Download as pdf or txt
Download as pdf or txt
You are on page 1of 172

OHTA501

Measurement of Hazardous Substances

STUDENT MANUAL
2023

ohtatraining.org
COPYRIGHT

Copyright © 2023 Occupational Hygiene Training Association Ltd (OHTA). All rights reserved.

You may view, download, and print this material for personal, non-commercial purposes, including
self-study and reference.

OHTA is a not-for-profit organisation with minimal income used for maintaining our website and
for administrative support. Please consider supporting OHTA through a donation at
https://www.ohtatraining.org/donate. OHTA is both a UK registered charity and a non-profit
organization (501c3) in the United States.

All materials are authored and edited by subject matter expert volunteers. If you use these
materials without providing support, it may not be possible for us to continue the development
and updating of our training materials. For that reason, we also ask you not to reproduce,
distribute or translate this material without seeking permission from [email protected]

Help power OHTA quality training materials for the years to come with a donation. All amounts
are appreciated.

DISCLAIMER

The information provided in this course is for educational purposes and is not intended as
professional or expert advice. The copyright holder has made efforts to ensure the accuracy of the
material but does not guarantee its completeness or suitability for any specific purpose.

Measurement of Hazardous Substances Page i


Table of Contents
Table of Contents
Acknowledgements............................................................................................................................. viii

Abbreviations ........................................................................................................................................ 9

References ........................................................................................................................................... 13

Index of Figures.................................................................................................................................... 16

Index of Tables..................................................................................................................................... 18

Chapter 1 Course Overview .................................................................................................................. 19


1.1 Introduction ........................................................................................................................................... 19
1.2 Aim of Course ........................................................................................................................................ 19
1.3 Learning Outcomes ................................................................................................................................ 19
1.4 Format of Manual .................................................................................................................................. 19

Chapter 2 Risk Assessment ................................................................................................................... 20


2.1 Introduction to Risk Assessment ........................................................................................................... 20
2.2 The Risk Assessment Process................................................................................................................. 21
2.3 Occupational Hygiene Risk Assessment Overview ................................................................................ 22
2.3.1 Risk Identification ........................................................................................................................... 22
2.3.2 Risk Analysis ................................................................................................................................... 24
2.3.3 Risk Assessment .............................................................................................................................. 25
2.4 Risk Assessment Tools ........................................................................................................................... 26
2.5 Non-Sampling Approaches .................................................................................................................... 26
2.5.1 Control Banding .............................................................................................................................. 27
2.5.2 Exposure Modelling ........................................................................................................................ 30
2.6 Documentation ...................................................................................................................................... 30
2.7 Periodic Review ..................................................................................................................................... 30
2.8 An Outline of an Approach to Risk Management .................................................................................. 31
2.9 Hierarchy of Controls ............................................................................................................................. 31
2.9.1 Elimination and Substitution .......................................................................................................... 31
2.9.2 Engineering Controls ...................................................................................................................... 31
2.9.3 Administrative Controls .................................................................................................................. 32
2.9.4 Personal Protective Equipment ...................................................................................................... 32
2.9.5 Information, Instruction and Training ............................................................................................ 32
2.9.6 Workplace Monitoring ................................................................................................................... 33
2.9.7 Health Surveillance ......................................................................................................................... 33
2.9.8 Emergency Procedures ................................................................................................................... 34
2.9.9 Management Role .......................................................................................................................... 34

Measurement of Hazardous Substances Page ii


Table of Contents
Chapter 3 Occupational Exposure Limits ............................................................................................... 35
3.1 Introduction to OELs .............................................................................................................................. 35
3.2 Definitions and Units ............................................................................................................................. 36
3.3 Time Weighted Average OELs................................................................................................................ 37
3.4 OELs for Extended Shifts ........................................................................................................................ 38
3.4.1 OSHA (Direct Proportion) Model .................................................................................................... 38
3.4.2 Brief and Scala Model ..................................................................................................................... 39
3.4.3 UK Approach ................................................................................................................................... 40
3.4.4 Quebec Model ................................................................................................................................ 40
3.5 Short Term Exposure Limits ................................................................................................................... 41
3.6 Ceiling Limit (C) ...................................................................................................................................... 41
3.7 Long Term Average (LTA) Exposure Limit .............................................................................................. 41
3.8 Excursion Limits ..................................................................................................................................... 41
3.9 Notations ............................................................................................................................................... 42
3.9.1 Biological Monitoring Limits ........................................................................................................... 42
3.9.2 Carcinogenicity ............................................................................................................................... 42
3.9.3 Sensitisation ....................................................................................... Error! Bookmark not defined.
3.9.4 Skin 43
3.10 Basis of OELs ........................................................................................................................................ 44
3.11 Application of OELs .............................................................................................................................. 45
3.12 Types Occupational Exposure Limits ................................................................................................... 45
3.13 Threshold Limit Values (TLVs) .............................................................................................................. 46
3.13.1 TLV-TWA ....................................................................................................................................... 46
3.13.2 TLV-STEL ....................................................................................................................................... 46
3.13.3 TLV-C ............................................................................................................................................. 47
3.13.4 Peak Exposures (Formally Excursion Limit) .................................................................................. 47
3.13.5 Mixtures........................................................................................................................................ 48
3.13.6 TLV Notations * ............................................................................................................................ 48
3.14 Australian Exposure Standards ............................................................................................................ 50
3.15 United Kingdom Workplace Exposure Limits (WELs) .......................................................................... 50
3.16 European Exposure Limits ................................................................................................................... 51
3.16.1 European Agency for Safety and Health at Work ......................................................................... 51
3.16.2 Scientific Committee on Occupational Exposure Limits ............................................................... 51
3.16.3 REACH Derived No Effect Limits ................................................................................................... 52
3.17 OSHA Permissible Exposure Limits ...................................................................................................... 52
3.18 NIOSH................................................................................................................................................... 53
3.19 AIHA ..................................................................................................................................................... 53
3.20 Germany – MAK Commission .............................................................................................................. 54
3.21 Limitations of OELs .............................................................................................................................. 54

Measurement of Hazardous Substances Page iii


Table of Contents
Chapter 4 Air Sampling Theory and Practice .......................................................................................... 56
4.1 Introduction ........................................................................................................................................... 56
4.2 Workplace Sampling Strategies ............................................................................................................. 56
4.3 Types of Surveys .................................................................................................................................... 58
4.3.1 Initial Appraisal............................................................................................................................... 58
4.3.2 Basic Survey .................................................................................................................................... 59
4.3.3 Detailed Survey ............................................................................................................................... 60
4.3.4 Routine Monitoring ........................................................................................................................ 60
4.3.5 Statistically Driven Approaches ...................................................................................................... 61
4.4 Who Should Be Sampled?...................................................................................................................... 62
4.5 When ..................................................................................................................................................... 62
4.6 Where? .................................................................................................................................................. 63
4.7 How? ...................................................................................................................................................... 63
4.8 Sample Numbers ................................................................................................................................... 64
4.8.1 Coefficient of Variation................................................................................................................... 65
4.8.2 Rappaport & Selvin ......................................................................................................................... 65
4.8.3 NIOSH ............................................................................................................................................. 67
4.8.4 AIHA ................................................................................................................................................ 67
4.8.1 The BOHS/NVvA Guidance ............................................................................................................. 68
4.9 How Long To Sample ............................................................................................................................. 69
4.10 Sampling Patterns ................................................................................................................................ 69
4.10.1 Sampling to Assess Acute or Chronic Effects ................................................................................ 71
4.11 Practicalities of Sampling Programmes ............................................................................................... 71
4.12 Personal Sampling ............................................................................................................................... 72
4.12.1 Breathing Zone ............................................................................................................................. 72
4.12.2 Operator Variability ...................................................................................................................... 72
4.13 Area Sampling ...................................................................................................................................... 73
4.13.1 General or Background Measurements........................................................................................ 73

Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling Methods ............................................. 74
5.1 Introduction to Dusts, Fumes and Fibres .............................................................................................. 74
5.2 Particulate Deposition ........................................................................................................................... 74
5.3 Particulate Air Sampling ........................................................................................................................ 76
5.3.1 General ........................................................................................................................................... 76
5.3.2 Sample Filters ................................................................................................................................. 77
5.3.3 Basic Sample Collection Procedure ................................................................................................. 80
5.4 Inhalable Dust ........................................................................................................................................ 81
5.4.1 IOM Sampling Head:....................................................................................................................... 81
5.4.2 Conical Inhalable Sampler (CIS) ...................................................................................................... 81
5.4.3 SKC Button Aerosol Sampler ........................................................................................................... 81
5.4.4 Pre-Loaded Cassettes ..................................................................................................................... 81
5.5 Respirable Dust ...................................................................................................................................... 82

Measurement of Hazardous Substances Page iv


Table of Contents
5.6 Thoracic Dust ......................................................................................................................................... 83
5.7 Fibres ..................................................................................................................................................... 84
5.8 Diesel Particulate Emissions .................................................................................................................. 85
5.9 Rosin Fume ............................................................................................................................................ 85
5.10 Air Sampling Pumps ............................................................................................................................. 86
5.11 Pump Calibration ................................................................................................................................. 88
5.11.1 Basics ............................................................................................................................................ 88
5.11.2 Calibration Procedure ................................................................................................................... 89
5.12 Calculation of Particulate Air Sampling Results ................................................................................... 91
5.12.1 Calculation of Sample Volume...................................................................................................... 91
5.12.2 Calculation of Particulate Mass .................................................................................................... 91
5.13 Calculation of Air Sample Result.......................................................................................................... 92
5.14 Calculation of 8h-Time Weighted Average .......................................................................................... 92
5.15 Particulate Air Sampling: Direct Reading Methods ............................................................................. 93
5.16 Particulate Air Sampling Selection Guide ............................................................................................ 94

Chapter 6 Gases and Vapours ............................................................................................................... 95


6.1 What Are Gases and Vapours? .............................................................................................................. 95
6.2 Fundamentals of Air Sampling for Gases and Vapours ......................................................................... 96
6.3 Active Air Sampling: Basics .................................................................................................................... 96
6.4 Sorbent Tubes ........................................................................................................................................ 97
6.4.1 General ........................................................................................................................................... 97
6.4.2 Sorbent Tubes: Breakthrough ......................................................................................................... 98
6.4.3 Sorbent Tubes: Common Varieties ................................................................................................. 99
6.4.4 Sorbent Tubes: Collection Efficiency ............................................................................................. 100
6.4.5 Sorbent Tube: Desorption Efficiency ............................................................................................. 100
6.4.6 Sorbent Tubes: Thermal Desorption ............................................................................................. 101
6.5 Filters ................................................................................................................................................... 102
6.6 Mixed Phase Exposures ....................................................................................................................... 102
6.7 Liquid Sample Media ........................................................................................................................... 103
6.8 Air Sampling: Diffusion Methods ......................................................................................................... 104
6.9 Grab Sampling Basics ........................................................................................................................... 106
6.9.1 Canisters ....................................................................................................................................... 107
6.9.2 Grab Sampling Bags ..................................................................................................................... 107
6.9.3 Colourimetric Tubes ...................................................................................................................... 108
6.10 Sample Analysis ................................................................................................................................. 108
6.11 Example Calculations of Results ........................................................................................................ 108
6.11.1 Air Volume Calculation ............................................................................................................... 108
6.12 Direct Reading Instruments: General ................................................................................................ 110
6.12.1 Direct Reading Instrument Limitations....................................................................................... 112
6.12.2 Direct Reading Instrument Cross Sensitivity ............................................................................... 112

Measurement of Hazardous Substances Page v


Table of Contents
6.13 Detector Tubes (Colorimetric Tubes) ................................................................................................ 113
6.13.1 Maintenance and Calibration ..................................................................................................... 114
6.13.2 A Primer on Explosion Safe Equipment....................................................................................... 116

Chapter 7 Sample Analysis ................................................................................................................. 121


7.1 Introduction ......................................................................................................................................... 121
7.2 Analytical Methods .............................................................................................................................. 121
7.2.1 Spectroscopy................................................................................................................................. 121
7.2.2 Chromatography .......................................................................................................................... 125
7.2.3 Other Analytical Techniques ......................................................................................................... 126
7.2.4 Detection Limits, Sensitivity, Chemical Interferences ................................................................... 127
7.2.5 Sources of Analytical Methods ..................................................................................................... 127
7.3 Laboratory Balances ............................................................................................................................ 128
7.4 Microscopy .......................................................................................................................................... 129
7.5 Quality Assurance of Analysis .............................................................................................................. 131
7.5.1 Internal Quality Control ................................................................................................................ 131
7.5.2 External Quality Assurance........................................................................................................... 133

Chapter 8 Other Sampling Tools ......................................................................................................... 134


8.1 Bulk Sampling ...................................................................................................................................... 134
8.2 Surface Contamination Measurements ............................................................................................... 134
8.3 In-Situ XRF Metal Analysis ................................................................................................................... 135
8.4 Skin Exposure ....................................................................................................................................... 135
8.4.1 Direct ............................................................................................................................................ 136
8.4.2 Indirect.......................................................................................................................................... 136
8.5 Confined Spaces................................................................................................................................... 138
8.5.1 Identification and Nature of Hazards ........................................................................................... 138
8.5.2 Monitoring in Confined Spaces ..................................................................................................... 139
8.5.3 Breathing Air Quality .................................................................................................................... 141

Chapter 9 Presentation of Results ....................................................................................................... 142


9.1 Background .......................................................................................................................................... 142
9.2 General Report Content ...................................................................................................................... 142
9.3 Notes on Process Description .............................................................................................................. 144
9.4 Notes on Results and Discussion ......................................................................................................... 145
9.5 Notes on Conclusions and Recommendations .................................................................................... 145
9.6 Statistical Analysis Primer .................................................................................................................... 146
9.6.1 Statistical Distribution .................................................................................................................. 147
9.6.2 Mean and Standard Deviation ..................................................................................................... 147
9.6.3 Confidence Levels ......................................................................................................................... 150
9.6.4 Minimum Variance Unbiased Estimate (MVUE)........................................................................... 150
9.6.5 Log Probability Plots ..................................................................................................................... 151

Measurement of Hazardous Substances Page vi


Table of Contents
Chapter 10 Biological Monitoring ....................................................................................................... 153
10.1 Fundamentals of Biological Monitoring ............................................................................................ 153
10.2 Direct Biological Monitoring .............................................................................................................. 154
10.3 Biological Effect Monitoring .............................................................................................................. 154
10.4 General Considerations ..................................................................................................................... 154
10.5 Biological Half-Life ............................................................................................................................. 155
10.6 Sampling Time ................................................................................................................................... 155
10.7 Urine Specimen Acceptability ............................................................................................................ 156
10.8 Biological Standards........................................................................................................................... 157
10.8.1 Biological Exposure Indices ......................................................................................................... 157
10.8.2 Notations .................................................................................................................................... 157
10.8.3 UK Limits ..................................................................................................................................... 158
10.9 Confidentiality ................................................................................................................................... 158

Appendix A Introduction to Physiology and Toxicology ....................................................................... 160


A.1 The Human Body ................................................................................................................................. 160
A.1.1 Cardiovascular System ................................................................................................................. 160
A.1.2 Digestive System .......................................................................................................................... 160
A.1.3 Endocrine System ......................................................................................................................... 160
A.1.4 Immune System ............................................................................................................................ 160
A.1.5 Integumentary System ................................................................................................................. 161
A.1.6 Lymphatic System......................................................................................................................... 161
A.1.7 Muscular System .......................................................................................................................... 162
A.1.8 Nervous System ............................................................................................................................ 162
A.1.9 Reproductive System .................................................................................................................... 163
A.1.10 Respiratory System ..................................................................................................................... 163
A.1.11 Skeletal System........................................................................................................................... 163
A.1.12 Urinary System ........................................................................................................................... 164
A.2 Routes of Entry .................................................................................................................................... 164
A.3 Target Organs and Systems ................................................................................................................. 165
A.4 Concept of Dose Response .................................................................................................................. 166
A.4.1 Dose Response.............................................................................................................................. 168
A.4.2 No Observed Adverse Effect Level ................................................................................................ 168
A.4.3 Threshold ...................................................................................................................................... 169
A.4.4 Threshold of Intoxication.............................................................................................................. 171

Measurement of Hazardous Substances Page vii


Table of Contents
Acknowledgements

The Occupational Hygiene Training Association would like to express their appreciation to the
following individuals and organisations for their support and contributions during the
development and revision of this manual.

3M Aust Pty Limited Laurie Glossop


AIHA Markes International Ltd
AIOH Martin Axon
Airmet Scientific Pty Ltd Mary O’Reilly
Ajay Maira Megan Tranter
Alan Rogers Michael Connor
BlueScope Steel Pty Ltd Mike Slater
BOHS Phil Johns
BP International Limited Richard Topliss
Brian Cox Roger Alesbury
Coal Mines Technical Services Ron Terpstra
David O’Malley Russell Bond
Diamond Environmental Ltd SKC Inc
DOCEP/WorkSafe WA Steve Bailey
Doug Rhodes Ted Zellers
Dräger (Aust) Pty Ltd Terry McDonald
Genesis Environmental Ltd TestSafe Australia
Holly Fletcher Thermo Fisher Scientific
John Dobbie Tom Kupferer
Karen Bufton Trudy Bishop
Kenelec Scientific Pty Ltd TSI Incorporated

Measurement of Hazardous Substance Page 8


Acknowledgements
Abbreviations
AAS Atomic Absorption Spectroscopy
ACGIH American Conference of Governmental Industrial Hygienists
AIDS Acquired Immune Deficiency Syndrome
AIHA American Industrial Hygiene Association
AIOH Australian Institute of Occupational Hygienists
AM Arithmetic Mean
AREC Anticipation, Recognition, Evaluation and Control
ART Advanced Reach Tool
AS Australian Standard
AS/NZS Australian Standard/New Zealand Standard
BAT Biological Tolerance Values
BCIRA British Cast Iron Research Association
BEI® Biological Exposure Indices
BIOELV Binding Occupational Exposure Limit Values
BMGV Biological Monitoring Guidance Values
BOHS British Occupational Hygiene Society
C Ceiling Limit
CIS Conical Inhalable Sampler
Cl2 Chlorine
cm Centimetre
CNS Central Nervous System
COSHH Control of Substances Hazardous to Health
CS2 Carbon Disulphide
CV Coefficient of Variation
DNELs Derived No-Effect Levels
DRF Daily Reduction Factor
ECHA European Chemicals Agency
ERPGTM Emergency Response Planning Guidelines
ES Exposure Standard
FID Flame Ionization Detector
g/cm² Grams per Square Centimetre
g/L Grams per Litre
GC Gas Chromatography
GHS Globally Harmonized System of Classification and Labelling of Chemicals
GM Geometric Mean
GSD Geometric Standard Deviation

Measurement of Hazardous Substance Page 9


Abbreviations
H2 Hydrogen
H2S Hydrogen Sulphide
HCN Hydrogen Cyanide
HEG Homogeneous Exposure Group
HF Hydrofluoric Acid
HPLC High-Performance Liquid Chromatography
HSE Health & Safety Executive (UK)
IARC International Agency for Research on Cancer
ICP Inductively Coupled Plasma Spectrometry
ILO International Labor Organisation
IOELV Indicative Occupational Exposure Limit Values
IOM Institute of Occupational Medicine (UK)
IR Infra-red
IRSST Institut de recherche Robert-Sauvé en santé et en sécurité du travail
ISO International Standards Organisation
L Litre
L/m Litre per Minute
LD50 Lethal Dose 50%
LEL Lower Explosive Limit
LOD Limit of Detection
LOEAL Lowest Observed Adverse Effect Level
LOQ Limit of Quantitation
LTA Long term average
μg Microgram
μg/m³ Microgram per Cubic Metre
μm Micrometre
m³ Cubic Metre
MAK Maximum Workplace Concentration
MCE Mixed Cellulose Ester
MDA Methylene Dianiline
MDHS Methods for the Determination of Hazardous Substances
MEL Maximum Exposure Limits
mg/m³ Milligrams per Cubic Metre
MHSWR Management of Health and Safety at Work Regulations
Mins Minutes s
ml millilitre
MMMF Man Made Mineral Fibre
MOCA Methylene bis-orthochloroaniline

Measurement of Hazardous Substance Page 10


Abbreviations
MS Mass Spectrometer
MSDS Material Safety Data Sheet
MSHA Mine Safety & Health Administration (USA)
MVUE Minimum Variance Unbiased Estimate
N/A Not Applicable
NATA National Association of Testing Authorities (Australia)
NIOSH National Institute of Occupational Safety & Health (USA)
nm Nanometre
NMAM NIOSH Manual of Analytical Methods
NO Nitric Oxide
NO2 Nitrogen Dioxide
NOAEL No Observed Adverse Effect Level
NOHSC National Occupational Health & Safety Commission (Australia)
NTP Normal temperature and pressure (20 degrees C, 760 mm Hg) (note ACGIH TLV® defines NTP
conditions as 25 degrees C, 60 mm Hg)
NVvA Nederlandse Vereniging van Arbeidsdeskundigen
OD Outside Diameter
OEL Occupational Exposure Limits
OES Occupational Exposure Standards
OSHA Occupational Health & Safety Administration (USA)
PAT Proficiency Analytical Testing Programme
PCB Polychlorinated Biphenyls
PCM Phase Contrast Microscopy
PDM Personal Dust Monitor
PEL Permissible Exposure Limits
PM10 Particulate Matter less than 10 micrometres
PNA Polynuclear Aromatics
PNS Peripheral Nervous System
ppb Parts Per Billion
PPE Personal Protective Equipment
ppm Parts Per Million
ppt Parts Per Trillion
PTFE Polytetrafluoroethylene (Teflon)
PVC Poly-Vinyl Chloride
REL Recommended Exposure Limit
RPE Respiratory Protective Equipment
S (or SD) Standard Deviation
SCBA Self Contained Breathing Apparatus
SCOEL Scientific Committee on Occupational Exposure Limits

Measurement of Hazardous Substance Page 11


Abbreviations
SDS Safety Data Sheets
SEG Similar Exposure Groups
SEN Sensitisation
SIMPEDS Safety in Mines Personal Environmental Dust Sampler
SiO2 Silicon Dioxide
SK Skin
SMF Synthetic Mineral Fibre
SO2 Sulphur Dioxide
STEL Short Term Exposure Limit
STP Standard temperature and pressure (0 degrees C, 760 mm Hg).
T½ Half Life
TD Thermal Desorption
TDI Toluene Diisocyanate
TEL Tetra Ethyl Lead
TEM Transmission Electron Microscopy
TEOM Tapered Element Oscillating Microbalance
TLV® Threshold Limit Value
TLV-C TLV-Ceiling
TNT Tri-nitrotoluene
TWA Time Weighted Average
UK United Kingdom
UKAEA United Kingdom Atomic Energy Authority
UKAS United Kingdom Accreditation Service
USA United States of America
UV Ultra Violet
WA Western Australia
WASP Workplace Analysis Scheme for Proficiency
WEEL Workplace Environmental Exposure Levels
WEL Workplace Exposure Limits
WHO World Health Organisation
XRD X-ray Diffraction Spectrometry
XRF X-ray Fluorescence Spectrometry
Zn Zinc

Measurement of Hazardous Substance Page 12


Abbreviations
References

ACGIH (2007): Threshold limit values for chemical substances and physical agents and biological exposure
indices. ACGIH, 2007

AIHA (1991): A strategy for occupational exposure assessment. AIHA, 1991


AIHA (1998): A strategy for assessing and managing occupational exposures 2nd Edn. AIHA, 1998
AIHA (2006): A strategy for assessing and managing occupational exposures 3rd Edn. AIHA, 2006

AIOH (2007): Principles of Occupational Health & Hygiene. AIOH, 2007


AIOH (2017): Guideline for writing occupational hygiene reports. Australian Institute of Occupational
Hygienists, 3rd Edition; (https://shrtm.nu/QFlx,)

American Industrial Hygiene Association (AIHA) publication “A strategy for assessing and managing
occupational exposures”
AS/NZ4360: Risk management. Australian and New Zealand Standard 4360, 2004
AS2290: Electrical equipment for coal mines – Maintenance and overhaul. Part 3: Maintenance of gas
detecting and monitoring equipment. Australian Standard 2290.3, 1990
AS2985: Workplace atmospheres – Method for sampling and gravimetric determination of respirable dust.
Australian Standard 2985, 2004
AS2986: Workplace atmospheres – Sampling and analysis of volatile organic compounds by solvent
desorption gas chromatography. Part 1: Pumped sampling method, Part 2: Diffusive sampling
method. Australian Standard 2986, 2003
AS3640: Workplace atmospheres – Method for sampling and gravimetric determination of inhalable dust.
Australian Standard 3640, 2004
AS3853: Health and safety in welding and allied processes – Sampling of airborne particles and gases in the
operator’s breathing zone. Australian Standard 3853.1, 2006
Australian Institute of Occupational Hygienist (AIOH) publication “Simplified monitoring strategies”
BOHS (1993): Sampling strategies for airborne contaminants in the workplace. BOHS Technical Guide
No.11, 1993
BOHS/NVvA (2011) “Testing Compliance with OELs for Airborne Substances”
BSEN689 (1996): Workplace atmospheres – Guidance for the assessment of exposure by inhalation to
chemical agents for comparison with limit values and measurement strategy. British and European
standard 689, 1996
COSHH Regulations (2002): The control of substances hazardous to health regulations 2002 (as amended).
Approved Code of Practice and Guidance L5 (5th Edn), HSE Books, 2005
Dost, A.A. (1996): Monitoring surface and airborne inorganic contamination in the workplace by a field
portable x-ray fluorescence spectrometer. Ann. Occup. Hyg. J. 5, 589-610
European Standard EN 689:2018 “Workplace exposure. Measurement of exposure by inhalation to
chemical agents. Strategy for testing compliance with occupational exposure limit values”
Grantham, D. (2001): Simplified Monitoring Strategies. AIOH, November 2001

