take up and use of

oxygen in body tissues, e.g. carbon monoxide, hydrogen
sulphide, hydrogen cyanide.

Cancer

An autonomous growth of cells leading to tumours.

Tumours may be benign in which case they do not spread
to other sites. They may be malignant in which case they
tend to spread locally or to other sites and to recur when
removed.

Carcinogen

Induces malignant tumours in tissue, e.g. asbestos,

hardwood dusts, arsenic, benzene.

HSE 071
September 1995

31

Corrosive

Destroys or damages (burns) living tissue on contact. At

particular risk are the skin and eyes. If a corrosive is
inhaled as a mist or vapour the irritation to the lining of
the lungs may result in the lungs filling up with fluid
(pulmonary oedema) which can be life threatening, e.g.
mists from concentrated solutions of strong acids such as
sulphuric acid, or alkalis such as caustic soda.

Dermatitis

Dermatitis is usually caused by chronic exposure to agents

which remove the skin's natural oils causing it to become
dry and lose its elasticity. Types of dermatitis are:-

contact dermatitis: reddening, fissuring and crusting;

folliculitis (oil-acne) due to blockage of hair follicles

with consequent obstruction and inflammation;

hyperkeratosis with warts or papilloma which may

become malignant.

Genotoxic carcinogen

An agent capable of damaging the DNA in cells (see

mutagen)

Irritant

Produces local inflammation of the skin, eyes, nose or

lung tissue. Prolonged or repeated exposure of the skin to
an irritant may lead to contact dermatitis. Examples of
irritants are lime, fibreglass, ammonia, sulphur dioxide,
chlorine.

Local effect

This means that any toxic effect takes place at the point or
area of contact. (See also 'Systemic effect').

Malignant

Refer to 'cancer'.

Mutagen/mutation

Mutagens can damage the DNA in a cell which may lead

to a mutation, i.e. a permanent change of the properties of
a cell. Cancers caused by genotoxic chemicals are
believed to be started by damage to DNA. These
chemicals are termed mutagens and must be treated with
caution, e.g. ethylene oxide.

Narcotic

Induces dizziness, nausea and coma, e.g. organic solvents

such as alcohols, esters, ethers; hydrocarbon mixtures
such as gasoline.

Relative vapour density

The relative vapour density is the weight of a specific

volume of a gaseous chemical agent compared to the
weight of the same volume of air.
If the relative vapour density of a pure gas is less than 1
the gas will rise and collect at ceiling level (if indoors) or
disperse into the atmosphere (if outdoors).

32

Reproductive toxicity

May affect male or female fertility and/or cause nonheritable birth defects in off-spring, e.g. certain low
molecular weight glycol ethers.

Pneumoconioses

Generic term for lung diseases caused by some respirable

dusts such as crystalline quartz (silicosis) and asbestos
(asbestosis) where scar tissue (fibrosis) has resulted in a
loss of lung function.

Sensitiser

Causes an allergic reaction. This may include wheezing

and shortness of breath (asthma) for lung sensitisers, or a

HSE 071
September 1995

rash leading to allergic dermatitis for skin sensitisers, e.g.

isocyanates (lung), nickel metal (skin), epoxy resins
(skin).
Synergistic effect

This applies to mixtures which contain chemical agents

that act on the same organs, or by similar mechanisms, so
that the overall effect is considerably greater than the sum
of the individual effects, e.g. smoking and exposure to
asbestos fibres significantly increases the risk of
contracting lung cancer. (See also 'Additive effect').

Systemic effect

In this case the site of toxic effect is other than the point
of contact and pre-supposes that absorption has taken
place (See also 'Systemic toxicity')

Systemic toxicity

A generic term used to describe agents toxic to one or

more specific target organ(s) or body system(s). (See also
'Systemic effect').

HSE 071
September 1995

33

APPENDIX 3

34

OVERVIEW OF EXPOSURE MEASUREMENT

STRATEGY

HSE 071
September 1995

APPENDIX 4

CALCULATION FOR COMBINING FRACTIONAL

EXPOSURE MEASUREMENTS TO ALLOW
COMPARISON WITH A SPECIFIED REFERENCE
PERIOD

UNITS OF MEASUREMENT

1.1

Gases and Vapours

Two units are used to express the concentration of gases or vapours, viz.:-

parts per million (ppm), a measure of concentration by volume; or

milligrams per cubic metre of air (mg/m3), a measure of concentration by mass.