Measurement of Hazardous Substance Page 13


References
Hickey, J.L. & Reist, P.C., (1977): Application of occupational exposure limits to unusual work schedules.
AIHA Journal 38(ii): 613-621, 1977
HSE (1992): Biological Monitoring for Chemical Exposures in the Workplace. Guidance Note EH56

HSE publication HS(G) 173 "Monitoring strategies for toxic substances"


IRSST “Sampling Guide for Air Contaminants in the Workplace”
ISO (1995): Air quality – Particle size fraction definitions for health-related sampling. International
Standards Organisation, 2017
ISO (2018): Occupational Health and Safety Management Systems – Requirements with Guidance for Use.
International Standards Organisation, 2018
ISO (2018): Risk Management. International Standards Organisation, 2018
Kromhout H, Symanski E, Rappaport SM. (1993) A comprehensive evaluation of within- and between-
worker components of occupational exposure to chemical agents. Ann Occup Hyg; 37: 253–70.
Kromhout H, Symanski E, Rappaport SM. (1993) A comprehensive evaluation of within- and between-
worker components of occupational exposure to chemical agents. Ann Occup Hyg; 37: 253–70
MDHS 25/4: Organic isocyanates in air. Methods for the determination of hazardous substances. HSE,
March 2015
MDHS 35/2: Hydrogen fluoride and fluorides in air. Methods for the determination of hazardous
substances. HSE, April 1998
MDHS 82: The dust lamp. Methods for the determination of hazardous substances. HSE, March 1997.
MDHS 83/2: Resin acids in rosin (colophony) solder flux fume. Methods for the determination of hazardous
substances. HSE, July 2006
NIOSH (1977) Occupational Exposures Sampling Strategy Manual
NIOSH (1977): Occupational exposure sampling strategy manual. NIOSH January 1977
Oppl, R. Kalberlah, F, Evans, P.G. & Van Hemmem, J.J. (2003): A Toolkit for Dermal Risk Assessment and
management: An Overview. Ann. Occup. Hyg. Vol.47, No.8, 629-640, 2003
Ottoboni, M.A., (1997): The dose makes the poison: A plain English guide to toxicology, 2nd Edition
Ramachandran, G (2008) Toward Better Exposure Assessment Strategies—The New NIOSH Initiative Ann.
Occup. Hyg., Vol. 52, No. 5, pp. 297–301
Rappaport, S.M. and Selvin, S. (1987): A method for evaluating mean exposure from a lognormal
distribution. Am. Ind. Hyg. Assoc. J. 48, 374-379
Rappaport, S.M., Selvin, S. and Roach, S.A. (1988): A strategy for assessing exposures with reference to
multiple exposure limits. App. Ind. Hyg. J. 3, 310
SKC (2006): SKC Inc comprehensive catalog and sampling guide; www.skcinc.com
Tranter, M. (1999): Occupational Hygiene and Risk Assessment

Tranter, M. (2004): Occupational Hygiene and Risk Management, 2nd Edn


Western Australia Department of Mines & Energy (1997): Adjustment of exposure standards for extended
work shifts. Document No. ZME263AA, March 1999

Measurement of Hazardous Substance Page 14


References
http://ww.docep.gov.au/ResourcesSafety/Sectons/Mining_Safety/pdf_/MS%2
0GMP/Guidelines/MS_GMP_Guide_adjustmentexposurestandards.pdf
Wheeler, J.P. and Stancliffe, J.D. (1998): Comparison of methods for monitoring solid particulate surface
contamination in the workplace. Ann. Occup. Hyg. J. 7, 477-488
Wheeler, J.P. and Stancliffe, J.D. (1998): Comparison of methods for monitoring solid particulate surface
contamination in the workplace. Ann. Occup. Hyg. J. 7, 477-488
WHO (1997): Determination of Airborne Fibre Number Concentrations: A recommended method by phase
contrast optical microscopy (membrane filter method) published by the WHO (1997)
WHO (1997): Determination of Airborne Fibre Number Concentrations: A recommended method by phase
contrast optical microscopy (membrane filter method) published by the WHO (1997)

Measurement of Hazardous Substance Page 15


References
Index of Figures

FIGURE 2-1 EXAMPLES OF GHS PICTOGRAMS............................................................................................................23


FIGURE 3-1 TIME WEIGHTED AVERAGE (TWA) SUMMARY ..........................................................................................37
FIGURE 4-1 AIHA SAMPLE GUIDE ...........................................................................................................................67
FIGURE 4-2 BOHS/NVVA SAMPLING SCHEME ..........................................................................................................68
FIGURE 4-3 SAMPLING PATTERNS ............................................................................................................................70
FIGURE 5-1 THE DIFFERENCES BETWEEN THE DIFFERENT ISO FRACTIONS ......................................................................75
FIGURE 5-2 RESPIRABLE DUST SAMPLING TRAIN ........................................................................................................76
FIGURE 5-3 SAMPLING TRAIN PLACED ON WORKER....................................................................................................77
FIGURE 5-4 IOM SAMPLING HEAD ..........................................................................................................................80
FIGURE 5-5 CIS SAMPLER ......................................................................................................................................81
FIGURE 5-6 SKC BUTTON SAMPLER .........................................................................................................................81
FIGURE 5-7 PRE LOADED 37 MM PLASTIC CASSETTE ...................................................................................................82
FIGURE 5-8 MINI CYCLONE.....................................................................................................................................82
FIGURE 5-9 RESPICON SAMPLER..............................................................................................................................83
FIGURE 5-10 SCHEMATIC OF RESPICON STAGE IMPACTION ..........................................................................................83
FIGURE 5-11 3-PIECE CONDUCTIVE CASSETTE FOR FIBRE SAMPLING .............................................................................84
FIGURE 5-12 METAL COWL AND SAMPLING HEAD FOR FIBER SAMPLING .......................................................................84
FIGURE 5-13 DIESEL EMISSION PARTICULATE FILTER...................................................................................................85
FIGURE 5-14 SAMPLING FOR ROSIN BASED SOLDER FLUX FUME ...................................................................................85
FIGURE 5-15 DUAL SAMPLING HEAD SET..................................................................................................................86
FIGURE 5-16 DIAPHRAGM AIR SAMPLING PUMP SCHEMATIC.......................................................................................87
FIGURE 5-17 SOAP FILM METER .............................................................................................................................87
FIGURE 5-18 ROTAMETER ......................................................................................................................................88
FIGURE 5-19 ELECTRONIC FLOW METER...................................................................................................................88
FIGURE 5-20 CALIBRATION WITH BUBBLE FLOW METER..............................................................................................89
FIGURE 5-21 CALIBRATION WITH ELECTRONIC FLOW METER .......................................................................................90
FIGURE 5-22 DUST TRAK .......................................................................................................................................93
FIGURE 5-23 PERSONAL DUST MONITOR..................................................................................................................93
FIGURE 5-24 PRINCIPLE OF DUST LAMP....................................................................................................................94
FIGURE 6-1 SAMPLING TRAIN FOR SORBENT TUBE .....................................................................................................96
FIGURE 6-2 AIR SAMPLING TRAIN FOR SORBENT TUBE ................................................................................................97
FIGURE 6-3 SORBENT TUBE ....................................................................................................................................98
FIGURE 6-4 ILLUSTRATION OF BREAKTHROUGH CONCEPT ............................................................................................98

Measurement of Hazardous Substance Page 16


Index of Figures
FIGURE 6-5 MULTI-TUBE SAMPLE TUBE HOLDER .......................................................................................................99
FIGURE 6-6 THERMAL DESORPTION TUBES .............................................................................................................102
FIGURE 6-7 MIDGET IMPINGERS............................................................................................................................104
FIGURE 6-8 TYPICAL PASSIVE SAMPLERS .................................................................................................................104
FIGURE 6-9 3M DIFFUSION MONITOR ...................................................................................................................105
FIGURE 6-10 USE OF AIR SAMPLING PUMP TO FILL GRAB BAG...................................................................................107
FIGURE 6-11 DRÄGER TUBES AND BELLOWS SAMPLING PUMP ...................................................................................113
FIGURE 6-12 NEW (LEFT) AND USED (RIGHT) COLORIMETRIC TUBES ..........................................................................113
FIGURE 7-1 SCHEMATIC OF AN ATOMIC-ABSORPTION SPECTROMETER ........................................................................122
FIGURE 7-2 ATOMIC ABSORPTION SPECTROMETER...................................................................................................122
FIGURE 7-3 GRAPHITE FURNACE ...........................................................................................................................123
FIGURE 7-4 SCHEMATIC OF A SINGLE BEAM UV-VIS SPECTROPHOTOMETER .................................................................124
FIGURE 7-5 IR SPECTRUM FOR QUARTZ ..................................................................................................................125
FIGURE 7-6 GAS CHROMATOGRAPH.......................................................................................................................125
FIGURE 7-7 GAS CHROMATOGRAPH MASS SPECTROMETER .......................................................................................126
FIGURE 7-8 SAMPLING HEAD FOR ASBESTOS FIBRES .................................................................................................129
FIGURE 7-9 PHASE CONTRAST MICROSCOPY – AMOSITE FIBRES & SYNTHETIC MINERAL FIBRES ......................................130
FIGURE 7-10 CHRYSOTILE.....................................................................................................................................130
FIGURE 7-11 AMOSITE (1ST ORDER RED RETARDATION) ...........................................................................................131
FIGURE 9-1 NORMAL AND LOGNORMAL DISTRIBUTIONS ...........................................................................................147
FIGURE 9-2 AM AND GM OF LOGNORMAL DISTRIBUTIONS .......................................................................................150
FIGURE 10-1 DIAGRAM OF THE LAYERS OF THE HUMAN SKIN .....................................................................................161
FIGURE 10-2 RESPIRATORY SYSTEM .......................................................................................................................163
FIGURE 10-3 DOSE RESPONSE CURVE ....................................................................................................................169
FIGURE 10-4 VARIABILITY OF HUMAN EXPOSURE TO DOSE ........................................................................................170

Measurement of Hazardous Substance Page 17


Index of Figures
Index of Tables

TABLE 2-1 SOURCES OF INFORMATION ABOUT POTENTIAL CHEMICAL RISKS ...................................................................24


TABLE 2-2 RISK IDENTIFICATION ..............................................................................................................................26
TABLE 2-3 CONTROL BANDS FOR EXPOSURES TO CHEMICALS BY INHALATION .................................................................28
TABLE 3-1 OEL FACTORS .......................................................................................................................................44
TABLE 3-2 OEL DOCUMENTATION...........................................................................................................................45
TABLE 4-1 RAPPAPORT AND SELVIN SAMPLE NUMBER MODEL (Α= 0.05, Β= 0.10).........................................................66
TABLE 4-2 NIOSH SAMPLE SIZE GUIDE ....................................................................................................................67
TABLE 5-1 FILTER SELECTION GUIDE ........................................................................................................................79
TABLE 5-2 REQUIRED FLOW RATES FOR DIFFERENT CYCLONE TYPES ..............................................................................83
TABLE 5-3 COMPARISON OF DIFFERENT TYPE OF AIR SAMPLING PUMPS ........................................................................86
TABLE 5-4 CALIBRATION INTERVALS .........................................................................................................................90
TABLE 5-5 DATA FOR TWA EXAMPLE CALCULATION...................................................................................................92
TABLE 5-5 SUMMARY OF AIR SAMPLING GUIDE .........................................................................................................94
TABLE 6-1 SORBENT TUBES TYPES ...........................................................................................................................99
TABLE 6-2 SAMPLING FLOW RATES ........................................................................................................................108
TABLE 6-3 3M DIFFUSION MONITOR TEMPERATURE CORRECTION FACTORS ................................................................109
TABLE 6-4 DIFFUSION MONITOR DATA ..................................................................................................................110
TABLE 6-5 DIRECT READING INSTRUMENT CROSS SENSITIVITY ....................................................................................112
TABLE 6-6 CALIBRATION CLASSES ..........................................................................................................................115
TABLE 6-7 SUGGESTED MAINTENANCE SCHEDULE BASED ON INSTRUMENT USE ............................................................116
TABLE 6-8 EXPLOSIVE ZONE CLASSIFICATIONS..........................................................................................................117
TABLE 6-9 EXPLOSION PROOF CLASSIFICATION ........................................................................................................118
TABLE 6-10 MAXIMUM SURFACE TEMPERATURE / IGNITION TEMPERATURE ................................................................118
TABLE 6-11 LEVEL OF EXPLOSION PROTECTION AND EXPLOSION ZONES .......................................................................119
TABLE 9-1 NORMAL VS LOG NORMAL PARAMETERS .................................................................................................148
TABLE 9-2 RULES OF THUMB GSD VALUES .............................................................................................................149
TABLE 10-1 RECOMMENDED SAMPLING TIMES .......................................................................................................155
TABLE 10-2 OPTIMUM TIME FOR COLLECTING SAMPLES ...........................................................................................156
TABLE A-3 TARGET ORGANS, WITH AN OUTLINE OF THEIR PRINCIPAL FUNCTIONS.........................................................166

Measurement of Hazardous Substance Page 18


Index of Tables
Chapter 1 Course Overview

1.1 Introduction

This Course has been delivered by OHTA approved training providers for over 10 years and
reviewed by international experts on two occasions to ensure the information is accurate and
current. The latest update was 2023.

The mention of any method, product, manufacturer or vendor as examples in this manual should not in any
way be construed as either endorsement or recommendation of such by either OHTA, authors,
contributors, or editors of this manual.

1.2 Aim of Course


To provide students with a sound understanding of the techniques for assessing exposure to
hazardous substances in the workplace and with an understanding of how exposure information
can be used to assess risk.

1.3 Learning Outcomes


On successful completion of this module the student will be able to:
• Describe the general approach to occupational chemical health risk assessment,
including the role of atmospheric monitoring;

• Select appropriate equipment to measure specific airborne contaminants and devise a


suitable sampling strategy;

• Present the results in a form useful for health risk assessment purposes to enable
management to comply with relevant legislation.

1.4 Format of Manual


It should be recognized that the format presented in this manual represents the views of the
authors, contributors and or editors, and does not imply any mandatory process or format that
must be rigidly observed. Presenters using this manual may well choose to alter the teaching
sequence or course material to suit their requirements. In this regard the case studies are
provided as illustrative examples and alternate case studies relevant to a particular industry may
be used if desired.

In the final outcome, the aim of this manual is to transmit the principles of hazardous substances
measurement to attendees and provide guidance as to how those principles should be applied.

Measurement of Hazardous Substance Page 19


Chapter 1 Course Overview
Chapter 2 Risk Assessment

This section introduces the concept of risk assessment as it applies to occupational hygiene. Key
points of this chapter are as follows
✓ Hazard vs risk vs exposure

✓ Principles of risk assessment

✓ Qualitative vs. quantitative approaches

Risk assessment is a central part of occupational hygiene, the art and science of anticipation,
recognition, evaluation and control (AREC) of work place hazards. Risk assessment allows
occupational hygienists to evaluate whether controls are needed, or if they already exist whether
they need improvement.

The objective of this chapter is to discuss risk assessment as it applies to occupational hygiene
practice. Risk assessment encompasses all areas of human activities since all entail some degree of
risk. Much has been written about risk assessment, and the language used can be inconsistent in
definition and or application. The international standards organisation (ISO) approach (ISO 31000
Risk Management Practices: 2018) provides a useful frame work by which to examine and evaluate
occupational hazards as discussed below, and provides insight into what is involved in the risk
assessment process.

2.1 Introduction to Risk Assessment


Risk assessment in the context of occupational hygiene practice is generally an evaluation of risk of
adverse effect associated with a particular process of activity that uses substances associated with
particular hazards. In this publication, the terms “hazard” and “risk” will be treated solely in
relation to chemical risk and not in any broader concept. In the context of this course, “hazard”
and “risk” are not the same thing. A key role for occupational hygienists is establishing the level of
risk in workplace through the evaluation of hazards as discussed in this chapter.

Risk (uncontrolled)  hazard x exposure

One way to express the relation between risk, hazard and exposure is as follows:

Where risk is can be seen as an uncertainty of adverse outcome (worker illness for
example). Ideally, we might want zero risk, but in reality, this is impractical, so the
issue becomes what is acceptable risk, or how safe is safe? The issue of what is an
acceptable risk has been much discussed and is a variable quantity depending on

Hazard is an undesirable property of a particular substance, usually toxicity (long or


short term or both) or irritation. It is an intrinsic property and usually cannot be
changed without altering the substance itself. For example, a concentrated acid can
cause serious skin burns on contact, but very dilute acids generally do not, the key
hazard being concentrated acid in this example. Essentially, the threat is different.

Measurement of Hazardous Substance Page 20


Chapter 2 Risk Assessment
Exposure is an estimate of how much a person engaged in the process of interest
could be exposed to, typically by inhalation but also by skin contact for certain
substances. This variable is of central interest in occupational hygiene, and essentially
represents an estimate of potential dose. As discussed in this course, exposures are
evaluated against benchmarks, most commonly occupational exposure limits (OELs) as
discussed in Chapter 3. Exposure is essentially an indicator of risk. These exposures can
be measured (as discussed in this class), or they can be estimated in a variety of ways
(e.g., previous studies of same or similar processes, exposure modeling).

The AIHA (American Industrial Hygiene Association) offers the following definition for risk
assessment

Risk assessment is the determination of quantitative or qualitative value of risk related


to a concrete situation and a recognized threat (also called hazard). Quantitative risk
assessment requires calculations of two components of risk (R): the magnitude of the
potential loss (L), and the probability (p) that the loss will occur. Acceptable risk is a
risk that is understood and tolerated usually because the cost or difficulty of
implementing an effective countermeasure for the associated vulnerability exceeds
the expectation of loss.

From a risk assessment perspective, it can be deduced from the above equation that making
either term in the above equation zero, then the risk would also be zero. So, in occupational
hygiene practice, one might eliminate the hazard by using a substance that has a lesser hazard. For
example, solvent based paints can be replaced with water-based paints.

However, hazard elimination may not always be feasible so occupational hygiene practice would
be to turn to find ways of reducing exposures. For example, use enclosed processes rather than
open vessels, or use adequate ventilation, or even require respiratory protection. Exposure
measurements can then provide a tool to evaluate how effective controls might be in reducing
them or containing them within acceptable limits.

2.2 The Risk Assessment Process


ISO 31000:2018 Risk Management Principles defines risk as the effect of uncertainty. This
uncertainty could be positive, and one might be interested in increasing it, for a more desirable
outcome. In other words, how to optimize the chances of a good result. In other cases, uncertainty
(i.e., risk) could be unwanted, as for example from a catastrophic event or accident. In
occupational hygiene terms, one might think of risk in terms of how safe a process or activity
might be in terms of substances and or by-products involved. A safety engineer might look at a
process in terms of risk of direct injury (rather than long term effects). Many activities may have
good and bad risks (for example, financial investments). This course focuses on assessing risks
associated with chemical substances that may be encountered in the work place.

ISO 31000 definitions provide a framework by which to consider occupational health risk
assessment.

Measurement of Hazardous Substance Page 21


Chapter 2 Risk Assessment
Risk Management is generally defined as coordinated activities to direct and control
risks. The general principle is to create and protect value, which in the case of
occupational hygiene, is to protect worker health. Workplace health and safety
programs are in essence a risk management tool. Risk management is relevant to all
areas of human activity including agriculture, business, politics, and even our everyday
activities (e.g., driving to work). Often, the entire process is a continuum rather than in
the discrete steps described below that are part of the process. Without the need to
manage risks, or where risks may be considered negligible, there is no need to conduct
risk assessments. ISO’s guideline identifies three important components of risk
management as follows:

Risk Identification, which is to find, recognize and describe risks that will impact a
particular organisation. This is where anticipation and recognition of potential hazards
come in.

Risk Analysis the goal of which is to better understand the nature and characteristics
of identified risks, and where necessary, estimate the level of risk. This is where hazard
evaluation and control start.

Risk Evaluation which supports decisions made in the risk analysis process. How well
does the risk analysis compare with established criteria? This is where we refine hazard
evaluation, and adjust controls as needed

The concept of risk assessment is central to the occupational health and safety legislative
framework in many countries.

2.3 Occupational Hygiene Risk Assessment Overview


There are many guidelines and regulatory requirements for occupational hygiene risk assessment
(e.g., United Kingdom (UK) COSHH Regulations, Occupational Health & Safety Administration
(OSHA’s) general duty clause), all of which generally require identifying, analysing and evaluating
work related risks as they pertain to working with chemical substances and or by-products. In
some cases, there may be a mandated or recommended approach. Regardless, it is usually better
to follow a consistent approach.

This section is intended to provide an overview of risk assessment in terms of occupational


hygiene. In occupational hygiene, it is a qualitative approach rather than a quantitative analysis
that yields theoretical risks, based on assumptions made for the model used to calculate risk
values. This quantitative approach is often related to environmental exposures. It is beyond the
scope of this course.

2.3.1 Risk Identification


The process begins with gathering basic information about chemicals in the workplace. Many
locations keep chemical inventories, in some cases required by regulation. If there is no inventory,
it follows that one will need to be compiled for systematic risk identification. Obviously, it is critical
to keep inventories up to date, so therefore also wise to check with end users particularly for
anything that raises concerns. It’s also important to consider by-products from particular

Measurement of Hazardous Substance Page 22


Chapter 2 Risk Assessment
processes (e.g., welding fume, dust, etc.), as well as waste products, as these may pose additional
risks.

An important consideration in identifying chemical hazards are potential routes of exposures. Can
the substance of interest be breathed in? Is skin contact an issue? Ingestion is often another
possibility, although this is usually managed through good personal hygiene practices.

Physical properties are also important. Is a substance volatile (high vapours pressure)? Is in gas or
solid form. If solid, will it generate respirable dust?

Two good sources for identifying risks related to chemical substances at work are Safety Data
Sheets (SDS) as well as labels and signs on products and or containers and vessels.

The UN’s Globally Harmonized System of Classification and Labelling of Chemicals (GHS) is a
worldwide accepted system for classifying and communicating the hazards of industrial and
consumer chemicals. The GHS provides for universal pictograms to provide an indication of a
hazard that a substance might pose. These pictograms are supported by standard hazard
statement language within a particular SDS. In some instances, more than one pictogram may be
relevant Figure 2-1 shows examples of GHS pictograms.

Figure 2-1 Examples of GHS Pictograms

Oxidizer Flammables, Self-Reactive, Pyrophoric, Explosives, Self-Reactive, Organic


Self-Heating, Emits Flammable Gas, Peroxides
Organic Peroxides

Acutely Toxic Burns Skin, Damages Eyes, Corrosive to Gases Under Pressure
(severe) Metals

Carcinogen, Respiratory Sensitiser, Toxic to aquatic environment Acutely toxic (harmful), Irritant to skin, eyes
Reproductive Toxicity, Target Organ or respiratory tract, Skin sensitiser,
Toxicity, Mutagenicity Aspiration Toxicity Hazardous to the Ozone layer.

Measurement of Hazardous Substance Page 23


Chapter 2 Risk Assessment
Note, however, that just because a container may be labeled with one of the above pictograms, it
does not necessarily indicate there is a risk to workers. That would depend on whether there is
worker exposure, and if so, how much. For example, a small vial of a volatile solvent in a
laboratory hood is not the same as an open vat of the same solvent in a factory. This is part of risk
analysis, often blended with risk identification into one step, since the next question after “is there
exposure?” is “how much exposure is there?”

Other ways to identify potential chemical risks would be through employee interviews, company
records (e.g., illness and injury statistics), government and industry standards and associations, as
well as the scientific literature. The important thing is to be systematic to reduce the risk of
missing something. Table 2-1 Sources of Information about Potential Chemical Risks lists typical
sources of information.

Table 2-1 Sources of Information about Potential Chemical Risks

Collection Method Type of Information

Tasks Processes
Interviews of workers, managers and
Work practices Exposure controls
engineers
Health issues Maintenance

Interviews of occupational health and safety Health problems Work practices


personnel Patterns of problems Exposure history

Records:
Historic conditions Performance of engineering
Process standards controls
Standard operating procedures Chemical inventories
Production Past occupational hygiene
Usage amounts
Personnel monitoring reports
Medical Tasks
Past biological monitoring
Engineering Work histories results
Process flow diagrams

Governmental and non-governmental


Current exposure limits Proposed exposure limits
standards

Epidemiological studies
Literature Emerging issues
Toxicological studies

2.3.2 Risk Analysis


Having identified potential chemical hazards, the next step is to analyse the extent and magnitude
of potential risks associated with them. The following should be considered

• Who might be exposed directly and indirectly. Are there vulnerable workers (e.g.,
women of reproductive age)?

Measurement of Hazardous Substance Page 24


Chapter 2 Risk Assessment
• How is the work/process done? How are materials handled?

• The level, duration and frequency of exposure.

• What are the relevant occupational exposure limits (OELs)?

• Has this process been studied before? Is there previous data that can be used?

• Are there other ways to estimate exposures (e.g., modeling)?

• Presence and effect of control measures.

• Containment measures e.g., open vs. closed.

• Local exhaust ventilation e.g., fume cupboards; extraction hoods.

• Is there personal protective equipment (PPE) in use? What was the basis for selection?

• Housekeeping and site conditions.

• Are there standard operating procedures? Do they address the hazards of concern?

• Is there any history of reported adverse effects?

In some cases, it may not be possible to obtain complete information in which case one has to rely
on good occupational hygiene judgement.

2.3.3 Risk Assessment


Risk identification and risk analysis lead to risk assessment, which can also be seen as an
evaluation of how good the initial risk analysis. Initial analysis may show exposures of concern but
subsequent monitoring may show otherwise (good news), or we might discover the converse.

We have seen that occupational health related risks will be determined by:

• How much a worker is exposed to a hazardous substance (exposure)

• How the worker is exposed to the substance (inhalation, skin contact, i.e., route of entry
to the body)

• How severe are the adverse health effects under the conditions of exposure (health
hazards)

• The duration and frequency of exposure (a single short exposure or continuous long-
term exposure)

Although occupational hygiene risk assessments rely on estimates of exposures, the usual
outcome is qualitative or semi qualitative. In practice, qualitative assessment is usually used first
to screen risks and to highlight activities with higher risk. Subsequently, it may be necessary to

Measurement of Hazardous Substance Page 25


Chapter 2 Risk Assessment
conduct a more detailed study of exposures associated with higher risk activities to better assess
associated risks.

Generally speaking the outcome of an occupational risk assessment can be summarized as follows:

Table 2-2 Risk Identification

Risk Level Description

Unacceptable Significant risk e.g., exposure exceeds OELs. Exposure risk is not adequately
controlled. Further risk reduction is required.

Acceptable Exposures consistently below OEL. May need to consider routine monitoring for
change. Adequate controls such that its adverse health effects on worked are not
expected.

Inconclusive Insufficient information available to make a conclusion


Monitoring or more information is required to further define exposure.

Risk assessment can also be quantitative rather than descriptive. It may include factors such as
exposure monitoring data, modeling data, extrapolation from relevant studies to calculate
estimate risk values. Quantitative risk assessment is often used to determine OELs, or sometimes
to set exposure limits associated with a particular level of risk. Quantitative risk assessment
methods are beyond the scope of this course.

2.4 Risk Assessment Tools


There are various online tools to help with work health risk assessment such as

• UK’s Control of Substances Hazardous to Health (COSHH) Essentials e-tools (see


https://shrtm.nu/PS9Z)

• International Labor Organisation (ILO) Tool kit (see https://shrtm.nu/nYqk

• US Federal OSHA (see https://shrtm.nu/bcQy

Keep in mind that there may be specific requirements in different geographic areas, so best to find
out ahead of time to avoid wasted effort.

2.5 Non-Sampling Approaches


Air sampling is not always necessary to develop control strategies for certain processes. Instead,
one may be able use the concept of “control banding” which has achieved significant prominence,
especially in Europe. Commonly used approaches include the UK’s Control of Substances
Hazardous to Health (COSHH) Essentials and the ILO Chemical Control Toolkit.

The control banding approach focuses resources on exposure controls and describes how strictly a
risk needs to be managed. This qualitative risk assessment and management tool is intended to

Measurement of Hazardous Substance Page 26


Chapter 2 Risk Assessment
help small businesses by providing an easy-to-understand, practical approach to controlling
hazardous exposures at work.

It should also be recognized that all such systems provide general guidance based on the most
likely scenario and do not take account of individual process variations. While such systems are a
useful tool for small businesses, assessment of a workplace by an experienced occupational
hygienist may be (and in many cases is) required.

It is important to realize that non-sampling approaches such as COSHH Essentials and the ILO
Chemical Control Toolkit have some limitations, and may not be appropriate for situations, such as
some “hot” processes, open spray applications, gases, etc. However, COSHH Essentials scheme is
being progressively extended by the addition of industry and task-specific guidance for many
situations (see http://www.hse.gov.uk/pubns/guidance/index.htm. Control advice sheets are now
available for welding, metalworking fluids, silica exposures and low-level asbestos work. Particular
industries such as printing have also developed customized sheets for their own specialized
processes.

2.5.1 Control Banding


Control banding is a process in which a single control technology (such as general ventilation or
containment) is applied to one range or band of exposures to a chemical (such as 1 – 10 mg/m³)
that falls within a given hazard group (such as skin and eye irritants or severely irritating and
corrosive). Four main control bands have been developed for exposure to chemicals by inhalation:

• Band 1 – Use good industrial hygiene practice and general ventilation

• Band 2 – Use local exhaust ventilation

• Band 3 – Enclose the process

• Band 4 – Seek expert advice

For some activities, processes, tasks or jobs, experts can specify that respiratory protective
equipment (RPE) (in combination with other control approaches) is always necessary. The most
developed model for control banding has been established by the Health & Safety Executive (HSE)
of the United Kingdom (UK).

The principle of control banding was first applied to dangerous chemicals, chemical mixtures, and
fumes. The control banding process emphasizes the controls needed to prevent hazardous
substances from causing harm to people at work. The greater the potential for harm, the greater
the degree of control needed to manage the situation and make the risk “acceptable”.

The basis of these bands for exposures to chemicals by inhalation is detailed in Table 2-3 Control
Bands for Exposures to Chemicals by Inhalation.

Measurement of Hazardous Substance Page 27


Chapter 2 Risk Assessment
Table 2-3 Control Bands for Exposures to Chemicals by Inhalation

Band Target Range of


Hazard Group Control
No. Exposure Concentration

Use good industrial hygiene


>1 to 10 mg/m³ dust
1 Skin and eye irritants practice and general
>50 to 500 ppm vapours
ventilation

>0.11 to 1 mg/m³ dust Harmful on single


2 Use local exhaust ventilation
>5 to 50 ppm vapours exposure

>0.01 to 0.1 mg/m³ dust Severely irritating and


3 Enclose the process
>0.5 to 5 ppm vapours corrosive

Very toxic on single


<0.01 mg/m³ dust
4 exposure, reproductive Seek expert help
<0.5 ppm vapours
hazard, sensitiser*
* Exposure to any concentration of a sensitiser requires expert advice

This approach has been developed into web-based applications specifically to assist small and
medium-sized enterprises to do risk assessments for chemicals and mixtures of chemicals.

The most developed of these is COSHH Essentials. COSHH Essentials (http://www.coshh-


essentials.org.uk ) is a control banding tool that helps small and medium-sized enterprises to do
risk assessments for chemicals and mixtures of chemicals. This tool requires four pieces of
information:

• The type of task (e.g., mixing liquids, sack filling, manually cleaning and disinfecting
surfaces)

• The hazard classification from the material safety data sheet (MSDS) obtained from the
chemical manufacturer or supplier

• The volatility or dustiness of the chemical or product

• The amount used in the task (small quantities = grams or millilitres (ml); medium
quantities = kilograms or litres (L); large quantities = tons or cubic metres (m³))

The system then:

• Identifies the control band (control approach),

• Produces advice on controlling risk from the chemical used in the specified task, and

• Provides written guidance and documentation as a result of the assessment.

In British law, the duty to control risk remains with the employer. Both the web and paper versions
of the COSHH Essentials tools are designed to assist the small or medium-sized employer meet
regulatory requirements. COSHH Essentials is a free service and was developed by the HSE in
collaboration with British industry and trade unions.

Measurement of Hazardous Substance Page 28


Chapter 2 Risk Assessment
A similar approach to COSHH Essentials has been developed jointly by the ILO, World Health
Organisation (WHO) and United Nations Environment Programme and published as the ILO
Chemical Control Toolkit

The ILO Toolkit has five (5) stages which need to be followed. These are:

Stage 1: Find the hazard classification and match it to a hazard group. For common
solvents this has already been done and the information provided on the ILO website.
For other substances there is a need to establish the risk phrases for the substance and
then find the hazard group from the ILO website.

Stage 2: Establish the amount of substance to be used and use this to determine the
scale of use from the table supplied by the ILO.

Stage 3: Establish how much of the substance will escape to the atmosphere. This is
done via looking at the physical state of solids (e.g., pellets – low, crystalline – medium,
fine powders – high) or via comparison of the boiling point of liquids to a table
provided by the ILO.

Stage 4: Find the control approach by using a selection guide that has been prepared
by the ILO.

Stage 5: Find the task-specific control guidance sheet(s) from a table which links the
task description and the control approach.

Once the appropriate control approach has been determined it needs to be implemented and
maintained.

Control banding approaches have been developed in Belgium (REGETOX project), The Netherlands
(Stoffenmanager), and Norway (KjemiRisk). The World Health Organisation is working with its
Collaborating Centres to pilot control banding programmes in more than a dozen countries.

It is important to realize that non sampling approaches such as COSHH Essentials and the ILO
Chemical Control Toolkit are not appropriate for many situations. Such situations could include
some “hot” processes, open spray applications, gases, etc. However, the COSHH Essentials scheme
is being progressively extended by the addition of industry and task-specific guidance on many
situations; see http://www.hse.gov.uk/pubns/guidance/index.htm. Sheets are now available for
welding, metalworking fluids, silica exposures and low-level asbestos work. Particular industries
such as printing have developed customized sheets for their own specialized processes.

It should also be recognized that all such systems provide general guidance based on the most
likely scenario and do not take account of individual process variations. While such systems are a
useful tool for small businesses, assessment of a workplace by an experienced occupational
hygienist may be (and in many cases is) required.

Measurement of Hazardous Substance Page 29


Chapter 2 Risk Assessment
2.5.2 Exposure Modelling
Simple modelling approaches can also be helpful to estimate exposures, based on variables such
as contaminant emissions rate, room volume, dispersion patterns and worker locations. The
AIHA’s IHMOD2 is a useful Excel based tool in this regard (see https://tinyurl.com/y92mpsdo)

COSHH Essentials and the ILO’s Organisation’s Chemical Control Toolkit provide a simple method
to identify appropriate controls using basic toxicological information from labels and information
on volatility or dustiness and usage rates. The output from these models can be compared with
the control measures in use to assist in the evaluation of the suitability of the controls. More
sophisticated models, such as Stoffenmanager and the Advanced Reach Tool (ART) can provide an
estimate of exposure.

2.6 Documentation
Chemical exposure risk assessments should be documented. The information documented should
be proportional to anticipated risks. Besides regulatory requirements, reasons for documenting
the risk assessments include:

• To demonstrate to stakeholders that the process has been conducted properly;

• To provide evidence of a systematic approach to risk identification and analysis;

• To enable decisions or processes to be reviewed;

• To provide a record of risks and to develop the organisation’s knowledge database;

• To provide decision makers with a risk management plan for approval and subsequent
implementation;

• To provide an accountability mechanism and tool;

• To facilitate continuing monitoring and review;

• To provide an audit trail; and

• To share and communicate information.

Many statutory authorities require assessment records are kept for a number of years including
risk assessments, monitoring records, health surveillance records, maintenance examination, test
or training records (e.g., 5 to 50 years).

2.7 Periodic Review


Chemical exposure risk assessments should be reviewed periodically, depending on the risk level.
In some cases, this may be prescribed by regulation. Activities with higher risks may need to be
reviewed more frequently. They should also be reviewed if there is any reason to suspect previous
risk assessments are no longer valid, e.g., significant changes in the work processes such as use of
new substances, improvements in control methods etc.

Measurement of Hazardous Substance Page 30


Chapter 2 Risk Assessment
2.8 An Outline of an Approach to Risk Management
Risk assessments that identify risks that need to be controlled (i.e., managed) should result in the
development and implementation of a plan to manage and or control the risks such as codes of
safe practices, the use of ventilation, personal protective equipment etc. It is vital to have input
from all affected stakeholders (i.e., management, workers, occupational hygienists, etc.). To be
able to affect required or recommended operational change within an organisation. This is unlikely
to happen without commitment from senior management so that the necessary resources are
available. There are many approaches to developing occupational risk management plans,
including ISO 45000, which provides a useful frame work.

It is also important is the need to communicate the findings of risk assessments as well as
whatever requirements a risk management plan may have. This information needs to be shared
with both the management and the employees if there is benefit to be derived from risk
assessment.

Also critical is to implement a continuous cycle of improvement (e.g., plan, do, check, adjust), to
keep the risk management plan up to date and relevant.

2.9 Hierarchy of Controls


Occupational risk management approaches generally involve the hierarchy of controls as follows:

2.9.1 Elimination and Substitution


Elimination and substitution are the most effective methods to reduce hazards. However, this is
not always practical depending on the process. There may not always be a satisfactory alternative
process or substance. Some elimination and substitution questions to consider include:

• Can the process be eliminated?

• Can less hazardous substances be used? Can they be used in a less hazardous form (solid
rather than dust, or aqueous rather than solvent based)?

2.9.2 Engineering Controls


Engineering controls are designed to remove the hazard at the source so that the exposure be
eliminated or reduced such that the risk is acceptable. Some engineering control issues to consider
are:

• Can the process be enclosed (so that emissions are contained)?

• Can ventilation be used? General dilution or exhaust ventilation?

While engineering controls may appear to solve problems, they may not always be feasible due to
budgets and or other considerations. Some activities may be too infrequent or temporary to justify
a ventilation system. Moreover, controls such as ventilation require maintenance to ensure they
are operating as designed, and it’s important they are properly used. Nevertheless, engineering
controls are seen as superior because they are intended to engineer out exposures, and hence

Measurement of Hazardous Substance Page 31


Chapter 2 Risk Assessment
reduce risk, although they can be costly investments that occupational hygienists may need to
justify.

2.9.3 Administrative Controls


Administrative controls centre around managing the risk rather than trying to reducing or
eliminate it through engineering controls. They include actions such as

• Reducing number of workers exposed (i.e., do it where/when there are fewer workers)

• Reducing the duration of exposure (e.g., use job rotation to reduce the exposure
duration for any individual)

• Are there safer ways to do the job (e.g., cover open containers when not in use)?

• Using codes of safe operating practices, and making sure affected people are trained on
them

This approach requires following specified procedures, but it can be challenging to modify human
behavior. Administrative controls in essence are about managing people to manage the risk.

2.9.4 Personal Protective Equipment


In essence, personal protective equipment is about posing a barrier between an unacceptable (or
potentially unacceptable) risk and the worker. Although it can be effective, it is the least reliable
way to reduce worker exposure because they allow worker exposure if they are not worn, or not
worn correctly. In other words, it’s necessary to train users on proper use, limitation and
maintenance of these devices. Moreover, the use of respirators generally imposes additional
requirements, often regulatory, such as written protocols for their use, medical evaluations. So
while they may appear to be initially cost-effective, they may not be so in the long term when
costs of administering a personal protective equipment are taken into account.

Note that in practice a combination of these measures may be required to control exposures,
including short term and longer-term actions. For example, respiratory protection may be used
until a ventilation system can be brought online.

All control measures should be reviewed at regular intervals to ensure that adequate control is
maintained. Routine checks, regular maintenance and appropriate supervising procedures are also
necessary.

2.9.5 Information, Instruction and Training


Training and information should be provided to workers so that they understand the risks to
health from chemical agents and the precautions to be taken. The extent of training will depend
on the level of risk, with more extensive training being required for workers who are exposed to
greater risks. The information collected during the assessment about the nature of the hazards
and the control measures required should be used in preparing information, instruction and
training.

Measurement of Hazardous Substance Page 32


Chapter 2 Risk Assessment
2.9.6 Workplace Monitoring
A health and safety program may specify routine monitoring as a check on the effectiveness of
controls. Additional monitoring may also be required if:

• New control measures have been implemented;

• Interim measures are in place while better controls are procured;

• Control measures have deteriorated or failed such that serious health effect could result:
e.g., carcinogens and allergens

• Required by regulation

Personal exposure monitoring should only be conducted by a professional Occupational Hygienist


or under the supervision of a professional Occupational Hygienist. Note that occupational
hygienists sometimes refer to workplace monitoring “quantitative exposure assessment”, which
should not be confused with quantitative risk assessment

2.9.7 Health Surveillance


Some health and safety programmes may require worker medical surveillance when one or more
of the following is applicable:

• Identifiable work-related disease or adverse health effect related to exposure;

• Reasonable likelihood that the disease or condition may occur;

• There are validated indicators of early signs of disease or adverse effect; and, or

• Exposures are liable to exceed limits prescribed in substance specific regulations that
require health surveillance.

Health surveillance should be conducted by or under the supervision of a health professional. Note
also that there may be requirements for preservation of patient confidentiality as well as for
retention of health surveillance data. US OSHA regulations for example may require employers to
retain medical and exposure records for 30 years following employee termination in some
instances, and European regulations require such records to be kept for 40 years from the last
entry.

Measurement of Hazardous Substance Page 33


Chapter 2 Risk Assessment
2.9.8 Emergency Procedures
Emergency releases of substances at work can result in exposures and hence present a risk of
adverse effect. Most health and safety programs address risks of leaks, spills or other uncontrolled
releases of chemicals by having an emergency plan that includes appropriate procedures for
prevention, and emergency response (i.e., personal protective equipment, first aid, safety showers
and eye wash facilities, evacuation procedures,
emergency procedures, etc.). In essence,
emergency procedures are the outcome of risk Case Study Risk Assessment
assessments applied to what-if scenarios.
Lifeguards on a windy beach. Seasonal work
Affected parties need to be trained on how to
(3 months a year), high turnover with few
recognize emergencies and how to respond.
lasting more than 3 seasons. The beach is
Emergency procedures regarding chemical
closed when winds exceed 25 knots due to
substances should be part of a comprehensive
high waves. You learn that sand has silica
health and safety plan.
and that it causes cancer. Are lifeguards at
risk?
2.9.9 Management Role
Risk ID: crystalline silica hazard.
As discussed above, management participation in
occupational health and safety programs is Risk Analysis: Your research shows that
essential. crystalline silica is associated with silicosis
and lung cancer in miners with 15 or more
The degree of prescription (i.e., need to follow a
years of exposure to dusty conditions.
specific approach) in occupational health and
safety legislation has diminished around the You also learn that beach sand particles are
world. Most statutory authorities have moved to much larger than silica particles in mines.
a risk-based approach whereby employers must Also it turns out that beach sand is less
determine risk for all operations within their biologically active than silica in mines.
organisation. This is where recommended
practices such as ISO are valuable as they provide In summary: Miners work in dusty
systematic approaches. Many statutory conditions, whereas beaches generally not
authorities produce guidance material, which dusty and would be closed when it’s too
essentially defines minimum standards, however windy. Most lifeguards work 3 months for
the onus is on the employer to establish the level three years or less, so a total of 0.75 years.
of risk associated with any activity. The miners in the study work for 15 years or
more.
Large mature organisations have generally
adopted risk management practices. However, Beach sand is less harmful than crystalline
small to medium enterprises still struggle with silica in mines
the concept because of limitations in resources.
Occupational hygienists fill an important role in What do you conclude?
establishing workplace risks through hazard
evaluation.

Measurement of Hazardous Substance Page 34


Chapter 2 Risk Assessment
Chapter 3 Occupational Exposure Limits

This chapter describes and discusses the concept of Occupational Exposure Limits (OELs):
✓ What are they?

✓ Why are they relevant?

✓ Where do they come from?

3.1 Introduction to OELs


Occupational exposure limits (OELs) generally refer to airborne concentration of substances that
should not cause ill health to a healthy adult when exposed. They do not necessarily define a
hazard.

OELs are commonly used as a reference value to compare the findings of exposure monitoring to
assess potential risks and or to prioritize control actions. The idea of exposure assessment is to
obtain a reliable estimate of worker exposure and to compare it to well-defined criteria, as part of
the risk assessment process.

OELs normally take three forms:

• Time-Weighted Average (TWA), usually averaged over 8 hours

• Short Term Exposure Limit (STEL), usually averaged over 15 minutes (Mins)

• Ceiling or Peak exposure limits, usually instantaneous values.

There are many sources of OELs worldwide such as

• Threshold Limit Values (TLVs®), a US voluntary standard recommended by American


Conference of Governmental Industrial Hygienists (ACGIH)

• Permissible Exposure Limits (PELs), set by OSHA and mandatory in US

• Workplace Exposure Limits (WELs) in the UK

• Maximale Arbeitsplatz-Konzentration (“maximum workplace concentration”) (MAK’s) in


Germany

OELs do not necessarily correspond between countries or sources for which reason it is important
to consider available OELs when evaluating air sampling data even though technically or legally
they may not be applicable to the work place under evaluation. Section 3.11 contains further
details on various OELs.

Measurement of Hazardous Substance Page 35


Chapter 3 Occupational Exposure Limits
3.2 Definitions and Units
OELs are reported in one of two units:

• Mass per unit volume (e.g., milligrams per cubic meter or mg/m³), typically used for
dusts, fumes and mists.

• Proportional by volume (e.g., parts per million or ppm), typically used for gases and
vapours. One percent is equivalent to 10,000 ppm, and one ppm is equivalent to
0.0001%.

It is possible to convert concentrations from mg/m³ to ppm, but for gases and vapours only, and
not dusts, fumes, or mists because the latter involves solids suspended in air rather than
gases/vapours mixed with air. The relevant conversion equation is

𝐶 𝑝𝑝𝑚 = 𝐶 𝑚𝑔/𝑚³ ∗ 24.45/𝑀𝑊 at NTP …Equation 3-1


Where C ppm represents concentration in parts per million

C mg/m³ is concentration in milligrams per cubic meter

24.45 is the molar volume of gas at NTP (25 degrees C and 760 mm Hg)

MW is the molecular weight of substance in question

Example:

The 8-hr OEL for Toluene is 50 ppm. What is the OEL in mg/m3?
24.45
𝐶 𝑝𝑝𝑚 = 𝐶 𝑚𝑔/𝑚³ ∗ 𝑀𝑊
, which re-arranged is same as
𝑀𝑊
𝐶 𝑚𝑔/𝑚3 = 𝐶 𝑝𝑝𝑚 ∗
24.45
Substituting in desired values… (MW for toluene is 92.1)

92.1
𝐶 𝑚𝑔/𝑚3 = 50 ∗
24.45
So OEL of 50 ppm toluene is equivalent to 188 mg/m3

This equation can be re-arranged to calculate OELs (as well as exposure data) in ppm from mg/m³
data.

Time is also a key component of OELs, and is used to average exposures over a specified period of
time to obtain a time weighted average (TWA). Figure 3-1 Time Weighted Average (TWA)
Summary provides a summary of the relationship between time and OEL.

Measurement of Hazardous Substance Page 36


Chapter 3 Occupational Exposure Limits
The most commonly used time limits associated with OELs are

• 8 hours, representing a full shift, or 8h-TWA)

• 15-minute short term exposure limit, (also known as STEL).

• Ceiling values (instant measurements)

In general, 8h-TWA OELs apply to substances that are chronically toxic (e.g., asbestos, heavy
metals), whereas 15-minute STELs commonly apply to substances that have acute (i.e., short term)
adverse effects (e.g., solvents, acid mists). Some substances have acute and chronic adverse
effects and so may have 15 mins STEL and 8h-TWA OELs. Irritant substances may also have a
ceiling OEL, which is an airborne concentration that should never be exceeded.

Figure 3-1 Time Weighted Average (TWA) Summary

Source: AIHA 1997

3.3 Time Weighted Average OELs


Time weighted average (TWA) OEL’s apply to long-term exposure to a substance over an 8-hour
workday, for a five-day working week, over the working life and should be applied to full shift
personal exposure estimates for substances with chronic effect(s).

When using TWA based OELs, it is important to adjust your results accordingly. In other words, it is
necessary to calculate 8h-TWAs to compare the results against an 8h-TWA OEL.

Measurement of Hazardous Substance Page 37


Chapter 3 Occupational Exposure Limits
The equation to calculate 8-hour time weighted average exposures is:

𝐶1 ∗ 𝑇1 + 𝐶2 ∗ 𝑇2 + . . . . . . . 𝐶𝑛 ∗ 𝑇𝑛 …Equation 3-2
8ℎ 𝑇𝑊𝐴 =
8

Where C1 is the concentration for Time period T1 (in hours)

C2 is the Concentration for Time period T2 (in hours)

Cn is the Concentration for Time period Tn (in hours)

Care is advised in making sure that time values are in the same units. If time T is
measured in minutes rather than hours, the denominator becomes 8*60 i.e., 480
minutes.

Example

You sampled an all-day painting project for xylene. The project involved three
samples: paint preparation for 30 minutes (result of 150 ppm), paint application
for 3 hours (i.e.) 180 minutes (result of 40 ppm), and then cleanup for 90 minutes
(result of 70 ppm). What is the 8h-TWA result? Assume zero exposure outside
the periods sampled.