The inter-conversion formulae are:a)

to convert mg/m3 to ppm:ppm = mg/m3 x 24.5 / Molecular Weight of chemical

b)

to convert ppm to mg/m3:mg/m3

= ppm x Molecular Weight / 24.5

Both formulae assume Normal Temperature and Pressure, i.e. 25C and 760 mm of
Mercury (1 bar).
1.2

Particulates
Airborne concentrations are usually expressed in mg/m3 as the 'Inhalable Fraction' or
'Respirable Fraction'.
Airborne concentrations of fibrous materials, e.g. Asbestos and Man Made Mineral Fibres
(MMMF) can be expressed either as mg/m3 or as fibres per millilitre of air (f/ml).

CALCULATIONS

2.1

Time Weighted Average 8-Hour Reference Periods

In order to compare exposure measurements with the appropriate 'Time Weighted Average
8-hour reference period' it is necessary to express the total exposure in any 24-hour period
as a single equivalent uniform exposure for 8 hours. This is represented mathematically
by:C1T1+ C2T1 + ........ + CnTn / 8 hours
Where 'C' is the occupational exposure and 'T' is the associated time in hours in any 24
hour period.
In the example given below the working shift has been taken as 8 hours.
Example:A maintenance technician is servicing the in-line blending equipment for mixing
tetramethyl lead into the gasoline blend stock. The work was scheduled for the whole day
but breaks were taken for coffee/tea, lunch etc.

HSE 071
September 1995

35

The work periods, sampling duration and exposure levels were:Working period

Sampling duration (h)

Exposure mg/m3

0800 - 1030

2.5

0.25

1030 - 1045

0.25

1045 - 1245

2.0

0.05

1245 - 1330

0.75

1330 - 1530

2.0

0.3

1530 - 1545

0.25

1545 - 1715

1.5

0.25

The 8 hour TWA is therefore:-

The OEL, as recommended by the ACGIH, for tetramethyl lead is 0.15 mg/m3.
The result is 1.5 x OEL which equates with an Exposure Rating of D. With a Hazard
Rating of 4 for alkyl lead compounds risk reduction measures must be applied. In the short
term it could be reasonably practicable to use respiratory and skin protection. If this were
not acceptable in the longer term, e.g. in the case of a frequent task, plans to implement risk
reduction measures by engineering means which control alkyl lead at source would need to
be introduced.
2.2

Short Term Reference Period

In order to check compliance with a STEL, exposure should be recorded as the average
over the specified short-term reference period and should normally be determined by
sampling over that period. For example:-

36

where the exposure period is less than 10 minutes the sampling result should be
averaged over 10 minutes. For example, if a 5-minute sample produces a level of 500
ppm and is immediately followed by a period of zero exposure then the 10-minute
average exposure will be 250 ppm;

where the exposure period is 10 minutes or longer measurements can be restricted

to 10 minutes and evaluated by reference to the STEL.

where data are required to evaluate risk in a specific task, the full duration of the
task should be sampled.

HSE 071
September 1995

APPENDIX 5

ADDRESS LIST

ACGIH:

Kemper Woods Centre, 1330 Kemper Meadow Drive, Cincinnati, OH 45240

BOHS:

Suite 2, Georgian House, Great Northern Road, Derby, England, DE1 1LT

CONCAWE:

Madouplein 1, B-1030, Brussels, Belgium

CEFIC:

Avenue E. Van Nieuwenhuyse 4 - Box 1, B-1160 Brussels, Belgium

CEN :

Rue de Stassart 36, B-1050, Brussels, Belgium

UK-HSE:

HSE Books, PO Box 1999, Sudbury, Suffolk, England, CO10 6FS

NIOSH:

US Government Printing Office, Superintendent of documents, Washington, DC

20402, USA

OSHA:

200 Constitution Avenue, N.W. Washington, DC 20210, USA

WHO:

1211 Geneva 27, Switzerland

HSE 071
September 1995

37