(150 ∗ 30) + (40 ∗ 180) + (70 ∗ 90)


8ℎ 𝑇𝑊𝐴 =
480

8ℎ 𝑇𝑊𝐴 = 37.5 𝑝𝑝𝑚

3.4 OELs for Extended Shifts


Most OELs assume a traditional 8-hour work day and a 40-hour work week. These need to be
adjusted where work schedules are extended or unusual to provide an equivalent level of
protection. This section discusses various approaches to adjusting OELs. Please note that
regulations in certain jurisdictions may prescribe a specific approach for estimating OELs for longer
shifts. The Australian Institute of Occupational Hygienists (AIOH) has published a position paper
that includes a comparison of calculated adjustments using the different approaches discussed
below for 13 substances (see https://shrtm.nu/DzHf, see Page 14). The AIOH position paper
includes pharmacokinetic approaches that are beyond the scope of this course.

3.4.1 OSHA (Direct Proportion) Model


The US Occupational Safety and Health Administration (OSHA)’s approach adjusts OELs directly
proportionally to the hours worked. This approach is appropriate for substances where the OEL is
based on estimated life-time excess risk (parts per million – years) rather than a specific toxic
threshold.

The OSHA approach adjusts 8h-TWA OELs as follows:

Measurement of Hazardous Substance Page 38


Chapter 3 Occupational Exposure Limits
𝐴𝑑𝑗𝑢𝑠𝑡𝑒𝑑 𝑂𝐸𝐿 = 8/ℎ ∗ 𝑂𝐸𝐿 …Equation 3-3

Where h indicates the number of hours worked

Example

A worker is exposed to toluene for a 12-hour shift. The 8-hr OEL for toluene is
50 ppm. Calculate the daily adjusted OEL using the OSHA Model
8
𝐴𝑑𝑗𝑢𝑠𝑡𝑒𝑑 𝑂𝐸𝐿 = ( ) ∗ 50 𝑝𝑝𝑚
12
𝐴𝑑𝑗𝑢𝑠𝑡𝑒𝑑 𝑂𝐸𝐿 = 0.667 ∗ 50 𝑝𝑝𝑚
𝐴𝑑𝑗𝑢𝑠𝑡𝑒𝑑 𝑂𝐸𝐿 = 33 𝑝𝑝𝑚

Note that OSHA has prescribed a specific method to derive long shift OELs for lead (see
29CFR1910.1025, and 29CFR1926.62), whereby the adjusted OEL for shifts longer than 8 hours is
derived as follows:

𝐴𝑑𝑗𝑢𝑠𝑡𝑒𝑑 𝑇𝑊𝐴 𝑂𝐸𝐿 (𝑃𝑏) = 400/ℎ mg/m3 …Equation 3-4


Where h indicates the number of hours worked.

3.4.2 Brief and Scala Model


This Brief and Scala Model OEL adjustment model, originally derived in the petroleum industry,
reduces the 8-hour OEL proportionally for both increased exposure and reduced recovery time.

The OEL can be adjusted by a Daily Reduction Factor (DRF), so that

𝐴𝑑𝑗𝑢𝑠𝑡𝑒𝑑 𝑂𝐸𝐿 = 𝑂𝐸𝐿 ∗ 𝐷𝑅𝐹 …Equation 3-5

Where DRF indicates daily reduction factor, as follows:


𝐷𝑎𝑖𝑙𝑦 𝑅𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝐹𝑎𝑐𝑡𝑜𝑟 = (8/ℎ) ∗ ((24 − ℎ)/16)
Where h = hours worked per day

The OEL can also be adjusted for week long exposures as follows:

𝑊𝑒𝑒𝑘𝑙𝑦 𝑅𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝐹𝑎𝑐𝑡𝑜𝑟 (𝑊𝑅𝐹) = (40/ℎ) ∗ ((168 − ℎ)/128)


𝐴𝑑𝑗𝑢𝑠𝑡𝑒𝑑 𝑂𝐸𝐿 = 𝑂𝐸𝐿 ∗ 𝑊𝑅𝐹 …Equation 3-6

Measurement of Hazardous Substance Page 39


Chapter 3 Occupational Exposure Limits
Example:

A worker is exposed to toluene for a 12-hour shift. The 8-hr OEL for Toluene is 50 ppm.
Calculate the daily adjusted OEL using the Brief and Scala Model
8 24 − 12
𝐴𝑑𝑗𝑢𝑠𝑡𝑒𝑑 𝑂𝐸𝐿 = ( ) ∗ ( ) ∗ 50 𝑝𝑝𝑚
12 16
𝐴𝑑𝑗𝑢𝑠𝑡𝑒𝑑 𝑂𝐸𝐿 = 0.5 ∗ 50 𝑝𝑝𝑚
𝐴𝑑𝑗𝑢𝑠𝑡𝑒𝑑 𝑂𝐸𝐿 = 25 𝑝𝑝𝑚

NOTE: The adjusted exposure limit should be calculated daily and weekly reduction factors. The
most conservative value (i.e., lowest should be used).

As shown in the two worked examples, use of the Brief and Scala Model yields a more
conservative OEL value (25 ppm) whereas use of the OSHA model resulted in a higher value for the
adjusted OEL (33 ppm).

3.4.3 UK Approach
The UK’s HSE’s approach is to convert air sampling results collected over long shifts into 8h-TWAs
(for direct comparison to 8h-TWA WELs) using a proportional approach as follows:

Example (From EH 40 Publication):

An operator works a 12-hour shift each day for 5 days, and then has seven days’ rest.
WELs are based on an 8-hour reference period each 24 hours in which an exposure
occurs; the seven days’ rest makes no difference. While at work, the operator is
exposed to 4 mg/m3. The WEL for the substance of concern is 5 mg/m3 (8h-TWA). Was
the WEL exceeded?
𝑠ℎ𝑖𝑓𝑡 𝑑𝑢𝑟𝑎𝑡𝑖𝑜𝑛 𝑖𝑛 ℎ𝑜𝑢𝑟𝑠
𝐴𝑑𝑗𝑢𝑠𝑡𝑒𝑑 8ℎ − 𝑇𝑊𝐴 𝐸𝑥𝑝𝑜𝑠𝑢𝑟𝑒 = ( ) ∗ 4 𝑚𝑔/𝑚3
8 ℎ𝑜𝑢𝑟𝑠
𝐴𝑑𝑗𝑢𝑠𝑡𝑒𝑑 8ℎ − 𝑇𝑊𝐴 𝐸𝑥𝑝𝑜𝑠𝑢𝑟𝑒 = 1.5 ∗ 4 𝑚𝑔/𝑚3
𝐴𝑑𝑗𝑢𝑠𝑡𝑒𝑑 8ℎ − 𝑇𝑊𝐴 𝐸𝑥𝑝𝑜𝑠𝑢𝑟𝑒 = 6 𝑚𝑔/𝑚3

So, it can be concluded that the operator’s exposure would have exceeded the WEL.
Corrective action would be required.

3.4.4 Quebec Model


This approach, developed by Institut de recherche Robert-Sauvé en santé et en sécurité du travail
(IRSST) in Quebec, Canada, is based on OSHA’s Direct Proportion model but also considers length
of daily shift as well as hours worked in a week in addition to toxicological properties of
substances of concern. For example, no adjustment is considered necessary for substances
regulated by a ceiling value, or for substances that are simple asphyxiants, malodorous or
irritating. On the other hand, a daily adjustment is recommended for substances that have acute
effects, and weekly adjustments for substances that have chronic effects.

Measurement of Hazardous Substance Page 40


Chapter 3 Occupational Exposure Limits
The Quebec model, presently in its 4th edition, offers adjustments based on shift duration as well
as length of work week. It may be downloaded at https://shrtm.nu/K6wR.

3.5 Short Term Exposure Limits


Short term exposure limits (STELs) are important supplements to TWA OELs. They are relevant
when evaluating exposures to substances that can cause short term health effects such as
intolerable irritation or central nervous system effects such as nausea or dizziness. Conformance
with relevant STELs will help to prevent acute and chronic adverse health effects.

STEL OELs are generally averaged over 15-minute intervals. Worker exposures should not exceed
the 15 min STEL for longer than 15 minutes, or for more than 4 such periods per work day.
Moreover, a minimum of 60 minutes should be allowed between successive exposures at the
STEL.

STELs should not be time adjusted

3.6 Ceiling Limit (C)


The ceiling limit (C) represents an instantaneous exposure concentration that should not be
exceeded at any time. Ceiling exposure limits are set to prevent short term effects such as physical
irritation, as sufficient evidence demonstrates such physical irritation may initiate, promote, or
accelerate adverse health effects through interaction with other chemical or biological agents or
through other mechanisms.

If real time data (i.e., direct measurement) is not feasible, it’s important to review the sampling
method to ensure that the sample volume allows the lab to report a limit of detection that is less
than the ceiling limit.

Ceiling limits should not be time adjusted.

3.7 Long Term Average (LTA) Exposure Limit


Long term average exposure limits have longer time periods, for example, months to a year and
are appropriate for substances which take longer to leave the body or affect the body for longer
periods of time. Limitations in scientific evidence supporting the establishment of many OELs is
recognized and therefore LTA OELs can be determined as ¼ of the 8 hour-TWA OEL.

LTA OELs should not be time adjusted.

3.8 Excursion Limits


Although many substances may not have a STEL, it is considered good practice to control short
term exposures (excursions) that exceed an 8h-TWA OEL value even if though a calculated 8-hour
exposure may not exceed the 8h-TWA OEL. Other approaches are that of the American
Conference of Governmental Industrial Hygienists (ACGIH) and the UK HSE based on excursion
limits.

Measurement of Hazardous Substance Page 41


Chapter 3 Occupational Exposure Limits
The ACGIH Threshold Limit Value (TLV®) guidance recommends limiting excursions in worker
exposure levels to 3 times the OEL for no more than a total of 30 minutes during the workday, and
under no circumstances should they exceed 5 times the OEL, provided the TWA OEL is not
exceeded. A process is not considered to be under reasonable control if these levels occur.

In the UK, an excursion limit of 3 times the workplace exposure limit (WEL) OEL is considered good
practice.

Relevant STELs or Ceiling limits take precedence over the peak exposure limits (formerly known as
excursion limits).

3.9 Notations
A notation is a designation in the OEL listing documentation that provides additional information
regarding a particular substance. These notations may indicate biological monitoring limits,
carcinogenicity, sensitisation and whether absorption through the skin should be considered. Each
of these types of notations are discussed below:

3.9.1 Biological Monitoring Limits


Biological monitoring notations indicate that there are biological indices of exposure for a
particular substance. These indices include blood measurements (e.g., blood lead levels) or urinary
measurements. These are further discussed in Chapter 10 of this manual.

Correct application of biological monitoring limits requires consideration of all routes of exposure,
including non-occupational sources (e.g., diet). Employee resistance may be encountered with
biological monitoring because of the use of invasive collection techniques e.g., urine and blood
sampling.

Biological monitoring can be valuable in evaluating accidental exposures associated with incidents,
such as chemical spills.

3.9.2 Carcinogenicity
A carcinogen is an agent capable of causing cancer. Evidence of carcinogenicity comes from
epidemiology, toxicology, and mechanistic studies. Note that not all carcinogens may have
designated OELs.

The International Agency for Research on Cancer (IARC) has the following carcinogen classification
scheme based on the strength of published evidence for carcinogenicity.

• Group 1 Carcinogenic to humans

• Group 2A Probably carcinogenic to humans

• Group 2B Possibly carcinogenic to humans

• Group 3 Not classifiable as to carcinogenicity to humans

Measurement of Hazardous Substance Page 42


Chapter 3 Occupational Exposure Limits
• Group 4 Probably not carcinogenic to humans

The results of IARC’s evaluation on the carcinogenicity of more than 900 substances have been
published in a series of monographs published since 1972. (See https://shrtm.nu/Hrs2.

Different jurisdictions use different schemes, so care needs to be taken regarding local notations.
ACGIH, OSHA and National Institute of Occupational Safety & Health (NIOSH) in the US have their
own classifications. In the UK, carcinogenicity is indicated by ‘Carc’ meaning the chemical can
cause cancer and or heritable genetic damage.

3.9.3 Sensitisation
The notation SEN or Sen refers to the potential for the chemical to produce sensitisation in
exposed workers. Sensitisation may relate to respiratory, dermal or conjunctival exposures. A
sensitised, subsequent exposure(s), even at very low levels, usually results in adverse allergic
reactions.

Example: Toluene diisocyanate (TDI) often found in two-pack paint is a respiratory


sensitiser and subsequent exposure can result in severe asthmatic reactions to those
sensitised.

In the UK, ‘Sen’ is used as the notation for sensitisers whereas the ACGIH TLV© uses ‘SEN’. The
AIHA uses DSEN for dermal sensitisers and RSEN for respiratory sensitisers.

When considering substances with a SEN/Sen notation it is important to understand:

• Occupational exposure limits are not meant to be protective of those who are sensitised.

• When there is a SEN/Sen notation, reference must be made to the documentation to


understand the nature of the sensitisation and the potency of the sensitiser.

3.9.4 Skin
The ‘Skin’ or ‘Sk’ notation indicates that the cutaneous route of exposure can contribute
significantly to the overall exposure. Cutaneous exposures include mucous membranes and the
eyes, either by contact with vapours or, of probable greater significance, by direct skin contact
with the substance. Typically, skin exposure results from handling substances without the use of
gloves or protective clothing, splashes or handling contaminated clothing and equipment.

Examples: Organophosphate pesticides (e.g., Malathion), and glycol ethers

Skin notations are not assigned on the basis of any harmful effects on the skin such as irritation or
allergic contact dermatitis but that it absorbs through the intact skin.

The use of a ‘Skin’/’Sk’ notation indicates that biological monitoring may be required to
supplement air sampling to quantify worker exposure. Skin notations also inform the selection and
use of control measures, for example the use of personal protective equipment to prevent skin
absorption.

Measurement of Hazardous Substance Page 43


Chapter 3 Occupational Exposure Limits
The OELs refer to exposures via the inhalation route only, and so take no account of any
absorption that may occur as a consequence of exposure via the cutaneous route.

3.10 Basis of OELs


OEL’s are based on the notion of a threshold of intoxication whereby there exists a dose
concentration which the human body is capable of tolerating and detoxifying without injury to
itself. These “threshold doses” below which no significant adverse effect is expected to occur in
most people are often derived from epidemiological and toxicological studies coupled with
occupational hygiene measurements.

Two commonly used toxicological concepts, used in the derivation of OELs are:

• NOEL: no observed adverse effect level

• LOEAL: lowest observed adverse effect level

Appendix A provides a review of these concepts, which are also discussed in W 507 Health Effects
of Hazardous Substances Course.

OELs for chemicals are established based on a number of factors including toxicity, physiological
response (biologic action). Examples of such factors include:

Table 3-1 OEL Factors

Type of Hazard Basis of OEL

Irritants Ability to cause inflammation of mucous membrane with which they come in
contact e.g., hydrochloric acid fumes, ammonia, ozone, acrolein.

Asphyxiants Ability to deprive the tissue of oxygen.


Simple asphyxiants e.g., nitrogen, carbon dioxide, helium.
Chemical asphyxiants e.g., carbon monoxide, cyanides.

Narcotic Depressant action upon the central nervous system, particularly the brain e.g.,
ether, chloroform.

Carcinogens Cancer causing substances e.g., asbestos, arsenic, vinyl chloride monomer

Toxic Effects Chronic adverse effects (e.g., lead, silica, solvents)

Overall, there is very limited human exposure data that can be used to derive OELs. In many cases,
OELs are derived from either animal studies, studies of similar but not identical industries or on
the notion that similar compounds (e.g., chlorinated hydrocarbons, or heavy metals) have similar
toxicological properties. In other cases, there are limited data, or the available data addresses
other routes of exposures. To address these issues, uncertainty factors (also known as safety
factors) are applied. These may range from 1 (as in the case of certain irritants for which there is
human data) to several thousand for carcinogens.

Measurement of Hazardous Substance Page 44


Chapter 3 Occupational Exposure Limits
Agencies that develop or recommend OELs usually have documentation that explains the basis for
the OEL in question. The following table summarizes this information:

Table 3-2 OEL Documentation

OEL Name Agency OEL Documentation

“Documentation of Threshold Limit Values for


TLV
US ACGIH Chemical Substances and Physical Agents and
Threshold Limit Value
Biological Exposure Indices" - see acgih.org

PEL Preambles to OSHA regulations.


US OSHA
Permissible Exposure Limit See osha.gov

Criteria for a Recommended Exposure Standard (ES)


REL
US NIOSH series of documents. See
Recommended Exposure Limit
https://www.cdc.gov/niosh/index.htm

SCOEL Scientific Committee on Occupational Exposure Limits


EU
Recommended Exposure Limits (SCOEL) - see https://tinyurl.com/y8amyun3

3.11 Application of OELs


OELs provide a useful reference point by which to compare air monitoring results. It is important
that air sampling data be representative of the employee exposures, and that the samples be
collected from employee breathing zones.

Before comparing results with relevant OELs, it is important to consider the following general
rules:

• Make sure that the units of measurements (i.e., results) are in the same units as the
relevant OEL

• Calculate relevant time weighted averages (TWA) of exposure, where relevant, to allow
direct comparison to TWA OELs. For extended shifts, see Section 3.4.

• If short term data was collected, it should be compared to STELs or Ceiling Values. If
there are no relevant listed value, then the data can be compared with the TWA value
(without calculating any time weighted average value).

3.12 Types Occupational Exposure Limits


There are numerous OELs in use worldwide. Some are enforceable by regulators (e.g., OSHA PELs),
others are advisory (e.g., ACGIH TLVs) and represent best practice.

This section provides an overview of various OELs commonly used by occupational hygienists in
various jurisdictions but is not intended to be an all-inclusive list. It’s wise to see what OELs are
relevant to any particular location an occupational hygienist may be working in. These are usually
available online. There are also specific publications and applications that are a compendium of

Measurement of Hazardous Substance Page 45


Chapter 3 Occupational Exposure Limits
OELS for different countries such as the German Institute for Worker Health and Safety’s (IFA)
downloadable GESTIS data base (see https://shrtm.nu/7CH3.

3.13 Threshold Limit Values (TLVs)


TLVs® were developed by the American Conference of Governmental Industrial Hygienists
(ACGIH), which was founded in 1938. TLVs, first established in 1941, are regularly reviewed and
updated, and generally represent best occupational hygiene practice. TLVs are listed in a booklet
that is updated annually. The basis for each TLVs is discussed in the Documentation of TLVs, first
published in 1961, and presently in its 7th edition. See www.acgih.org for further details.

There are three types of TLVs®

1. TLV-Time Weighted Average (TLV-TWA)

2. TLV-Short Term Exposure Limit (TLV-STEL)

3. TLV-Ceiling (TLV-C)

3.13.1 TLV-TWA
The time weighted average (TWA) Threshold Limit Value (TLV) is defined as:

“The TWA concentration for a conventional 8-hour workday and a 40-hour work week,
to which it is believed that nearly all workers may be repeatedly exposed, day after
day, for a working lifetime without adverse effect.”

However, during this eight-hour averaging period, excursions above the TLV- TWA are permitted
providing these excursions are compensated for by equivalent excursions below the standard
during the working day. Because some substances can give rise to acute health effects even after
brief exposures to high concentrations, it is prudent that excursions above the TWA concentration
should be restricted, moreover, the magnitude of excursions is an indication of the true degree of
effective control over the release of contaminants from a process.

3.13.2 TLV-STEL
The ACGIH has recommended short-term exposure limits (STELs) for many substances that exhibit
acute (i.e., short-term) adverse health effects. STELs are defined as:

“A 15-minute TWA exposure that should not be exceeded at any time during a
workday, even if the TWA is within TLV-TWA. The TLV-STEL is the concentration to
which it is believed that workers can be exposed continuously for a short period
without suffering from:

• Irritation

• Chronic or irreversible tissue damage

• Dose-rate dependent toxic effects, or

Measurement of Hazardous Substance Page 46


Chapter 3 Occupational Exposure Limits
• Narcosis of sufficient degree to increase the likelihood of accidental injury, impaired self-
rescue, or materially reduced work efficiency.”

The TLV-STEL is not a separate, independent exposure guideline, but it supplements the TLV-TWA
where the recognized acute effects from a substance whose toxic effects are primarily of a chronic
nature.

Exposures above the TLV-TWA up to the TWA-STEL should be less than 15 minutes, should occur
fewer than four times a day, with at least 60 minutes between successive exposures.

3.13.3 TLV-C
The ACGIH has also recommended ceiling limits for certain substances. These ceiling limits are
defined as:

“The concentration that should not be exceeded during any part of the working
exposure. If instantaneous measurements are not available, sampling should be
conducted for the minimum period of time sufficient to detect exposures at or above
the ceiling value.”

The ACGIH believes that TLVs® based on physical irritation should be considered no less binding
than those based on physical impairment. There is increasing evidence that physical irritation may
initiate, promote, or accelerate adverse health effects through interaction with other chemical or
biological agents or through other mechanisms.

Ceiling values are instantaneous guidelines that should not be exceeded at during any part of
working exposures. They are best evaluated using direct reading instruments. If none exist, then
sampling duration should be the minimum necessary to detect exposures (often 5-10 minutes)

3.13.4 Peak Exposures (Formally Excursion Limit)


The ACGIH revised its terminology in 2016 to replace the term “Excursion Limit” with “Peak
Exposures” In practice, the actual concentration of airborne substances can and does vary
significantly. For many substances with a TLV-TWA there is no TLV- STEL. However, excursions
above the TLV-TWA should be controlled even if the recommended 8-hour TLV-TWA is not
exceeded. Excursion limits are applied to TLV-TWAs that DO NOT have TLV-STELs.

Peak worker exposure levels may exceed 3 times the value of TLV-TWA for no more than 15
minutes during the workday, on no more than 4 occasions spaced one hour apart during a work
day. Under no circumstances should peak exposures exceed 5 times the TLV-TWA. Additionally,
the relevant 8h-TWA should not be exceeded for an 8-hour work period.

A process is not considered to be under reasonable control if these levels occur (3 times the
workplace exposure limit (WEL) in the UK), where the toxicological data exists to establish a TLV-
STEL or TLV-C these values take precedence over the excursion limits.

Measurement of Hazardous Substance Page 47


Chapter 3 Occupational Exposure Limits
3.13.5 Mixtures
When two or more hazardous substances have a similar toxicological effect on the same target
organ or system, their combined effect rather than that of either individually, should be given
primary consideration. In the absence of information to the contrary, different substances should
be considered as additive where the health effect and target organ or systems is the same.

The ACGIH approach does not calculate a combined OEL for a mixture of substances. Instead,
measured exposures would be considered as exceeding TLVs when:

𝐶_1/〖𝑂𝐸𝐿〗_1 + 𝐶_2/〖𝑂𝐸𝐿〗_2 + ⋯ 𝐶_𝑛/〖𝑂𝐸𝐿〗_𝑛 ≥ 1 …Equation 3-7

Where C1 is the airborne concentration and TLV1 is the corresponding threshold limit
value.

The additive formula applies to simultaneous exposures for hazardous agents with TWA, STEL and
Ceiling values.

3.13.6 TLV Notations *


* Special Note – Section 3.9 of this Manual is a general discussion about the use of Notations in
lists of OELs. This section discusses Notations in the annual list of TLVs
specifically.

A notation is a designation that appears as a component of the adopted TLV® value to provide
additional information with respect to the particular chemical:

3.13.6.1 Biological Exposure Indices (BEIs®)


The notation BEI® is listed when a BEI® (or BEIs®) is (are) recommended for the substance.
Biological monitoring is recommended for such substances to determine the exposure from all
sources, including dermal (skin) ingestion or non-occupational.

Most BEIs® are based on a direct correlation with the TLV® (i.e., the concentration of the
determinant that can be expected when the airborne concentration is at the TLV) with an
assumption that there is no exposure by skin absorption or ingestion. Further information can be
found, in the TLV book (published annually), or in the documentation for the TLVs® and BEI® for
these substances.

Correct application of BEIs® requires significant knowledge of the accompanying documentation


and may be valuable in evaluating what exposure has actually occurred in an incident. Employee
resistance may be encountered with this type of monitoring as many BEIs® require the use of
invasive collection techniques.

3.13.6.2 Carcinogenicity
“A carcinogen is an agent capable of inducing benign or malignant neoplasms. Evidence of
carcinogenicity comes from epidemiology, toxicology, and mechanistic studies”.

Measurement of Hazardous Substance Page 48


Chapter 3 Occupational Exposure Limits
The ACGIH system uses the following notation related to carcinogenic potential. These notations
differ from IARC’s approach (see Section 3.9.2):

• A1 Confirmed Human Carcinogen: The agent is carcinogenic to humans based on the


weight of evidence from epidemiologic studies.

• A2 Suspected Human Carcinogen: Human data are accepted as adequate in quality but
are conflicting or insufficient to classify the agent as a confirmed human carcinogen; OR,
the agent is carcinogenic in experimental animals at dose(s), by route(s) of exposure, at
site(s), of histologic type(s) or by mechanism(s) considered relevant to worker exposure.
A2 is used primarily when there is limited evidence of carcinogenicity in humans and
sufficient evidence of carcinogenicity in experimental animals with relevance to humans.

• A3 Confirmed Animal Carcinogen with Unknown Relevance to Humans: The agent is


carcinogenic in experimental animals at relatively high dose, by route(s) of
administration, at site(s), of histologic type(s) or by mechanism(s) that may not be
relevant to worker exposure. Available epidemiologic studies do not confirm an
increased risk of cancer in exposed humans. Available evidence does not suggest that
the agent is likely to cause cancer in humans except under uncommon or unlikely routes
or levels of exposure.

• A4 Not Classifiable as a Human Carcinogen: Agents which cause concern that they could
be carcinogenic for humans but which cannot be assessed conclusively because of a lack
of data. In vitro or animal studies do not produce indications of carcinogenicity which are
sufficient to classify the agent into one of the other categories.

• A5 Not Suspected as a Human Carcinogen: The agent is not suspected to be a human


carcinogen on the basis of properly conducted epidemiologic studies in humans. These
studies have sufficiently long follow-up, reliable exposure histories, sufficiently high
dose, and adequate statistical power to conclude that exposure to the agent does not
convey a significant risk of cancer to humans, OR, the evidence suggesting a lack of
carcinogenicity in experimental animals is supported by mechanistic data.

3.13.6.3 Sensitisation
The notation SEN refers to the potential for the chemical to produce sensitisation which may
relate to respiratory, dermal or conjunctival exposures. Once a person has become sensitised,
subsequent exposure to the agent, even at very low levels, usually results in an adverse allergic
reaction.

Example: Toluene diisocyanate (TDI) often found in 2-pack paints is a respiratory sensitiser and
subsequent exposure can result in severe asthmatic reactions to those sensitised.

When considering substances with a SEN notation it is important to understand:

• Occupational exposure limits are not meant to be protective of those who are sensitised.

Measurement of Hazardous Substance Page 49


Chapter 3 Occupational Exposure Limits
• When there is a SEN notation, reference must be made to the documentation to
understand the nature of the sensitisation and the potency of the sensitiser.

• Some bodies (e.g., AIHA) use different notation to indicate specific sensitisation, e.g.,
DSEN for dermal sensitisers, RSEN for respiratory sensitisers.

3.13.6.4 Skin
The Skin notation refers to the potential significant contributions to the overall exposure by
cutaneous route, including mucous membranes and the eyes, either by contact with vapours or, of
probable greater significance, by direct skin contact with the substance. Typically, skin exposure
occurs from splashes, wearing of contaminated clothing, or handling materials without adequate
protective clothing and or gloves (e.g., organophosphate pesticides, glycol ethers).

It is important to note that skin notations are not assigned on the basis of any harmful effects on
the skin such as irritation or allergic contact dermatitis. Substances with a skin notation are not
necessarily harmful to the skin.

The use of a skin notation is to alert the user that air sampling alone is not sufficient to quantify
worker exposure, biological monitoring may also be required in addition to changes to work
practices including the use of personal protective equipment to prevent cutaneous absorption.

3.14 Australian Exposure Standards


The first edition of an Australian list of exposure standards (ES) was published in 1990 by
WorkSafe Australia as “Exposure Standards for Atmospheric Contaminants in the Occupational
Environment - Guidance Note and National Exposure Standard.”. These standards were based on
ACGIH TLV® list but also cross-referenced exposure standards from Germany, Sweden and the UK.
Specific differences included reference to Workplace Exposure Standards and the use of Peaks
rather than Ceilings.

The second edition was published in October 1991, and a third edition in May 1995 by the
National Occupational Health and Safety Commission. Australian Exposure Standards for more
than 700 substances are now published on the Safe Work Australia website:
https://tinyurl.com/y878tse3. These standards also have notations in regards to carcinogenicity,
sensitisation.

Australia’s Work Health Safety Act requires that employers maintain exposures not only below
exposure standards but as low as reasonably practical.

3.15 United Kingdom Workplace Exposure Limits (WELs)


The UK Health & Safety Commission has established Workplace Exposure Limits (WELs) for a
number of substances hazardous to health as part of The Control of Substances Hazardous to
Health Regulations.

HSE’s publication EH40 Workplace Exposure Limits (see https://tinyurl.com/yajjckvs, includes the
list of substances assigned WELs and provides more detailed guidance on their use. WELs are

Measurement of Hazardous Substance Page 50


Chapter 3 Occupational Exposure Limits
maximum acceptable levels of exposure that should not be exceeded. Moreover, exposure should
be reduced below the limit as far as is reasonably practicable by applying the principles of good
occupational hygiene practice. The listing includes: 8-hour TWA, STEL, the Comments Column
containing Safety & Risk Phrases plus the Carcinogen, Skin, Respiratory Sensitiser and Biological
Monitoring Guidance Value notations.

Note that WELs also address substances for which no short-term limit is specified. HSE
recommends that a figure of three times the long-term limit be used as a guideline for controlling
short-term peaks in exposure. Some workplace activities give rise to frequent short (less than 15
minutes) periods of high exposure which, if averaged over time, do not exceed either an 8-hour
TWA or a 15-minute TWA.

3.16 European Exposure Limits

3.16.1 European Agency for Safety and Health at Work


There are two kinds of Occupational Exposure Limit Values set by the European Agency for Safety
and Health at Work.

• Indicative (Directive 98/24/EC on chemicals)

Indicative Occupational Exposure Limit Values (IOELVs) have been established when an
assessment of the available scientific data indicates that a threshold can clearly be
identified below which exposure to the substance should not have an adverse impact on
human health.

IOELVs do not consider feasibility factors (including socio-economic and technical).


Published values are available from https://tinyurl.com/y76v2se9 in a series of lists (2000,
2006, 2009, and 2017)

• Binding (Directive 2004/37/EC which applies to carcinogens and mutagens)

Binding Occupational Exposure Limit Values (BIOELVs) reflect socio- economic and
technical feasibility factors, as well as the same factors used to derive IOELVs

European Agency for Safety and Health at Work OEL values can be 8-hour TWA, short term, and/or
biological limit values and can be supplemented by further information such as notations and
routes of absorption.

3.16.2 Scientific Committee on Occupational Exposure Limits


The European Commission’s Scientific Committee on Occupational Exposure Limits (SCOEL) also
recommends exposure limits for a number of substances. SCOEL’s summary table (Available from
https://tinyurl.com/y76tuzlz) provides links to detailed reports outlining the basis of their
recommendations.

Measurement of Hazardous Substance Page 51


Chapter 3 Occupational Exposure Limits
3.16.3 REACH Derived No Effect Limits
REACH Regulation allows manufacturers and importers of chemical substances to place their
substances on the European market only if they possess sufficient knowledge of the substances'
toxicological data. Manufacturers and importers must compile relevant information on the
substances' properties and register it in a central database maintained by the European Chemicals
Agency (ECHA) which provides guidance documents for compliance. The substance-specific
information required by REACH also includes occupational exposure limits in the form of DNELs
(derived no-effect levels).

A DNEL is required for each population anticipated to handle a particular substance (e.g., workers,
end users, humans via the environment, etc.). Certain vulnerable sub-populations (e.g., children
and pregnant women) may also need to be considered. Recall that OELs are generally focused on
healthy adult workers. Thus, any given substance may have several different types of DNELs as
follows:

• Acute – inhalation, systemic effects

• Acute – inhalation, local effects

• Acute – dermal, local effects

• Long-term – inhalation, systemic effects

• Long-term – inhalation, local effects

• Long-term – dermal, systemic effects

• Long-term – dermal, local effects

• Long-term – oral, systemic effects (not relevant to workers)

ECHA has developed guidance documents for the development of DNELs (see
https://shrtm.nu/KH1c). The German Social Accident Insurance Scheme maintains a current list of
DNELs through the GESTIS program. They are available from

https://shrtm.nu/yMW9

3.17 OSHA Permissible Exposure Limits


In the US, the Occupational Safety and Health Administration established Permissible Exposure
Limits (PEL) in 1970. Most are based upon the 1968 Threshold Limit Values OSHA. Since 1970 has
also promulgated PELs and substance specific regulations for approximately 30 substances (e.g.,
asbestos, benzene, lead, and vinyl chloride). Due to the US regulatory process, many OSHA OELs
are outdated, even though they continue to be enforceable.

OSHA PELs are contained in Title 29 of the US Code of Federal Regulations, which has three tables
of interest as follows:

Measurement of Hazardous Substance Page 52


Chapter 3 Occupational Exposure Limits
Table Z-1: See https://shrtm.nu/p6sP for about 400 substances.

Table Z-2: See https://shrtm.nu/PwjQ for about 20 substances.

Table Z-3: See https://shrtm.nu/p8AZ for mineral dusts.

Note also that more than half of US states have their own state OSHA programs that are required
to be “at least as effective as” Federal regulations. However, it is possible that state-set OELs
regulations may be more restrictive (i.e., lower) than Federal PELs.

3.18 NIOSH
National Institute of Occupational Safety and Health (NIOSH) in the US has established
Recommended Exposure Limits (RELs). They are available on CD-ROM or
http://www.cdc.gov/niosh.

It should be noted that NIOSH is directed to recommend limits that will ensure protection of “all”
workers rather than “nearly all” workers, as with ACGIH TLVs. Consequently, many RELs are lower
than existing OELs (e.g., PELs or TLVs).

3.19 AIHA
From 1980, the American Industrial Hygiene Association (AIHA) produced Workplace
Environmental Exposure Levels (WEELs) which, were updated annually until 2013, when the
development of WEELs was transferred to the Occupational Alliance for Risk Sciences (OARS),
managed by Toxicology for Risk Assessment. Updated WEEL values may be found on
https://www.tera.org/OARS/WEEL.html.

WEELs are intended to provide guidance on exposure levels for substances for which there is (was)
neither legal nor authoritative limits (e.g., benzyl alcohol, butylene oxide). WEELs include
recommendations for 8-hour TWA, Ceiling limit and a Short-Term TWA limit plus Skin, Dermal
sensitiser and Respiratory sensitiser notations.

The AIHA also publishes Emergency Response Planning Guidelines (ERPGTM). These should be
used for risk assessments when considering exposures of either the workforce or for the public for
accidental releases. There are three levels of ERPGs guidelines:

• ERPG–1: The maximum airborne concentration below which nearly all individuals could
be exposed for up to 1 hour without experiencing more than mild, transient adverse
health effects or without perceiving a clearly defined objectionable odor.

• ERPG–2: The maximum airborne concentration below which nearly all individuals could
be exposed for up to 1 hour without experiencing or developing irreversible or other
serious health effects or symptoms that could impair an individual’s ability to take
protective action.

• ERPG–3: The maximum airborne concentration below which nearly all individuals could
be exposed for up to 1 hour without experiencing or developing life-threatening health
effects.

Measurement of Hazardous Substance Page 53


Chapter 3 Occupational Exposure Limits
ERPGs may be purchased either for individual substances or in a handbook that also includes
WEELs from AIHA (www.aiha.org ).

3.20 Germany – MAK Commission


In Germany, the Commission for the Investigation of Health Hazards of Chemical Compounds in
the Work Area (MAK Commission) is responsible for determining the current state of research
relating to the health risks posed by substances and materials used at the workplace and for
advising public authorities accordingly. The MAK Commission draws up proposals for MAK values
(maximum concentration at the workplace) for volatile chemicals and dusts, BAT values (biological
tolerance values), and also develops procedures to analyse chemical substances in the air and in
biological materials. Substances that are carcinogenic, germ cell mutagenic, sensitising or
percutaneously absorbed, as well as those that pose a risk to the embryo or fetus, are classified
accordingly.

MAK and BAT values may be found in https://tinyurl.com/yd5hsk95 or,


https://tinyurl.com/y7ceo7s5. Every year the proposals for the MAK and BAT values and the
classifications are published and presented to the German Federal Minister of Labour and Social
Affairs. The Ministry’s Committee of Hazardous Substances subsequently reviews the proposals
and makes a recommendation for their inclusion in the Hazardous Substances Ordinance.

3.21 Limitations of OELs


OELs are useful tools for occupational hygienist. However, like all tools they have certain limitation
as listed below:

• Safe vs Unsafe: OELs do not divide between safe and unsafe exposures but are guides to
assist in making conclusions about exposure risk. It is considered good practice to reduce
exposure to at least less than 50% of the OEL, or as far below it as is reasonably
practicable.

• Enforceability: Certain OELs in certain countries are legally enforceable, and may carry
civil and criminal penalties. Exceeding these values places a regulatory responsibility on
employers to control these exposures. However, there may be lower recommended
OELs that may represent more up to date information regarding the risks associated with
a particular substance although they may not necessarily be enforceable.

• Healthy Workforce: OELs are generally developed for working populations assumed to
be healthy. They do not consider the general population that may include those who are
very young, old, infirm or disabled. OELs are generally not relevant to community
exposures.

• Adjusting OELs for unusual and extended work schedules, needs to consider effects such
as synergism (where the combination of exposures can result in an effect greater than
the sum of effects of each individual substance) and potentiation (where one agent can
increase the potency of another).

Measurement of Hazardous Substance Page 54


Chapter 3 Occupational Exposure Limits
• Not all substances have OELs: It is impossible to develop appropriate OELs for each of
the hundreds of thousands of chemicals on the market. However, there are techniques
by which to derive values based on analogy with certain compounds (e.g.,
hydrocarbons). In addition, in recent years certain bodies, in particular NIOSH, have
published methodologies for the setting of Occupational Exposure Bands (OEBs) for
substances for which there is no official OEL. The setting of an OEB is outside the scope
of this course, but for the benefit of anyone who is interested, details of the NIOSH
methodology can be found at https://wwwn.cdc.gov/Niosh-oeb/

• Often regulatory standards include consideration of non-health-based factors when


setting OELs including engineering feasibility, economic impact on business/country,
analytical limits etc. Recommended OELs such as the ACGIH TLVs® and AIHA’s WEELs are
usually health based and do not take any such factors into consideration.

• For some chemicals, there are likely to be several OELs in existence which have been set
by different countries and scientific authorities. When deciding on which OEL to use,
consider the OEL most likely to provide the best worker protection i.e., a health/science
based OEL such as the ACGIH TLVs as well as the applicable country OEL that must be
complied with which may be different.

• OELs apply to personal exposure data rather than to either area or static monitoring
data which may not correspond with worker exposure.

Expert help can be provided by toxicologists, exposure scientists and occupational hygienists with
experience in the setting of OELs as well as the application of OELs in the workplace, if needed.

Measurement of Hazardous Substance Page 55


Chapter 3 Occupational Exposure Limits
Chapter 4 Air Sampling Theory and Practice

4.1 Introduction
Occupational hygienists often use air sampling to evaluate worker exposures for various reasons,
including risk assessment and/or evaluating engineering controls. A sampling strategy is essentially
a plan that defines the goals of the air sampling and how those goals will be achieved.

4.2 Workplace Sampling Strategies


A workplace sampling strategy is essentially a plan to collect data about worker exposure. A
sampling strategy, like any other experimental design, cannot be formulated until the objectives of
the exercise are clearly understood and documented. The concept of just collecting a few samples
to see how “good” or “bad” a workplace may be, is potentially biased and may not give an
accurate picture of workplace exposures.

The plan will depend on what its objectives are. In other words, what is (are) the question(s) that
need to be answered.

A possible objective of a monitoring strategy is to provide analytical information about the


workplace, which workers and management can use to ensure that, as far as is reasonably
practicable, no-one in that workplace suffers injury or illness as a result of exposure to hazardous
contaminants. Other objectives could include: determining exposures in response to complaints,
determining compliance with respect to various recommended occupational health exposure
limits, or to evaluate the effectiveness of engineering controls installed to minimize workers
exposure.

Thus, when developing any monitoring strategy, it is important to ask the fundamental question:
“How will the data generated from this exercise be used?” Without a reasonable answer to this
question the survey merely becomes the collection of data “for the sake of it”, which can turn out
to be a wasteful and meaningless exercise in retrospect.

The British Occupational Hygiene Society (BOHS 1993) also suggests other factors should be
considered before developing any monitoring programme. These include:

• The requirement for a qualitative risk assessment and appraisal of the workplace prior to
doing any measurements.

• The need to obtain measurements other than those of airborne contaminant


concentrations, e.g., wipe tests to determine surface cleanliness as a way of assessing
the potential for skin contact or measurements of ventilation plant performance.

• Any requirements for biological monitoring and the integration of these into the overall
survey strategy.

• Any requirements for monitoring overall performance or auditing the process.

Measurement of Hazardous Substance Page 56


Chapter 4 Air Sampling Theory and Practice
• Any other health hazards which may exist within the workplace, e.g., noise or biological
hazards, etc. which may also need to be considered.

• Any environmental or personal characteristics of the workers which may affect the
measurement.

Once these factors have been assessed it is appropriate to develop a workplace exposure sampling
strategy. In doing so it is appropriate to consider the following:

• What type of sample(s)? (area vs personal)

• Where should the sampling device be located?

• How many samples should be taken?

• How long should the sampling interval be?

• What periods during the work day should the employee’s exposure be determined?

• How should the samples be taken?

• What contaminants are likely to be present?

• What is (are) the expected concentration(s)?

• What (if any) compounds are present which may interfere with the sampling (or
analytical) procedure?

• What analytical methods are to be used and what (if any) constraints will these places on
sampling techniques?

When developing a sampling strategy, it is important to understand that the variability of the
workplace environment is such that no universal approach is possible to cover all possible
situations.

The inconsistency of the workplace, in terms of density and intensity of activity, variability of
activity, variability of exposure cloud and the influence of uncontrolled factors such as wind
direction, employee practices, etc. results in the fact that data can only be related to the situation
being studied at the time it was studied.

Any exposure assessment based on a single worker for a single day will have errors of space
(location) and time and we will have little to link this outcome to the real situation.

Individual measurements will not necessarily represent the group, but by accounting for as many
influencing factors as is practicable, we can ensure that some assessments are substantially better
than others.

Other factors affecting the measurement results include:

• The choice of monitoring equipment

Measurement of Hazardous Substance Page 57


Chapter 4 Air Sampling Theory and Practice
• The choice of the sampling method

• The choice of the analytical method

• The skill level of persons conducting the sampling and analysis

All the above factors need to be considered when considering a sampling strategy. It is important
to appreciate that monitoring the workplace does not in itself protect anyone, it merely provides
information; however, in some circumstances the mere act of monitoring does raise awareness of
the workforce and management which often results in initiatives to reduce exposure, regardless of
the actual results of the measurements.

The sampling system should be appropriate to the situation being studied and part of an overall
occupational hygiene monitoring strategy.

Guidance on the assessment of exposure can also be obtained from other sources such as BSEN
689 (1996) “Workplace Atmospheres – Guidance for the Assessment of Exposure by Inhalation to
Chemical Agents for Comparison to Limit Values and Measurement Strategy”.

4.3 Types of Surveys


Regulatory authorities throughout the world have different approaches to the design of
monitoring surveys. Some bodies are very prescriptive whereby individual workers in a workplace
are listed in regulation to be monitored at set frequencies using prescribed methods. In recent
years this approach has changed, with a move by some authorities to a risk-based approach.

In such situations it is not unusual for a common approach to be adopted with the following
components:

• Initial appraisal

• Basic survey

• Detailed survey

• Routine survey

While the names given to these components may be different in various countries and some
components may be combined (e.g., initial appraisal and basic survey), the concept remains the
same.

4.3.1 Initial Appraisal


In many situations this is commonly referred to as a “walkthrough survey” and has the objective of
being able to provide sufficient information to answer these questions:

• What are the potential exposures?

• Where and when do they occur?

Measurement of Hazardous Substance Page 58


Chapter 4 Air Sampling Theory and Practice
• Can the exposures be prioritized in terms of risk?

• Is further evaluation necessary?

• If further evaluation is necessary what is the preferred approach?

As previously indicated, collection of sufficient information to answer these questions is


paramount. While the walkthrough survey provides valuable information on the process, (e.g.,
materials being used and current controls), it may be necessary to seek further details. Such
information regarding the substances being used could include:

• Physical properties. For example, boiling point, vapours pressure, relative evapoursation
rate, dustiness, particle size distribution, ability to sublime, etc.

• What form is the substance? Is it a gas, vapours, mist, fume, or if it is an aerosol, is it


fibrous?

• Hazardous nature of the substance. This could include any known toxic effects in man
(both acute and chronic); other indications of toxicity (e.g., animal studies, in vitro tests,
structural factors, etc.); any special toxic potential (carcinogenicity, respiratory
sensitisation, reprotoxicity, etc.); and any indication of increased hazard from exposure
to mixtures of substances.

• Potential routes of entry to the body.

• Any effects on skin (e.g., corrosion, dermatitis) or mucous membranes (e.g., drying,
irritation).

• Any available exposure limits and the documentation for these.

During this initial information collection stage, the use of direct reading instruments or detector
tubes may be helpful in identifying emission sources or employees with potentially significant
exposures. Talking to the employees about the work that they do can also provide useful
information during a walk-through survey.

This information will be very limited and should only be used to support observations. At the
conclusion of the information collection exercise, it may be possible to make a reasonable
assessment of potential risk. It should at least provide sufficient information to decide if a more
detailed study is required or if a non-sampling approach would be effective.

4.3.2 Basic Survey


A basic survey is generally required when one or more of the following situations arise:

• The initial appraisal suggests that unacceptable exposures may be present in the
workplace.

• A new process is being started up.

Measurement of Hazardous Substance Page 59


Chapter 4 Air Sampling Theory and Practice
• Substantial changes have been made to the process, operations or control measures.

• Unusual, infrequent or intermittent processes or operations are to be conducted, e.g.,


maintenance.

• An occupational exposure limit has been set where one did not previously exist.

A basic survey will have limited objectives but these should include obtaining sufficient
information to answer the following questions:

• Does an exposure problem exist as suggested by the initial appraisal?

• Is available engineering, or other, controls adequate and likely to remain so?

• Is a more detailed survey necessary and what strategy should it follow?

In some cases, an initial appraisal may be followed by a detailed survey without the intermediate
step of a basic survey. This depends on what was found during the initial assessment and the skill
and experience of the hygienist performing the evaluation.

4.3.3 Detailed Survey


A detailed survey has a clear objective, usually to obtain reliable measurements of personal
exposures for comparison to exposure standards, reach conclusions regarding exposure levels and
decide (if necessary) what measures need to be taken to control unacceptable exposures. Thus,
for a detailed survey, results need to be representative of personal exposures so personal
sampling techniques are normally used. Moreover, the appropriate measurement period must be
used if the results are to be compared to an exposure standard which has a specific reference
period.

In addition, all aspects of the survey need to be reviewed to ensure errors which may affect results
are minimized. In many cases statistical based sampling techniques are adopted and detailed
statistical analysis of the data undertaken.

No matter what the circumstances, the essential questions of: “Who?, When?, Where and How?”
remain central to the development of an effective monitoring strategy.

4.3.4 Routine Monitoring


When developing a routine monitoring strategy, four issues need to be considered. These are:

• The frequency at which the monitoring survey is conducted

• The sampling methodology

• The number of samples required to meet the goals of the exercise

• The type of analysis of data that will be undertaken

Measurement of Hazardous Substance Page 60


Chapter 4 Air Sampling Theory and Practice
There are no set rules for the frequency of monitoring except where it is defined in local
legislation. Some mathematical models have been developed. However, such models are very
reliant on the quantity and quality of available data.

Irrespective of the above, there are a few simple guidelines which can be used to help in the
decision process regarding the frequency of routine surveys.

• How close are exposures to the relevant exposure standard – as exposures approach the
exposure standard more frequent monitoring will be required (as distinct from being
either well below or excessively above the exposure standard).

• The effectiveness of controls – in a well-controlled environment where the likelihood of


control failure is low, monitoring frequency can be reduced.

• The process cycle – monitoring frequency will need to match the process cycle. This is
especially important in situations where periodic events occur (e.g., maintenance
shutdowns) or irregular process cycles.

• The temporal variability of exposures - consideration needs to be given so as to take


account of seasonal and shift variations (e.g., increased production on night shift).

• The variability of exposure - in a process where a high level of variability of exposure is


present, increased monitoring would be required to establish the reason for such
variability.

Other factors that need to be considered are:

• Changes in sampling methods

• Changes in analytical methods

• Changes in behavior patterns of workers

Such changes can affect the survey results from year to year and some understanding of these
issues is necessary if data from varying years is to be compared.

4.3.5 Statistically Driven Approaches


The problem of how to correctly (or more accurately) measure workplace exposures has been the
subject of debate within the occupational hygiene profession for many years.

In the last 25 years there has been a gradual move to statistically based monitoring programmes
where the workforce is divided into groups of similar exposures called “Homogeneous or Similar
Exposure Groups” (HEGs or SEGs) and a statistically based subset of each group is monitored on a
random basis for an extended period of time. In essence, employees are placed into groups (SEGs)
based on past monitoring data or via using the knowledge of persons working in a plant as to
possible exposures.

Measurement of Hazardous Substance Page 61


Chapter 4 Air Sampling Theory and Practice
A number of persons in each group are then monitored and it is assumed that the exposures
measured represent that of the whole group (SEG).

Once sufficient data has been collected a statistical analysis of the exposures can be undertaken to
establish the level of compliance to the relevant exposure standard and to provide an indication in
the variability of the data.

While statistically based sampling and evaluation of workplace exposures is very useful in giving a
more accurate picture of employee exposures, it should not be considered as being the absolute
test. There are many assumptions (and thus potential errors) in such programmes but by
controlling as many influencing factors as is practicable a better estimate of exposure will be
guaranteed.

Where considered appropriate, evaluation of workplace exposures should be conducted using


non-biased (random) sampling programmes using the concept of SEGs Survey Design.

4.4 Who Should Be Sampled?


The question of whose exposure should be monitored can be answered only by reference to the
objectives of the proposed survey and the details of the observed work practices. If the process
only involves several workers doing exactly the same thing, then the task is relatively easy,
however if the process involves large numbers of persons doing different tasks, then the choice of
who to monitor becomes more difficult.

In many basic surveys the practice is to target “worse case” situations, however there is merit in
including some workers who are expected to have lower exposures. This provides a level of quality
control in respect to the initial appraisal and the choice of “worse case” individuals sampled.

4.5 When
The choice of when to monitor is directly related to what process or tasks give rise to significant
exposures. The other major factor that must be considered is the toxicology of the substance
under consideration.

For example, it is important to undertake short term sampling for acutely toxic substances
because they are fast acting, whereas longer sampling would be more appropriate for substances
that are chronically toxic.

The other point to consider when considering when to monitor is the type of exposure standard
appropriate to the substance of concern (e.g., TWA, STEL, Ceiling or Peak). These are generally
related to the toxicological properties of the substance.

As a general rule it is reasonable to state that if the objective of the survey is to evaluate the
exposure of a worker during a specific task, then the monitoring duration should equal the whole,
or a representative part, of the task.

Measurement of Hazardous Substance Page 62


Chapter 4 Air Sampling Theory and Practice
4.6 Where?
Potential sources of contaminants of interest should be identified when developing a sampling
strategy to identify where samples should be collected. Direct reading instruments (See Section
6.12) are useful in this regard, although results obtained would not generally represent personal
exposures. Air samples should be collected on representative individuals working with or around
contaminants of interest, during operations of interest (e.g., routine work, maintenance activity).
Actual samples would be placed in employee breathing zones (see Section 4.12).

Note that while fixed location (i.e., static) sampling is of use to identify either where workers may
be exposed, or whether controls are effective, or where there may be leaks, or other purposes, its
limitation is that its results represent a specific location rather than actual worker locations (See
Section 4.13). In many cases, sampling for compliance with OELs requires personal air monitoring.

4.7 How?
The selection of sampling equipment and analytical methods will in general result from the
properties of the contaminant under investigation. Other factors that will come into the equation
include:

• Legislative requirements

• The accuracy and precision required

• Intrinsic safety requirements

• The need for subsequent laboratory analysis

• Transport of samples to the laboratory

• Portability of equipment

In all cases it is prudent to use sampling methods from recognized authorities (e.g., National
Standards, NIOSH, OSHA, HSE).

Both the sampling method and the analytical method are subject to error and thus what may be
the most desirable choice from one standpoint may not be from the other.

Ultimately the choice will be a compromise, often dependent on the experience of the
occupational hygienist and the working relationship between the hygienist and the laboratory that
will perform the analysis.

The BOHS (1993) suggests the following considerations when selecting the sampling method.

• Is the sampling device (and collection medium) suitable for collecting the contaminant of
interest and is the medium compatible with the subsequent analytical method?

• Is sufficient known about the dynamics of the collection process so that any variables
can be accounted for in the design of the sampling programme?

Measurement of Hazardous Substance Page 63


Chapter 4 Air Sampling Theory and Practice
• A number of factors can influence the selection of the sampling device and collection
medium, but in practice they are generally limited to:

• For aerosols, what is the most appropriate device to collect the size range of particles of
interest? Are wall losses (material which sticks to the sampling head and does not lodge
on the filter), either within the sampling head or train, of an order such that account
needs to be taken of them?

• For mists, especially, does possible vapours loss need to be taken into account?

• For gases and vapours sampled from a mixed atmosphere does preferential sorption of
one or more contaminants take place in the collection medium? Does the presence of
high water-vapours levels affect sorption characteristics of the sampling medium or the
presence of particulate material adversely affect the collection characteristics?

• With all contaminants, is the total capacity of the collecting medium sufficient to cope
with the likely loading of the contaminant given the intended sampling rate over the
proposed sampling period?

Other issues (such as the number of samples) need to be addressed but these will be discussed in
Section 4.8.

4.8 Sample Numbers


An occupational hygiene challenge in air sampling is to determine the appropriate numbers of
samples to achieve the stated goals of an air sampling strategy. The answer depends on what
information is required from the exercise. Some examples would be:

• Compliance – The number of samples is sometimes prescribed in legislation so the


decision process may be straight forward. In other cases, it is necessary to collect
enough samples to be able to demonstrate compliance. For very low exposures this may
be just a few samples but as exposures approach the exposure standard this will require
many more samples.

• Epidemiology – Such exercises invariably involve collecting as much data as possible and
is usually limited by time, budgets and resources.

• Corporate Requirements – Again, such programmes usually have specific requirements


but in many organisations are based on one or more of the statistical monitoring
approaches.

• Degree of Confidence – In such cases an increased level of confidence (99% as against


95%) will result in a significant increase in sample numbers.

Some general “rules of thumb” have been proposed (e.g., 1 in 10 workers should be sampled or a
minimum of 3 samples with a spread of less than 25%), however such approaches should be used
with care as they could significantly affect the quality of the data.

Measurement of Hazardous Substance Page 64


Chapter 4 Air Sampling Theory and Practice
While it is possible to obtain a reasonable approximation of an exposure distribution with 6-10
samples, as the exposures approach the exposure standard 30 or more measurements may be
necessary to ensure the distribution of exposures is well defined.

4.8.1 Coefficient of Variation


Grantham (2001) describes the use of estimates of the mean and the standard deviation (S or SD)
of previous data to derive sample numbers as follows:

𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒𝑠 = (𝑡_(𝑣𝑎𝑙𝑢𝑒 ∗) 𝐶𝑉/𝐸)^2 …Equation 4-1

Where

𝑡_(𝑣𝑎𝑙𝑢𝑒 ∗) is the t-statistic for the number of degrees of freedom (n-1, with n
being the number of originals samples).

CV is the coefficient of variation

E is acceptable error rate

4.8.2 Rappaport & Selvin


[Reference – Am Ind Hyg Ass J, 1987 Apr;48(4):374-9]

This is another method that requires prior data. It essentially determines the number of samples
needed to test the mean exposure of a lognormal distribution of exposures against an OEL. Table
4-1 summarizes the process.

To use Table 4-1, one must first estimate an F value as follows:

𝐹 = (𝑠𝑎𝑚𝑝𝑙𝑒 𝑚𝑒𝑎𝑛)/𝑂𝐸𝐿 …Equation 4-1

Secondly, one needs to have an estimate of the Geometric Standard Deviation. You should be able
to estimate this using the preliminary data. An easy way to do this would be to use the AIHAs
IHSTAT, an Excel based approach (See https://shrtm.nu/S9VM. Or, it can be done in Excel.

Before using Table 4-1 Rappaport and Selvin Sample Number Model (α= 0.05, β= 0.10), you need
to understand what α and β mean:

α= 5% chance that it is claimed that the workplace complies with the exposure standard
when in fact it does not.

β= 10% chance that it is not claimed that the workplace complies with the Exposure
Standard when in fact it did.

Measurement of Hazardous Substance Page 65


Chapter 4 Air Sampling Theory and Practice
IHSExample
Say you had some previous data from 5 samples, with a mean of 60 ppm and a
standard deviation of 15 ppm. Assuming an acceptable error rate of 10%, how any
samples would be needed?

Step 1 would be to look up the t-value for 4 degrees of freedom in a reference table.
That value corresponds to 2.776.

Step 2 would be to estimate the co-efficient of variation as follows

𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝐷𝑒𝑣𝑖𝑎𝑡𝑖𝑜𝑛
𝐶𝑉 =
𝑀𝑒𝑎𝑛
15
𝐶𝑉 = 60 or 0.25
Step 3 would be to insert values into the equation. So

0.25 2
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒𝑠 = (2.776 ∗ ) 𝑜𝑟 21.4 (22 𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔 𝑢𝑝)
0.15
So, using the preliminary data from the boxed example above (60 ppm average), assuming an OEL
of 120 ppm, if the preliminary data had a Geometric Standard Deviation (GSD) of 2.0, one would
need to collect 21 samples. Note, however, that if the preliminary data represents a greater
percentage of the OEL than the 50 percent value in this example, the number or recommended
samples increases. In other words, as the mean of the exposures approaches the exposure
standard, more samples are necessary to make an accurate judgement as to whether the exposure
standard is exceeded. The same is the case where the data is more scattered (higher GSD), one
would need substantially more samples. However, if the data exceeds the OEL (calculated F > 1),
assuming no changes in the processed monitoring, additional sampling is less useful.

Table 4-1 Rappaport and Selvin Sample Number Model (α= 0.05, β= 0.10)

Fraction Geometric Standard Deviation (GSD)


of the OEL
F 1.5 2.0 2.5 3.0 3.5

0.10 2 6 13 21 30
0.25 3 10 19 30 43

0.50 7 21 41 67 96
0.75 25 82 164 266 384
1.25 25 82 164 266 384

1.50 7 21 41 67 96
2.00 2 6 11 17 24
3.00 1 2 3 5 6

Measurement of Hazardous Substance Page 66


Chapter 4 Air Sampling Theory and Practice
4.8.3 NIOSH
NIOSH’s 1977 approach is on SEGs (Similarly Exposed Groups). The number of samples SEG can be
determined from Table 4-2 and the exact sampling days should be determined using random
number tables.

Table 4-2 NIOSH Sample Size Guide

Sample size n for top 10% (τ= 0.1) and 95% confidence (α= 0.05)

Source: NIOSH 1977


Size of Group (N) 12 13-14 15-16 17-18 19-21 22-24 25-27 28-31 32-35 36-41 42-50 ∞

Required No. of
Measured 11 12 13 14 15 16 17 18 19 20 21 29
Employees (n)

If N <= 11 then n = N

Such an approach should ensure that at least one result should be within the top 10% of
exposures with 95% confidence. However, following NIOSH’s recommendations may result in
collecting more samples than needed to obtain a reasonable estimate of exposures.

Figure 4-1 AIHA Sample Guide

Source: AIHA 1998 – Used with permission of the American Industrial Hygiene Association (2007)
4.8.4 AIHA
The AIHA (1998 and 2006)
indicates that there is a point of
diminishing returns in respect to
the number of samples required
to adequately define an
exposure profile. Fewer than six
(6) measurements leave a great
deal of uncertainty about the
exposure profile, while more
than ten (10) provides additional
refinement in exposure
estimates but the marginal
improvement is rarely cost
effective, as indicated in Figure
4-1.

Measurement of Hazardous Substance Page 67


Chapter 4 Air Sampling Theory and Practice
4.8.1 The BOHS/NVvA Guidance
The British Occupational Hygiene Society (BOHS) in conjunction with its sister organisation in the
Netherlands, Nederlandse Vereniging van Arbeidsdeskundigen (NVvA), have also developed some
guidance on measurement strategies specifically for determining compliance with OELs. The
approach is designed to take account of both between worker and within worker variability. It
does not, however, give general guidance on conducting a survey of exposure in the workplace.

Sample numbers are based on statistical considerations. During the first phase, 3 samples from
workers selected randomly, are taken from a SEG and if all of these are below 10% of the OEL then
it can be concluded that the limit is unlikely to be exceeded. If one or more of the results is above
the limit, then this indicates that it can be exceeded. In either case no further sampling is required.
Otherwise at least 2 more samples are required from each of the same 3 workers. Including the
original 3 samples this will give a total of at least 9 results which can then be analysed using the
recommended statistical tests. Figure 4-2 provides a summary of the BOHS/NVvA sampling
scheme.
Figure 4-2 BOHS/NVvA Sampling Scheme
During a basic
survey, it may only
be possible to take a
few samples due to
practical
considerations or
because only a few
workers carry out
the work. It may still
be possible to arrive
at valid conclusions
about exposure in
such circumstances
by taking account of
observations and
other types of
evidence providing
care is taken when
interpreting the
results, bearing in
mind the typical
exposure profiles
discussed above.
Source: BOHS/NVvA

Measurement of Hazardous Substance Page 68


Chapter 4 Air Sampling Theory and Practice
4.9 How Long to Sample
In many cases, occupational hygienists may be collecting samples to evaluate 8h-TWAs, in which
case the sampling period will last a full shift. In other cases, sampling times will be shorter because
the process of interest is shorter or because one is interested in 15-minute exposures.

However, it is also important to review the analytical method of detection for the proposed
method of analysis. Although this information may be listed in the documentation for the
proposed method, it is important to discuss this with the laboratory BEFORE undertaking
sampling. Knowledge of the limit of detection (LOD) dictates the minimum sampling volume and
therefore the length of sampling time required. In some cases, it may not be possible to measure
15-minute exposures because the sample volume is not large enough to contain detectable
quantities of the contaminant of interest.

Example
You have been asked to collect air samples for a metal that has an OEL of 0.1 mg/m 3
(i.e., 100 µg/ m3). Exposure controls appear adequate so you estimate that exposures
might be about 10% of the OEL. The lab where you plan to have the samples analysed
tells you the analytical limit (LOD) of detection is 10 µg per sample. Using a flow rate (FR)
of 2 liters per minute (i.e., 0.002 m3/min), how long should you collect the sample for to
get a detectable amount of metal on the sample?

The minimum sampling time (t in minutes) can be calculated as follows:


𝐿𝑂𝐷
𝑡= 𝑚𝑖𝑛𝑢𝑡𝑒𝑠
%𝑂𝐸𝐿 ∗ 𝐹𝑅

i.e.:
10
𝑡= 𝑚𝑖𝑛𝑢𝑡𝑒𝑠
10 ∗ 0.002
Which works out to be 500 minutes. So, you’d have to sample for at least a full shift (8 hours).

4.10 Sampling Patterns


When designing a sampling strategy there are a number of different sampling approaches that can
be adopted. These are usually based on the contaminant, type of survey, work patterns and
process variability. These include:

• Grab samples

• Partial period consecutive samples

• Full period consecutive samples

• Full period single samples

In some countries this is referred to as:

• Grab sampling

Measurement of Hazardous Substance Page 69


Chapter 4 Air Sampling Theory and Practice
• Task duration sampling

• Short period sampling (less than the task duration and sometimes taken consecutively)

• Full shift sampling

Irrespective of the nomenclature used the fundamental concept is similar. These different
approaches are shown Figure 4-3 Sampling Patterns
graphically in Figure 4-3.

What is important to appreciate


is that the sampling approach
adopted must take into account
the exposure pattern of the
person being sampled if
representative data is to be
obtained. In the following
discussion “period of interest”
can refer to either the period
upon which the exposure
standard is based (8 hours in
many cases) but also in modern
working patterns to the period
of exposure while conducting a

Source: NIOSH 1977


task. It is for the hygienist to
make a judgement as to what is
their “period of interest” for the
exercise being conducted.

• Grab Samples – are


samples lasting only a few minutes or seconds. They are usually taken using direct
reading instrumentation during an initial survey (walkthrough survey) to highlight
potential exposures or sources of exposure. Other types of grab samples are canisters or
bags (into which air is drawn for later laboratory evaluation), and color indicator
detector tubes.

• Partial Period Consecutive Samples – consists of one or more samples of equal or


unequal duration covering only a part of the period of interest. The major problem with
this approach is how to estimate the exposure that occurred during the period not
sampled. NIOSH (1977) recommend that at least 70-80% of the full period is sampled.

Some international standards indicate that in situations where exposures are likely to be constant
as little as 50% of the full period need be sampled. In all cases professional judgement plays a
significant role in choosing the best approach.

• Full Period Consecutive Periods – these cover the full period of the relevant standard
(e.g., 8 hours for an 8-hour TWA exposure standard or 15 minutes for a STEL). This
approach is very useful in those situations where the process is intermittent, thus giving

Measurement of Hazardous Substance Page 70


Chapter 4 Air Sampling Theory and Practice
data not only on the TWA exposure but also the variation in exposures in relation to the
process. This approach can also be useful in situations where sampling media may get
overloaded if sampling is carried out for single extended periods of time such as 8-hours.

• Full Period Single Samples – are normally carried out to establish the average exposure
of workers during their normal work day. Such samples enable the results to be
compared directly to an OEL based on an 8-hours TWA.

4.10.1 Sampling to Assess Acute or Chronic Effects


The toxicology air contaminants of concern can have a significant influence on the design of
sampling strategies. For example, chronic acting substances such as crystalline silica (quartz) are
sampled over an extended period (e.g., full shift duration) while acute acting substances should be
sampled over a time period in accordance with the appropriate STEL or if the onset of an effect is
rapid the appropriate use of alarmed direct reading instrumentation may be appropriate.

In some instances, it may be appropriate to sample for both the full shift and over short periods as
a substance may have both TWA and STEL exposure standards (e.g., trichloroethylene).

4.11 Practicalities of Sampling Programmes


While the previous sections (see also Section 4.8) describe the various approaches to sampling and
the number of samples to be collected, there are a number of practical issues that also need to be
addressed.

The first of these is cost effectiveness. Large statistically-based monitoring programmes are very
difficult to undertake in terms of the equipment required, the resources necessary to undertake
the exercise and the ongoing disruption to the process. Consequently, it is rare for such
programmes to be implemented outside of multi-national corporations and thus the question
arises “what can reasonably be done?”

For example, a single person operating without any assistance will find it difficult to calibrate,
distribute, monitor and recalibrate more than five sample collection devices at one time. Given
this, it is important that the quality of the monitoring be excellent, the persons and situations
determined for monitoring be appropriate and the collection of data be such that any
abnormalities in results can be explained.

Obviously, professional judgement and experience are major factors in this situation but provided
the basics are clearly understood and correctly applied, a good assessment of worker exposure
can be made.

The relationship between observations (work practices, control measures, dustiness of process,
etc.) and measurements cannot be over-stated; it is better to have fewer samples that can be
clearly interpreted than a large number of samples with limited data which can’t. The balance
between what is reasonably possible to achieve and what is necessary to obtain a picture of
exposure needs to be assessed for each and every exercise. If one person cannot achieve what is
necessary to obtain an exposure profile, then extra resources will be required.

Measurement of Hazardous Substance Page 71


Chapter 4 Air Sampling Theory and Practice
Unfortunately, there is a shortage of good quality well trained people to perform sampling
exercises in the workplace, which may well limit what can be done.

The final limitation on sampling programmes, in many cases, is the process itself. In some
situations, the processes (e.g., batch process which occurs infrequently), do not lend themselves
well to statistically-based random sampling monitoring exercises. An evaluation of each process is
required before considering what can be reasonably achieved.

4.12 Personal Sampling

4.12.1 Breathing Zone


As the main route of entry into the body for many substances is via inhalation, it is logical that any
estimate of exposure of such substances should be conducted in a location consistent with normal
inhalation patterns of workers. By convention, this has been deemed the “breathing zone” and is
defined by some statutory authorities (e.g., Australian Standard AS2985) as:

“A hemisphere of 300 mm radius extending in front of the face and measured from the midpoint
of a line joining the ears.”

Samples collected in the breathing zone of a worker are termed “personal samples” and are
directly linked to workplace exposure standards.

Research in wind tunnels has demonstrated that the location of the sampling head can result in
significant concentration differences over short distances. To avoid such variations, it is common
practice to attach sampling heads in the area of the worker’s lapel but still within the breathing
zone.

The other variable in the sampling head location equation is worker practices, which may have a
significant influence on exposure. One such case occurs when a worker inserts his or her head into
a reaction vessel to monitor the process.

Such actions may give rise to incredibly high exposures of short duration. The sampling device
needs to be positioned in such a manner within the breathing zone to collect the contaminant of
concern.

One approach to overcome (or at least minimize) some of the difficulties if factors are significantly
influencing the exposure cloud, is the use of dual lapel sampling – that is, collecting duplicate
samples on the worker with one sample collected on the left lapel and the other sample collected
on the right lapel. This at least gives some estimate over the variation in the exposure profile over
relatively short distances.

4.12.2 Operator Variability


The concentration of contaminants in the workplace is subject to both temporal and spatial
variation and thus likely to be in a constant state of flux. This is not only due to changes in the
process, but also ventilation rates, climatic conditions, etc.

Measurement of Hazardous Substance Page 72


Chapter 4 Air Sampling Theory and Practice
For workers, the range of tasks undertaken during a work day can dramatically influence an
exposure pattern and concentrations. In many cases individual approaches to performing the
same task (e.g., left or right-handed shoveling) may (and often does) result in significant exposure
differences between workers performing the same task.

Such factors must be considered when designing a sampling strategy so as to ensure their
influence on the exposure levels is taken into account.

4.13 Area Sampling

4.13.1 General or Background Measurements


Samples which are not taken on the individual in the breathing zone are generally referred to as
static (or area) samples. Such samples do not normally correlate well with actual personal
exposures but they still do have a useful role. Static samples are useful for the following purposes:

• To check the performance of control devices.

• As a surrogate for personal exposures, when a clear correlation between the results
from static samples and personal samples has been established.

• In identifying and quantifying contaminant sources in the workplace and in delineating


areas of unacceptable contamination.

• As part of the process for assessing trends in baseline concentrations.

• Are sometimes the only realistic means of measurement when certain types of
continuous monitoring are required.

• As the only realistic method of sampling high volumes of air (e.g., asbestos clearance
monitoring, or where there is a very low exposure limit and the sampling method LOD is
not low enough).

It should be understood that workplace exposure standards are linked to personal sampling and
the use of static or area samples for health assessment is not generally accepted.

Measurement of Hazardous Substance Page 73


Chapter 4 Air Sampling Theory and Practice
Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling
Methods

This section describes and discusses airborne dusts, fumes and fibres and methods available to
evaluate airborne concentrations. This section addresses:
✓ What are dusts, fumes and fibres?

✓ Particulate deposition in the lung and why it's important

✓ Basics of Particulate Air Sampling

✓ Air Sampling Pump use and Calibration

✓ Commonly Particulate Air Sampling Methods

✓ Particulate Air Sampling Calculations

✓ Direct Methods for Particulate Air Sampling

This section provides and overview of some generally accepted practices and procedures used to
evaluate airborne exposures to dusts, fumes and fibers, for which there are many accepted
methods, including those developed by HSE (UK), and NIOSH (US).

5.1 Introduction to Dusts, Fumes and Fibres


Airborne dust is one of the most common issues in work places notably mines, quarries, cement
mills and construction sites. It originates from applying forces such as crushing on a parent
material, which may be either natural (e.g., mining ores), or man-made (e.g., asbestos products,
building components, etc.). Dust typically consists of particles larger than 0.5 µm.

Fume can be defined as the condensation product of materials vapoursized during hot processes
(e.g., smelting, or welding). Fume particles are typically smaller than 0.05 µm and tend to
agglomerate.

Fibres are generally defined as particles with an aspect ratio (length to width) of ≥ 3:1.

Particulates is a collective noun generally used to refer to aerosols such as dust, fumes, mists, and,
smoke.

The adverse effects of dusts, fumes and fibres depend on particle size and chemical composition.
Particle size is important because it influences where in the body the particles may be deposited.
Chemical composition is important to understand the intrinsic toxic (i.e., hazard) properties of the
material in question.

5.2 Particulate Deposition


The fraction of particles that are inhaled depends on factors such as speed and direction of air
movement around the body, rate of breathing, whether breathing is through the mouth or nose.

Measurement of Hazardous Substance Page 74


Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling Methods
Inhaled particles may then be deposited along the respiratory tract or may even be exhaled with
exhaled breath.

Figure 5-1 The Differences Between the Different ISO Fractions

Source: TSI Inc, Reproduced with Permission


Over the years, various terms (e.g., total dust, total inhalable dust, inspirable dust) have been used
regarding airborne particles, sometimes inconsistently. However, the general consensus is that the
International Standards Organisation (ISO 1995) conventions are most appropriate. ISO 1995 has
defined three sampling conventions (inhalable, thoracic and respirable) for use in assessing
potential health effects of airborne particles in the workplace.

Inhalable fraction: The mass fraction of total airborne particles inhaled through nose and mouth.
In general terms the inhalable fraction includes all particles <100 µm, though it may include larger
particles, although there is no data to support this.

Thoracic fraction: The mass fraction of inhaled particles that penetrate the respiratory system
beyond the larynx.

In general terms the thoracic fraction includes all particles <50 µm and having a 50% cut (of total
airborne particles) of about 10 µm.

Respirable fraction: The mass fraction of inhaled particles that reach unciliated airways (alveoli)
where gas exchange takes place. In general terms the respirable fraction includes all particles
<16 µm (majority <10 µm) and having a 50% cut at about 4 µm.

The importance of the above deposition curves cannot be overstated as this links the potential
health effect with the sampling device necessary to assess the potential health risk.

Measurement of Hazardous Substance Page 75


Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling Methods
For example, consider the following dust Figure 5-2 Respirable Dust
examples, common in the international mining Sampling Train
environment, coal and lead dust. If we first
consider the health effect of each:

• Coal dust: Gives rise to the respiratory

Source: University of Wollongong


disease “pneumoconiosis” whereby normal
lung tissue is replaced by fibrous scar issue
due to the long-term inhalation of coal
dust. Here, the issue is respirable dust.

• Silica Dust: Prolonged exposure to


respirable silica is associated with scarring
of the upper lobes of the lung (silicosis), as
well as with lung cancer. These effects do
not occur if silica dust is too large to be respirable.

• Lead dust: Lead is a systemic poison which has been associated with kidney dysfunction,
increased blood pressure and sperm abnormalities. Historically the major toxic effect of
lead has been on the blood system, resulting in anemia. Thus, inhalable fraction is of
greatest interest.

5.3 Particulate Air Sampling

5.3.1 General
Exposures to airborne particulates can be evaluated through traditional air sampling methods that
involve drawing air at a known flow rate through a pre-weighed membrane filter for a specified
time, and later submitting the filter to a laboratory for gravimetric analysis (i.e., post sample
weight to determine mass of particulate collected over a specified time). These filters may be
mounted in different housings (or sampling heads) as detailed in Sections 5.4 to 5.9.

In earlier times, it was common practice for industrial hygienists to weigh sample filters before and
after. Nowadays, sample filters are weighed before and after in a laboratory.

Airborne particulates are typically sampled using a sampling train that consists of a calibrated air
sampling pump connected to the sample filter via a short length of tubing as shown in Figure 5-2
which shows a sampling train for respirable dust.

Sampling trains can also be assembled for other types of particulates, as described in Sections 5.4
to 5.9.

Once assembled, and calibrated (see Section 6.3), the sampling train is installed on a worker of
interest. The pump is usually attached to the worker's belt. It's a good idea to have spare web
belts or a suitable harness to mount the air sampling pump if the worker is not wearing a belt.
Some practitioners have also used vests to hold the equipment and reduce worker inconvenience.

Measurement of Hazardous Substance Page 76


Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling Methods
It is important to place the Figure 5-3 Sampling Train Placed on Worker
sampling head near the worker's
breathing zone as shown in Figure
5-3.

The standard convention for


placing the sampling head is in a
worker's breathing zone. In the
case of welding fume evaluations, Sampling
if possible, the sample head needs head
to be placed inside the welding
helmet, rather than outside as this
will overestimate actual exposure.

The following sections provide


details on commonly used

Source: University of Wollongong


particulate sampling methods and
is not intended to be all inclusive.
Other methods may be specific to
certain industries, jurisdictions and
regulations (local or national). Sampling

Practicing occupational hygienists pump

are advised to be familiar with


local requirements in addition to
industry standards.

Exposures to airborne particulates can also be achieved through direct reading real-time
instruments as discussed in Section 5.3.1

5.3.2 Sample Filters


There are a variety of airborne particulates of occupational hygiene interest that are captured
onto different filter media for subsequent analysis for the contaminant of interest from the air
being sampled.

The choice of collection media will normally be dictated by the choice of sampling method, and by
analytical considerations. In general, there are three types of mechanisms which capture particles
during filtration. These are:

• Interception (impingement) – This occurs when the particle is smaller than the pore of
the filter.

• Inertial Impaction – This occurs with a change in direction of airflow and requires high
velocities and dense fibre packing of filters.

• Diffusion – This occurs with very fine particles and occurs at low flow rates and is
assisted by electrostatic forces.

Measurement of Hazardous Substance Page 77


Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling Methods
There are a number of properties that are desirable (but not always present) in filter media. These
include:

• High collection efficiency that is known

• Manageable resistance (particularly as the load on the filter increases)

• Low moisture picks up or loss

• Low electrostatic properties

• Compatibility with the selected analytical technique

• Low cost

Not all these properties are achievable in one filter so the selection of a particular filter media for
a particular measurement becomes one of compromise.

The filter selection guide below shows which filters can be used for particular contaminants, but
local or statutory requirements may necessitate using an alternative.

Notwithstanding the information provided above, many Occupational Hygienists choose not to use
mixed cellulose ester filters for metal fume – metal dust analysis due to the poor electrostatic
properties which make them difficult to weigh. Alternatives commonly used include glass fibre or
polyvinyl chloride.

One aspect of filter selection that is sometimes confusing concerns pore size. When sampling for
respirable dust (50% cut at 4 µm), it is not uncommon to use a filter (PVC) of nominal pore size 5
µm. This seems illogical but since most membrane filters allow air to follow a tortuous path,
aerosols smaller than 1 µm are commonly captured. However, this does not apply to
polycarbonate filters which allow air to pass straight through because of how they are built.

Two other features of filters are critical and can cause significant errors in gravimetric analysis if
not considered. These are moisture and electrostatic charge.

In the case of some filters (especially membrane filters), moisture pick-up or loss can be
significant. This can be corrected for by the process of “equilibration”. This process requires that
sample filters and a suitable number of blanks be placed in clean containers with the lids slightly
ajar, in the balance room where they are to be weighed. They are then left for a suitable time to
come to equilibrium with the balance room atmosphere (overnight, but this may depend on the
filter type) before weighing. At the end of the sampling exercise the process is repeated and a
correction made for any gain or loss of mass in the blank filters (this should be minimal if the
balance room atmosphere is well controlled).

The other critical issue is electrostatic charge. This can be overcome by the use of a static
eliminator (usually an Americium 241 or Polonium 210 source). A high voltage static eliminator
may be used but it should be checked to ensure that it does not punch holes through the filter.

Measurement of Hazardous Substance Page 78


Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling Methods
Table 5-1 Filter Selection Guide

Material Main Properties Air Sampling Applications

Mixed Cellulose Ester Hydrophilic Metal dust analysis


(MCE) Readily soluble for atomic absorption Asbestos and man- made fibres
analysis
Readily rendered transparent for
transmitted light microscopy
Dissolves and clear easily

Polyvinyl Chloride (PVC) Hydrophobic Gravimetric analysis of dusts


(Pure homopolymer) Non-oxidizing surface Silica-free Hexavalent chromium
Low ash Quartz analysis by IR
Low tare weight for gravimetric analysis spectrophotometry

Polytetrafluoroethylene Hydrophobic Alkaline dusts


(Teflon) Inert to solvents, acids and bases Polynuclear aromatics (PNA)
Autoclavable Pesticides

Polycarbonate Hydrophobic Scanning electron microscopy


Microscopically smooth surface Asbestos fibres
Straight-through pores
Extremely thin (10 –20 µm) and
transparent
Autoclavable

Silver Wide solvent compatibility Bromine


Higher temperature tolerance Asbestos by TEM
Autoclavable Silica by x-ray diffraction
Uniform porosity and thickness

Source: SKC Inc – Reproduced with permission


Glass Fibre (MMMF) Partially hydrophobic Pesticides
Higher temperature tolerance Coarse gravimetric analysis
Autoclavable
Isocyanates
High particulate retention
Ethylene glycol

Quartz Low level metals content Particulate Matter less than 10


High temperature 300°C micrometres (PM10)
Autoclavable Diesel particulates
Autoclavable
Cellulose AA HPCL
Uniform strength
Ashless (Type 40)

One final aspect needs to be considered and that is the transportation of dust-laden filters after
collection. Experience has shown that the layer of dust on the filter is fragile and any shocks or
vibration may cause loss of material unless precautions are taken. The safest way is to deliver
samples to the lab is by hand. If not possible, then filters should be carefully packed to avoid
dislodging collected dust from the filter.

Measurement of Hazardous Substance Page 79


Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling Methods
5.3.3 Basic Sample Collection Procedure
As indicated above, air sampling for particulates requires assembling a sample train consisting of a
calibrated air sampling pump connected to the appropriate air sample collection device (also
known as sampling head). Sections 5.4 to 5.9 provide details on commonly used particulate air
sampling heads.

The following are the basic steps for air sampling:

• Calibrate pump flow rate with sampling head attached (see Section 5.4.1)

• Place pump on worker of interest. Record relevant information (e.g., Name, location, job
classification, work activities, date, temperature, engineering controls, personal
protective equipment used, anticipated breaks, etc.) The use of a standard form to
collect information consistently is recommended (e.g., AIHA’s).

• Secure air sampling head in worker's breathing zone.

• Turn pump on, and record time. Allow worker monitored to go about their business.

• Periodically verify that pump is still in operation by inspection of pump mounted flow
meter. Inspect and review processes of interest to verify activities monitored are as
expected. Keep detailed notes. You will find them useful later when reviewing the
results.

• At the end of the sampling period, note time, and record flow rate at end of sampling
period. Post sampling flow rates should be within ± 5% of pre-sample flow rates. If the
difference is greater, the sample should be considered invalid.

• Use the difference in the start and end times to calculate Figure 5-4 IOM Sampling
the period sampled in minutes. Head

• Carefully remove the air sample filter cassette, weigh if


analysing on-site, or package and send to the lab. You
will need to calculate the sample volume (i.e., product of
sample time and average before and after flow rate). Be
sure to indicate units of measure for volumes (i.e., how
many cubic metres or litres).

• See Section 5.11.2.2 for example calculation.


Courtesy: University of Wollongong

Sections 5.4 to 5.9 provide details on commonly used


particulate sampling methods and is not intended to be all
inclusive. Other methods may be specific to certain industries,
jurisdictions and regulations (local or national). Practicing
occupational hygienist are advised to be familiar with local
requirements in addition to industry standards.

Measurement of Hazardous Substance Page 80


Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling Methods
Exposures to airborne Figure 5-5 CIS Sampler
particulates can also be achieved
through direct reading real-time
instruments as discussed in

Source: HSE – Reproduced with Permission


Section 5.15.

5.4 Inhalable Dust


There are a number of sample
collection devices for measuring
airborne inhalable dust as
detailed below. A number of
comparative studies conducted
over the

years indicate that the Institute


of Occupational Medicine (IOM) Sampling Head has been shown to give the best agreement to the
ISO criteria for inhalable dust under the widest range of workplace conditions and is therefore the
preferred method of sampling inhalable dust in many (but not all) countries.

5.4.1 IOM Sampling Head:


This device (Figure 5-4 IOM Sampling Head) was developed by the UK Institute of Occupational
Medicine (IOM). It consists of a single orifice entry and a filter contained within a cassette. The
sampler requires a sampling pump operating at 2 L/mins and an appropriate filter.

5.4.2 Conical Inhalable Sampler (CIS)


Figure 5-6 SKC Button
This device (Figure 5-5) was developed in Germany. It is
Sampler
known as either the Conical Inhalable Sampler (CIS) or GSP
sampler. It requires a sampling pump operating at 3.5
L/min. This device can also be used with porous foam plugs
and specific cassettes so as to sample the respirable or
thoracic fractions.
Source: SKC - Reproduced with Permission

5.4.3 SKC Button Aerosol Sampler


This device (Figure 5-6 SKC Button Sampler) was originally
developed for the collection of inhalable bioaerosols but
has been found to closely follow the ISO sampling criteria
for inhalable dust when operated at a flow rate of 4 L/min.

5.4.4 Pre-Loaded Cassettes


The commonly used approach in the United States of
America (USA) is to use 37-mm pre-weighed PVC membrane
filter loaded into a plastic cassette (Figure 5-7) to measure
“total particulate dust not otherwise regulated”, sampled at a flow rate of 1 to 2 L/min per NIOSH

Measurement of Hazardous Substance Page 81


Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling Methods
Method 0500. Note that this approach does not correspond to ISO criteria so it should not be used
to sample for that purpose.

Figure 5-7 Pre-Loaded 37 mm Plastic


5.5 Respirable Dust Cassette

The respirable fraction of airborne dust can be


collected using any of several miniature cyclones
developed over the past 30+ years. These
cyclones separate airborne particulates into
respirable from non-respirable fractions and
allow the collection of the respirable fraction
onto a pre-weighed membrane filter, usually
mounted in a sampling cassette.

Source: University of Wollongong


Available cyclones include British Cast Iron
Research Association (BCIRA), Safety In Mines
Personal Environmental Dust Sampler (SIMPEDS),
Dorr-Oliver, and Aluminum. All operate under
the same principle (see Figure 5-8), albeit at
different flow rates. All require a steady flow rate
to select aerosol into the correct fraction (i.e.,
50% cut at 4 µm) as listed in

Figure 5-8 Mini Cyclone

Source: HSE - Reproduced with Permission

Measurement of Hazardous Substance Page 82


Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling Methods
Table 5-2 Required Flow Rates for Different Cyclone Types

Cyclone Type Required Flow Rate (L/m)

BCIRA Cyclone 2.2

SIMPEDS Cyclone 2.2

Aluminum Cyclone 2.5

10 mm Nylon Cyclone (Dorr-Oliver) 1.7

SKC Cyclone Model 225-69 3.0

5.6 Thoracic Dust


It should be noted that in practice it is unusual for there to be a need to measure airborne dust in
the thoracic size range. One exposure limit that does specify the thoracic fraction is for sulfuric
acid mist, although being a mist strictly speaking this is not a dust.

There are several different approaches to measure the thoracic fraction of airborne dust. One
device, the “Respicon” (Figure 5-9 Respicon Sampler) is a multistage impactor that traps the
various size fractions on to individual collection filters of 37 mm diameter (Figure 5-10 Schematic
of Respicon Stage Impaction). A sampling pump operating at 3.1 L/mins is required as is a 4 µm
stage 1 cut module.

Figure 5-9 Respicon Sampler Figure 5-10 Schematic of Respicon Stage


Impaction
Sour Source: TSI, Inc. - Reproduced with Permission

Source: TSI, Inc. - Reproduced with Permission

A second approach to measuring the thoracic fraction is the use of polyurethane foam filters
specifically designed to separate the individual fractions. These foam filters can be inserted into

Measurement of Hazardous Substance Page 83


Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling Methods
either the IOM or CIS
Figure 5-11 3-Piece Conductive Cassette for Fibre Sampling
sampling head (see Figure
5-10 and Figure 5-5) to act
as size selection devices,
Conductive 50 mm cowl
with the individual dust
fractions being collected on
membrane filters.

Source: University of Wollongong


A third device called the CIP
10 has been developed in
France by the French
National Institute for
Research and Safety. It is
based on the novel method 25 mm MCE Filter
of separation using annular
impaction within a rotating
housing containing a
miniature filter made of polyurethane foam. The device comes in three versions depending on the
inter-connectable selector that is installed. Both the respirable and inhalable versions operate at a
flowrate of 10 L/min, but the thoracic version operates at 7 L/min. - for details of how the CIP 10 is
used see https://airsamplingdevices.com/video-ppts/.

5.7 Fibres
Samples for airborne asbestos or synthetic mineral fibres (SMF) are usually collected on to an
open-faced membrane filter in a three-stage cassette fitted with an electrically conductive cowl.
This method uses optical microscopy to count fibres in a section of the membrane filter that is
dissolved with acetone in the lab instead of gravimetric analysis used for particulates.

Airborne fibres are collected on to mixed cellulose ester (MCE) membrane filters instead of
commonly used pre-weighed PVC filters. Membrane pore size is typically 0.8µm although 1.2µm is
used in some countries.
Figure 5-12 Metal Cowl and Sampling Head for Fiber Sampling
Source: Gully Howard Technical - Reproduced with
Permission

Measurement of Hazardous Substance Page 84


Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling Methods
MCE membrane filters are preferred for airborne Figure 5-13 Diesel Emission Particulate
fibre sampling because they can be dissolved in Filter
acetone to allow mounting of a section of the
filter onto slides that allow fibre counting by

Source: SKC, Inc. Reproduced with Permission


optical microscopy.

Figure 5-11 3-Piece Conductive Cassette for Fibre


Sampling shows a widely used filter assembly
used for airborne fibre monitoring:

Personal fiber air samples are usually collected at


1-4 L/m whereas samples collected following
asbestos removal are collected at rates of 8-15
L/m. The latter requires mains electricity so is not
suitable for personal sampling.

Figure 5-12 Metal Cowl and Sampling Head for Fiber Sampling shows original metal design for fibre
filter collection.

5.8 Diesel Particulate Emissions


Nowadays, diesel particulate emissions (DEP) exposures can be evaluated using a specialty
cassette as shown in Figure 5-13.
Figure 5-14 Sampling for Rosin
This device (Figure 5-13 Diesel Emission Particulate Based Solder Flux Fume
Filter) contains an integral precision-jeweled
impactor that screens out particles >1 µm. This is
important for workplaces where there may be other
airborne particulates such as coal mines. The DEP
sample is collected into a heat-treated quartz filter to
facilitate laboratory analysis.

The DEP cassette can be used in conjunction with a


cyclone where airborne dust levels are high enough
to potentially overload the built-in impactor.

5.9 Rosin Fume


Source: HSE - Reproduced with Permission

The UK Health & Safety Executive has developed a


unique method for sampling of rosin acids in rosin
(also known as colophony) solder flux fume (see
method MDHS 83/2).

Sampling in this case is performed by using a 13 mm


Millipore Swinnex type sampling head containing a 5
µm pore size mixed cellulose ester filter. Sample rates
of between 1 and 2 L/mins are recommended,

Measurement of Hazardous Substance Page 85


Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling Methods
depending on the fume load in the atmosphere. The sampling head is attached to the worker’s
safety glasses as indicated in Figure 5-14.

5.10 Air Sampling Pumps Figure 5-15 Dual Sampling Head Set

Typically, calibrated air sampling pumps are used


to draw air through the appropriate sample filter.
Pumps are connected to the sample filter via
short lengths of flexible tubing, often Tygon or

similar material. Most pumps are battery


operated to allow an operator to wear the
sampling train so as to collect personal breathing
zone samples. However, in some circumstances,
electrically powered pumps can be used to collect
area air samples.

Source: SKC
There are three types of air sampling pumps:
diaphragm, rotary vane and piston. Table 5-3
Comparison of Different Type of Air Sampling
Pumps compares these types of pumps.

Table 5-3 Comparison of Different Type of Air Sampling Pumps

Diaphragm Piston Rotary Vane

Power Consumption Low Medium High

Battery Size Small Medium Large

Weight Low Medium High

Repair Simple Difficult Moderate

Cost Cheap High Medium

Flow Smoothness Strongly pulsating Mildly pulsating Smooth

Pressure Drop Limits About 5 kPa None None

Valve Problems Can leak Can leak No valves

The most commonly used type of pump in industrial hygiene work is the diaphragm pump. Its
principle of operation is illustrated in Figure 5-15.

Most particulate air sampling pumps have an operating range of 0.5 to 5 L/M, although most
particulate air sampling methods call for 1 to 2.5 L/M.

There are a variety of available air sampling pumps from different manufacturers. The following
are useful features for particulate air sampling pumps:

Measurement of Hazardous Substance Page 86


Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling Methods
• Automatic flow control: Automatic flow Figure 5-16 Diaphragm Air Sampling
control ensures that flow rates remain Pump Schematic
constant over the sampling period as the
sample builds up on the filter creates
additional loading (back pressure) on the
pump. Excessive back pressure can reduce
sample air flow rates, and can also result in
early pump shut off.

Source: BOHS Reproduced with Permission


• Pulsation dampening: This is critical when
sampling using a cyclone as variations in
air flow alter the cutoff point of the
sampling device. Pulsation dampening is
needed on reciprocating pumps but is not
necessary on rotary vane pumps (see Table
5-3).

• Capacity to operate at a reasonable back


pressure: As material builds up on the
capture filter the back pressure on the sampling pump will also increase. Capacity is
related to, but slightly different from, automatic flow control. The latter concerns the
pump automatically speeding up as back pressure increases in order to keep the flow
rate constant throughout the sampled period. Capacity is about the maximum back
pressure that the pump can overcome.

• Ability to set flowrates over a reasonable flow range: Necessary as capture devices vary
in flow rate requirements.

• Good battery capacity: This allows continuous operation for the full duration of a work
shift.

• Intrinsically safe: This is a mandatory requirement for those pumps that are used in
workplaces where the risk of an explosion may be high (e.g., coal mines, oil refineries).
Figure 5-17 Soap Film Meter
• Battery charge: Some types of pump battery (e.g.,
Nickel-Cadmium) have an unusual characteristic in
that they can develop a "memory effect" if
Source: SKC - Reproduced with Permission

operated for short periods and then recharged.


Subsequently, these types of batteries may only
operate for short periods. This can be overcome by
“cycling” the battery. This entails running the pump
(can be after the sampling period) until the battery
is nearly exhausted and then recharging it. This
cycle should be repeated several times. If after this
process the battery still has a “memory effect” a
new battery should be installed. This effect is less
common with newer Nickel Metal Hydride
batteries. Modern chargers are designed to adjust

Measurement of Hazardous Substance Page 87


Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling Methods
the flow of current to the battery so that they are maintained on “trickle” charge
(instead of overcharging) so that they are ready for use. Some chargers also have a
discharge/recharge feature that makes battery cycling very simple.

• Internal flowmeters: Flow meters built into sampling pumps are generally not
considered accurate, and so should not be relied upon for calibration purposes (see
Section 5.11). However, they provide a quick visual indicator that the pump is running
(or not).

5.11 Pump Calibration

5.11.1 Basics
The accurate analysis of atmospheric dust concentrations is dependent on the determination of
the mass of dust, fume or fibre on the collection media (either gravimetrically, chemical analysis or
microscopy) and the total volume of air sampled (i.e., total number of m³ of air sampled).

The purpose of pump flow calibration is to set the sample flow rate at the specified rate, and to
verify sample flow rate at the end of the sampling period. The sample volume can be calculated
based on average flow rate (provided it remains within a range of accepted variability, usually ±
5%) and sample time (see Section 5.12).
Figure 5-18 Rotameter Figure 5-19 Electronic Flow Meter
Source: SKC- Reproduced with Permission

Source: University of Wollongong

Good occupational hygiene practice requires that a path of traceability is established and
maintained. This is via use of either a primary or secondary standard. Primary standards are
directly traceable to a national standard and are not significantly affected by variables such as
temperature and pressure. However, primary standards are often impractical for field use, so it is
common practice to use secondary standards. Examples of primary standards are:

• Soap film meters (also known as bubble burette) - See Figure 5-17 Soap Film Meter

• Wet test gas meter

Measurement of Hazardous Substance Page 88


Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling Methods
• Bell spirometer

A secondary standard references a primary standard. As such, secondary standards need to be


calibrated at regular intervals against a primary standard. In the case of rotameter use, it will be
necessary to correct for differences in atmospheric temperature and pressure between site of
rotameter calibration and site of rotameter use.

In certain countries, some electronic calibration units (e.g., BIOS Frictionless Piston) are considered
primary standards. However, third party accreditation bodies do not agree.

Examples of secondary standards commonly used in occupational hygiene monitoring are:

• Electronic meters Figure 5-20 Calibration with Bubble Flow Meter

• Rotameters

Rotameters can have two


different types of floats. With
the ball type of float the air flow

Source: University of Wollongong


reading is taken at the centre-
line of the ball. With the cone
type of float the air flow reading
is taken at the top of the float.

Figure 5-18 and Figure 5-19


show some typical secondary
standards.

5.11.2 Calibration Procedure

5.11.2.1 General Practices


When measuring or setting sampling pump airflow, the following points should be considered:

• Always calibrate a sampling pump with a sample head identical to what will be used in
the field. Figure 5-20 Calibration with Bubble Flow Meter shows a calibration set up for
vapours sampling.

• Allow the sample pump to stabilize for at least 5 minutes after it has been switched on.
Adjust the flow to the required flow rate.

• Measure the pump flow rate until three consecutive results are within ±2% of the mean.
This accuracy is easily achievable using an electronic calibrator, which is the preferred
technique. It is also achievable with a soap film meter, but it may not be

• possible using a rotameter. Use the mean value of the three consecutive results for
airflow calculation (Section 5.12).

Measurement of Hazardous Substance Page 89


Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling Methods
• Changes in environmental conditions can Figure 5-21 Calibration with Electronic
adversely affect the accuracy of a Flow Meter
calibration device.

Source: University of Wollongong


Flow rate measurements at altitudes
differing by more than 500 m from
calibration of secondary standard.

• Temperature differing by more than 15°C


from that at the previous calibration.

The following suggested calibration schedule for


sampling equipment is provided as guidance only
and reference should be made to national standards or local statutory authorities.

5.11.2.2 Suggested Calibration Intervals


Table 5-4 Calibration Intervals
[As Suggested by A Group Of Experienced Occupational Hygienists]

Item Maximum Interval Between Successive Comments


Calibrations

Pumps On use Flow check

Pumps: Direct Initially 12 months but after 3


and Indirect consecutive tests (i.e., two years) with
Automatic Flow results within ±5%, the interval can be
Control lengthened to three years

Rotameters Monthly for 3months. If results are Calibrated against a primary flowmeter
within ±3%, interval can be extended over range of use
(one-year small bore and two years large
bore)

Soap Film Meter On commissioning Check volume marks

Electronic Meters Monthly for three months then if Calibrated against a primary flowmeter
measurements are within ±3% of over range of use
expected results, the interval can be
extended to six months

Stop Watch Every 6 months Against a national time system (speaking


clock) over at least one hour (see UKAS
requirements for asbestos sampling
accreditation)

Balances 1 month One point check


(Electronic) 6 month Repeatability check
12 months Service
36 months Full range calibration by external
accredited calibration authority

Measurement of Hazardous Substance Page 90


Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling Methods
5.12 Calculation of Particulate Air Sampling Results

5.12.1 Calculation of Sample Volume

Example Sample Volume Calculation:

Let the pre-sample flow rate be 2.0 L/m


Let the post-sample flow rate be 1.9 L/m
Note this is acceptable since the difference before and after is 5%.
Then the average flow rate (FR).
2.0 + 1.9
FR =
2
FR = 1.95 L/m

Now, let's say you sampled for 7.75 hours at that average rate. That is equivalent to 7.75*
60 minutes.
Then, the volume, V litres, would be given by the following:
V = FR (L/min) ∗ Time (min)
V = 1.95 ∗ 7.75 ∗ 60
i. e. V = 906.75 litres or 0.907 m3

It's important to indicate air sample volume units (litres or m3) when submitting samples to
the lab.

5.12.2 Calculation of Particulate Mass


Most dust samples are analysed gravimetrically to establish the total amount of dust on the filter
(usually in mg). This is done by subtracting the pre-weight of the filter from the post weight of the
filter and correcting for moisture pick-up or loss via a blank correction. Thus, the weight of the
dust on the filter is:

𝑀𝑎𝑠𝑠 = 𝑃𝑜𝑠𝑡 𝑆𝑎𝑚𝑝𝑙𝑒 𝐹𝑖𝑙𝑡𝑒𝑟 𝑊𝑒𝑖𝑔ℎ𝑡 − 𝑃𝑟𝑒 𝑆𝑎𝑚𝑝𝑙𝑒 𝐹𝑖𝑙𝑡𝑒𝑟 𝑊𝑒𝑖𝑔ℎ𝑡 − 𝐵𝑙𝑎𝑛𝑘 𝐶𝑜𝑟𝑟𝑒𝑐𝑡𝑖𝑜𝑛 …Equation 5-1

Example Dust Mass Calculation:

Let the pre-sample weight of filter be 5.76 mg.


Let the post-sample weight of filter be 7.84 mg.
Let the blank correction be - 0.01 mg.
Then the corrected mass on the filter, m (in mg) is given by
𝑚 = 7.84 − 5.76 − (−0.01)

𝑚 = 2.09 𝑚𝑔

Measurement of Hazardous Substance Page 91


Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling Methods
5.13 Calculation of Air Sample Result
To calculate the air concentration of dust (usually in mg/m³), it is necessary to know the mass
collected over the sampling period (see Section 5.12.2 above), as well as the volume of air that
flowed through the filter during sample collection (see Section 5.12.1 above).

So, say that your dust sample contained 2.09 milligrams of dust, and that you sampled 0.907 m³ of
air. That is equivalent to a dust air concentration of:

𝐷𝑢𝑠𝑡 𝐶𝑜𝑛𝑐. (〖𝑚𝑔/𝑚〗^3) = (2.09 𝑚𝑔)/(0.907 𝑚^3 )

𝐷𝑢𝑠𝑡 𝐶𝑜𝑛𝑐. = 2.30 〖𝑚𝑔/𝑚〗^3 …Equation 5-2

5.14 Calculation of 8h-Time Weighted Average


The equation to calculate 8-hour time weighted average exposures is:

8ℎ 𝑇𝑊𝐴 = (𝐶_1 ∗ 𝑇_1 + 𝐶_2 ∗ 𝑇_2+ . . . . . . . 𝐶_𝑛 ∗ 𝑇_𝑛)/8 …Equation 5-3

Where C1 is the concentration for Time period T1 (in hours)


C2 is the Concentration for Time period T2 (in hours)
Cn is the Concentration for Time period Tn (in hours)

Care is advised in making sure that time values are in the same units. If time T is measured in
minutes rather than hours, the denominator becomes 8*60 i.e., 480 minutes.

Consider the following data:

Table 5-5 Data for TWA Example Calculation

Working Period Sampling Duration (h) Dust Exposure Result (mg/m3)

08:00 to 10:30 2.50 0.32

10:45 to 12:45 2.00 0.07

13:30 to 15:30 2.00 0.20

15:45 to 17:00 1.25 0.10

What is the worker's 8h-TWA dust exposure based on the above results?

Note that there is no exposure data between 10:30 to 10:45, 12:45 to 13:30 and 15:30 to
15:45, which would correspond to breaks and lunch. Assume zero exposure for these
periods.

Using the equation above, the 8h-TWA exposure would be given by the following:

8ℎ 𝑇𝑊𝐴 = ((0.32 ∗ 2.5) + (0 ∗ 0.25) + (0.07 ∗ 2) + (0 ∗ 0.75) + (0.2 ∗ 2) + (0.25 ∗ 0) + (0.1 ∗ 1.25))/8

𝑖. 𝑒 8ℎ 𝑇𝑊𝐴 = 0.18 𝑚𝑔/𝑚^3 …Equation 5-4

Measurement of Hazardous Substance Page 92


Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling Methods
5.15 Particulate Air Sampling: Direct Reading Methods
There are a number of instruments that measure airborne particulate matter in real time. Many
have data logging capabilities, Figure 5-23 Personal Dust Monitor
which allow minute by minute data

Source: Thermo Fisher Scientific- Reproduced with Permission


that can be very useful in
evaluating sources and or activities
associated with dust exposures.

Direct reading particulate air


monitors include the TSI Dust Trak,
and Thermo Scientific's Personal
Dust Monitor (PDM). There are also
other devices available such as the
RAM and MiniRAM, not discussed
in this manual. Users of any direct
reading instrument are urged to be
familiar with each instrument's use,
calibration and limitations before
use.

The TSI Dust Trak (Figure 5-22) uses laser photometry to detect light scattered by airborne dust
particles. It can be very useful for evaluating dust control procedures and for pinpointing emission
sources.

The instrument response depends on the size, shape and reflectivity of the airborne particles
rather than on particle mass. Some instruments can give a mass readout, but this is only accurate
if calibrated for the specific dust in question. Please refer to the manufacturer's instructions for
further details.

Note that environments with elevated airborne moisture (e.g., sprays, water mist, etc.), will cause
this instrument to over-respond (i.e., read higher
than true). This issue, common to most optical Figure 5-22 Dust Trak
detection-based instruments, needs to be taken
into consideration.
Source: TSI Inc. Reproduced with Permission

Thermo Fisher Scientific developed Personal Dust


Monitor (PDM) for the US coal mining industry that
uses a tapered element oscillating microbalance
(TEOM to measure dust mass. It uses an internal
heater to overcome moisture issues.

The dust lamp is an instrument that visually


highlights airborne dust particles. Its application is
explained in MDHS 82. It is based on the “Tyndall
effect”, essentially light scattered by particles
suspended in air, discovered by John Tyndall in the
mid 1800’s.

Measurement of Hazardous Substance Page 93


Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling Methods
Essentially, a bright beam of light is shone through the area where it is thought a particle cloud
may be present. The particles present diffract the incident light and an observer looking up the
beam to the source of the illumination (at an angle of about 5 – 15°) can see the dust particles.
The process is described schematically in Figure 5-24 and can be a powerful tool if linked to
photography or digital video equipment.
Figure 5-24 Principle of Dust Lamp

Source: HSE - Reproduced with


Permission
This device has been included to demonstrate how a simple beam of light can be used to
investigate possible sources of dust exposure but as with most things some level of knowledge and
skill is required to achieve good results (see MDHS 82).

5.16 Particulate Air Sampling Selection Guide


Table 5-6 provides basic guidance on the selection of the appropriate sampling head, capture
mechanism and flow rate for a range of contaminants. It is based on the experience of the authors
and may not reflect local statutory requirements.

Table 5-6 Summary of Air Sampling Guide

Collection Flowrate
Contaminant Sampling Head Comments
Medium (L/min)
0.8 µm pore size
Asbestos and MCE
Open face with 1–4 Requires conductive cowl (3-piece
synthetic mineral membrane
conductive cowl (8 – 16 in UK) cassette).
fibres filter
See Section 0
5.0 µm pore size
Respirable dust Miniature
PVC 1.7 – 3.0 Depends on type of cyclone used
(including silica) cyclone
See Section 0
5.0 µm pore size
PVC or
IOM (or Filter can be subsequently
Inhalable dust glass fibre 2
equivalent) analysed for metals, etc.)
filter
See Section 5.4
Welding + other IOM (or
PVC 2 0.8 µm pore size
metal fumes equivalent)
5.0 µm pore size
MCE
Rosin solder flux Millipore, Flow rate depends on fume load
membrane 1-2
fume Swinnex in atmosphere.
filter
See Section 5.9
PVC= Polyvinyl Chloride MCE= Mixed Cellulose Ester

Measurement of Hazardous Substance Page 94


Chapter 5 Dusts, Fumes and Mists: Health Effects and Sampling Methods
Chapter 6 Gases and Vapours

This section describes and discusses general methods and procedures to evaluate airborne
concentrations of gases and vapours. This section addresses:
✓ What are gases and vapours?

✓ Basics of Air Sampling for Gases and Vapours

✓ Active Sampling Methods

✓ Sorbent Tubes

✓ Liquid Sample Media

✓ Passive Diffusion Monitors

✓ Example Calculations

✓ Direct Reading Instruments

Review of relevant air sampling documents should be part of sample planning to get key
information such as sample flow rates, sample collection media, limits of detection. Documents to
consider would be NIOSH's Manual of Analytical Methods (NMAM) and the HSE's Methods for the
Determination of Hazardous Substances (MDHS). In some jurisdictions, relevant regulations
provide specific sampling details (e.g., OSHA certain substance-specific rules such as for asbestos,
benzene, cadmium, lead.). Agencies such as UK's Health and Safety Lab and commercial labs are
also useful resources as are some occupational hygiene equipment suppliers such as Casella, MSA,
SKC etc.

6.1 What Are Gases and Vapours?


Gases are formless fluids that expand to occupy the space of any enclosure they happen to be in.
They are neither solid nor liquids. Examples of gases of occupational hygiene interest are
ammonia, carbon monoxide, chlorine and nitrogen oxides.

Vapours are the gaseous phase of a liquid at room temperature. They result from evapoursation of
molecules from the surface of a liquid into the gaseous phase. Examples of occupational hygiene
interest are solvents such as acetone, benzene, gasoline, as well as mercury in its elemental form.

You may hear the term fume in connection to solvents, paints etc. Technically, fume applies to
finely divided particulates associated with hot processes (e.g., welding), so it is incorrect to talk
about solvent fumes when you mean solvent vapours.

Some vapours are associated with certain solids. Here, molecules are going from solid to vapours
phase in a process known as sublimation. One common example is dry ice (solid carbon dioxide).
Other examples are arsenic, iodine, naphthalene (moth balls).

Measurement of Hazardous Substance Page 95


Chapter 6 Gases and Vapours
6.2 Fundamentals of Air Sampling for Gases and Vapours
There are four general methods for sampling gases and vapours in air

• Active Sampling

• Passive Sampling

• Grab Sampling

• Direct Reading Instruments

The first two approaches involve lab analysis. In the case of grab sampling, a volume of air is
collected into a container (e.g., an evacuated flask, or a Tedlar bag) which is then sent to a
laboratory for analysis for specified substances (see Figure 6-1 Sampling Train for Sorbent Tube. In
the case of active sampling, air is drawn through a sorbent tube that absorbs the gas or vapours of
interest (see Sections 6.3 and 6.4). The sorbent tube is submitted to the lab for analysis after the
sampling period. Active air sampling is the most commonly used approach in occupational hygiene
for solvent vapours.

The third method, passive sampling, is a method whereby vapours of interest are allowed to
diffuse into a sorbent material usually in a badge-type assembly, usually worn on the lapel. After a
specified period of exposure, the badge is sealed, packaged and shipped to a lab for analysis.
Further details on this method may be found in Section 6.9.

The fourth method, which involves the use direct reading instruments, is further discussed in
Section 6.12.

6.3 Active Air Sampling: Basics


Active air sampling uses a sampling train, similar to particulate air sampling (see Section 5.3),
except that air is drawn at a much lower rate (typically 0.050 to 0.200 L/m instead of 1 - 4 L/m)
through an adsorbent tube (e.g., charcoal) instead of a filter. After lab analysis to determine the
mass of contaminant collected in the sorbent tube, one can calculate air concentration based on
Figure 6-1 Sampling Train for Sorbent Tube the volume of air that passed through the
sorbent.

Figure 6-1 and Figure 6-2 shows a typical


Source: SKC - Reproduced with Permission

active air sampling train used with a


sorbent tube.

Air sampling pumps used for sorbent tube


sampling are usually referred to as low flow
pumps. Some air sampling pumps used for
particulate air sampling may be converted
for low flow use through the use of
manufacturer supplied accessories (e.g.,
adjustable low flow holder shown in Figure
6-2 Air Sampling Train for Sorbent Tube). As

Measurement of Hazardous Substance Page 96


Chapter 6 Gases and Vapours
with particulate air sampling, these pumps would be attached to a worker's belt, with the sorbent
tube located in the breathing zone. There are also available specialty low flow air sampling pumps
that are much smaller and lighter, and are thus less burdensome for a worker to wear. The smaller
pumps can be worn in a pocket rather than on a belt (see Figure 6-2).

In organic vapours sampling, total volume of air collected is most important rather than low
pulsation flow; hence, some low flow pumps do not have as sophisticated flow control systems as
dust sampling pumps.

As with particulate air sampling, the sampling flow rate needs to be set to the rate specified in the
sampling method. In other words, the air sampling pump needs to be calibrated (with the sorbent
tube in place), just as with dust air sampling before use, and verified after use. If the final (i.e., post
sampling) flowrate differs from the initial flowrate by greater than ±5% (UK and US), the sample
should be discarded and sampling repeated if possible. Australian Standards (AS) allow a greater
variability (±10%) in flow rate before and after sampling. However, this is considered too high by
many occupational hygienists. A variability of ±5%
Figure 6-2 Air Sampling Train for
represents best practice.
Sorbent Tube
Keep in mind that adsorbent tubes need to be
sealed after use, and that there are limits to how

Source: 3M Australia - Reproduced with Permission


long the sample can be kept before is analysed. Sorbent
This is usually specified in the sampling method. If Tube
you are collecting samples over several days, it is a Holder
good idea to keep samples in a refrigerator. In
addition, it should be noted that some samples
may need to be refrigerated immediately after
sample collection and shipped cold, such as by
using dry ice or freezer packs. Low Flow
Air Sampling
6.4 Sorbent Tubes Pump

The use of sorbent tubes is based on the concept


of adsorption whereby the gas or vapours of
interest is collected by passing it over the surface of solid sorbent media such as activated
charcoal, silica gel, porous polymers and molecular sieves, on to which the contaminant of interest
is adsorbed. Section 6.4.1 describes different types of sorbent media. Collection efficiencies are
affected by factors such as temperature, humidity, sampling rate, other contaminants and
breakthrough (see Section 6.4.2).

6.4.1 General
The adsorbent material is usually packed in a sealed glass tube as shown in Figure 6-3 Sorbent
Tube. Before sampling, both ends of the glass tube need to be carefully broken off and the tube
connected into the sampling train, usually via a sample tube holder. The printed arrow on the
sampling tube shows the direction of the airflow. Insert the tube so arrow points towards the
pump. If there is no arrow on the tube, insert the tube with the smallest sorbent section (referred
to as the back-up section) into the tube holder so air flows through the main (largest) bed first.

Measurement of Hazardous Substance Page 97


Chapter 6 Gases and Vapours
At the end of the sampling period, after verifying flow rates (see Figure 6-3 Sorbent Tube), seal the
ends of the tubes using the plastic caps that are provided with the sample tube. Be careful of
sharp edges, and of using too much pressure to avoid shattering the tube and injuring yourself.
After labeling the tube(s), it (they) needs to be sent to the lab for the required analysis. If you are
batching samples over several days, it is good practice to store them under refrigeration. Please
check the sample methods for maximum hold times (i.e., how long one can keep samples before
analysis after which they become void).

Sample analysis involves separate desorption of each section of sorbent tube (i.e., front and back
sections). This is commonly done using either solvents (e.g., carbon disulphide) or thermal
methods in the lab.
Figure 6-3 Sorbent Tube

Source: SKC Inc – Reproduced with permission


Direction of sample flow

Main sorbent bed

Back up sorbent bed

Foam separator

6.4.2 Sorbent Tubes: Breakthrough


Breakthrough occurs when the sorbent is saturated and can adsorb no further contaminant from
the air sampled, and can thus underestimate actual exposures. Figure 6-4 Illustration of
Breakthrough Concept illustrates the concept using a sponge model. When a dry sponge is put in a
water stream, it initially absorbs
Figure 6-4 Illustration of Breakthrough Concept
water without letting it through.
Once it becomes saturated, water
passes through.
Source: SKC, Inc.: Reproduced with permission

Breakthrough can occur for any of


the following reasons:

• Sample rate is too high,


reducing contact time with
sorbent material

• Large sample volumes

• Sample media has reduced


affinity for sorbent medium

Measurement of Hazardous Substance Page 98


Chapter 6 Gases and Vapours
• Allowing too long between sample collection and sample analysis

To address breakthrough, and avoid underestimating, sorbent tubes contain two layers, front and
back. Each layer is analysed separately. NIOSH air sampling methods define breakthrough as
having occurred when the back layer contains 20% or more of the quantity of the contaminant(s)
collected in the front layer. UK Guidelines (MDHS para 69) define breakthrough as occurring when
the back layer contains 10% of the front layer. Where breakthrough is noted, the process or
activity should be re-evaluated after reducing sample volumes (e.g., reduced sample flow rates, or
multiple samples over shorter periods).

6.4.3 Sorbent Tubes: Common Varieties


There are a variety of sorbent tubes used in occupational hygiene air sample collection. The most
commonly used are charcoal and silica gel tubes.

Table 6-1 Sorbent Tubes Types

Type Use Issues Comments

Charcoal Best for non-polar organic Can't use for polar Coconut shell, crushed and
vapours (e.g., substances. conditioned at high
hydrocarbons, ketones, temperature and low O2.
Poor recovery for reactive
esters, ethers).
compounds such as Carbon disulphide (CS2)
Also chlorinated solvents. aldehydes, amines, commonly used to desorb.
phenols, low molecular
Thermal desorption with
weight alcohols.
specialty tubes.

Silica Gel Acid gases, polar Water and methanol


substances (e.g., commonly used to desorb.
glutaraldehyde, amines)

There are also specialty sorbent tubes such Figure 6-5 Multi-Tube Sample Tube Holder
as:

• Chromosorb and XAD-2: Used for


certain pesticides
Source: SKC Inc., Reproduced with Permission

• Florisil: PCBs (Polychlorinated


biphenyls)

• Polyurethane foams (PUF):


Pesticides and polynucleated
hydrocarbons

• Thermal Desorption (TD) (see Figure


6-6 Thermal Desorption Tubes)
Typically used in conjunction with
an automated GC analysis
instrument that can be set up to run a large batch of samples overnight

Measurement of Hazardous Substance Page 99


Chapter 6 Gases and Vapours
Sorbent tube selection should be made in accordance with the corresponding air sampling method
such as those from NIOSH, OSHA, HSE or local standards organisations and industry guides such as
the SKC website – see https://www.skcinc.com/catalog/index.php for the contaminant of interest.

Sometimes an occupational hygienist may want to measure exposure to a variety of airborne


vapours that require the use of different sorbent tubes. This can be done using a multi-tube
holder, such as the triple tube holder seen in the photo here. This enables the personal sampling
to be carried out using a single sampling pump on each employee, rather than requiring the use of
multiple sampling pumps. It is important that the flow rate through each of the tubes is calibrated
before and after use with all of the sampling tubes in position.

6.4.4 Sorbent Tubes: Collection Efficiency


While adsorption of a contaminant from the atmosphere on to a tube of some specific type is a
very effective way of collecting the contaminant, difficulties arise during the laboratory analysis in
the recovery of that analyte from the tube.

Basically, the problem is that it is not possible to extract 100% of a given contaminant from a
sorbent tube. If not accounted for, it will lead to errors in the calculation of an exposure. To
overcome this, the lab establishes a “desorption efficiency” for each batch of samples. The general
approach is to load (i.e., spike) sample tubes from a batch with varying amounts of the
contaminant of interest and to then analyse them as normal. In other words, the idea is to
compare mass detected via analysis against the mass added. The percentage recovered (e.g., 80%
or 0.8) is deemed the desorption efficiency for that particular batch of tubes, and for that
particular contaminant.

It is important that the laboratory understand the reasons for this process and be familiar with the
appropriate methods to establish such values. Some tube manufacturers publish a list of typical
desorption efficiencies for common contaminants as a guide for the laboratory.

6.4.5 Sorbent Tube: Desorption Efficiency


Factors that can affect the collection efficiency of adsorption tubes include:

• Temperature – adsorption, an exothermic process decreases with temperatures.

• Humidity – charcoal's great affinity for water vapours reduces its collection of other
contaminants.

• Sampling flow rate - if sampling pump flow rates are too high, contaminant residence
times may be too short to be adsorbed resulting in collection losses.

• Channeling – Improper packing of sorbent can create channels or gaps in the bed
through which the gases can flow more easily and thus not be adsorbed on to the
sorbent.

• Overloading of sorbent tubes can occur if concentrations/sampling times are too long or
by the presence of other contaminants including water vapours.

Measurement of Hazardous Substance Page 100


Chapter 6 Gases and Vapours
The manufacturers’ information and standard sampling methods e.g., NIOSH, OSHA, HSE, ISO
Standards Australia etc. should be referred to for specific details pertaining to the sampling for the
particular contaminant.

6.4.6 Sorbent Tubes: Thermal Desorption


The use of solvents such as carbon disulphide [CS2] to extract volatile organic compounds (VOCs)
from charcoal tubes was developed in the 1970s. This approach has the following limitations:

• Potential low desorption efficiencies, meaning not all the contaminant is extracted.
Typical desorption efficiencies are in 80% range, less under high humidity conditions or
when sampling for substances with marked polar characteristics.

• Lower reproducibility when desorption efficiencies are low.

• Solvent impurities may mask contaminant of interest.

• Difficult to reliably measure substances with similar physical properties as extraction


solvent.

• About 0.1% of the solvent extract is actually analysed, thus resulting in a dilution factor
of 1,000, raising limit of detection.

• Detection limits in the range of 0.1 ppm.

• Work with CS2 in the lab requires appropriate measures to minimize its hazards.

Thermal desorption (i.e., the use of heat to drive off contaminants adsorbed onto the solid sample
media) addresses these limitations and offers the following advantages:

• Much higher desorption efficiencies (in 95% range).

• Analysis of entire sample instead of an aliquot.

• Analysis based on mass spectrometry.

• No solvent related effects.

• Detection limits that are 103 to 104 times better than solvent extraction, making it
possible to detect contaminants in parts per billion (ppb) or parts per trillion (ppt) range.

For these reasons, some vapours and gas sample methods that require solvent extraction have
been superseded by thermal desorption methods in Europe.

However, thermal desorption sample collection requires specialty sampling tubes. The “industry
standard” is ¼ inch (6.4 mm) OD x 3½ inch (88.9 mm) long stainless-steel sorbent tube pre-packed
with the sorbent of choice, most commonly Tenax. In addition, a ¼ inch brass SwageLok type
storage cap (fitted with a PTFE ferrule) for the non-sampling end of the tube, and a diffusion cap at
the end of the tube is normal practice as shown in Figure 6-8.

Measurement of Hazardous Substance Page 101


Chapter 6 Gases and Vapours
A suitable sorbent must be selected for the compound or mixture to be sampled. If more than one
sorbent is required (due to the different volatilities of the compounds in question), two or more
samplers packed with different sorbents should be exposed simultaneously.

In contrast with the glass sorbent tubes described in Section 6.4.3, the stainless-steel thermal
desorption tubes can be reused many times. It is therefore essential that the stainless-steel
thermal desorption tubes are always pre-conditioned before they are used for sample collection
to ensure that there is no contaminant on them, by the laboratory putting the tubes through a
pre-set heating sequence. Once sampling or analysis is completed, tubes should be recapped with
the brass storage caps as soon as possible and returned to a clean environment for storage.

An additional point to note is that each thermal desorption tube can only be analysed once. In
contrast, it may be feasible to re-analyse a glass sorbent tube sample if some of the liquid
desorption solution has been retained by the lab.

Specific details including the general handling of thermal desorption tubes, sorbent selection, tube
conditioning, post sampling short- and long-term storage should be obtained from the
manufacturer before use.

6.5 Filters
Some mists and vapours require samples to be collected on to specialty filters. For example,
certain pesticide and isocyanate air sampling methods require the use of glass fiber filters.

For some contaminants it may be necessary to use a filter impregnated with a stabilizing agent or
a backing pad treated with a collection media where the contaminant may be present in the
gaseous form or in both the
Figure 6-6 Thermal Desorption Tubes particulate and gaseous form.

An example of this is:


Source: Markes International Ltd – Reproduced with

• Fluoride - PTFE (Teflon)


membrane filter with sodium
carbonate treated cellulose
backing pad

6.6 Mixed Phase Exposures


In certain circumstances, an air
contaminant of interest may be
permission

present in more than one phase.


For example, mists may also be
associated with related
component vapours, or certain solids may have appreciable vapours pressures. In such cases, it is
important to sample both phases of the contaminant of interest to avoid under estimation of
exposures.

The following examples illustrate approaches issues for mixed phase sampling:

Measurement of Hazardous Substance Page 102


Chapter 6 Gases and Vapours
Example 1: Coke Ovens

The “traditional method” for sampling and measurement for coke oven emissions was to collect
samples onto membrane filters that were extracted with benzene to report results as the
“Benzene Soluble Fraction of the Total Particulate Matter”. However, polyaromatic hydrocarbons
emitted from coke ovens are present in both particulate and vapours phases and hence sampling
for just the particulate phase underestimates coke oven emission measurements. Modern
sampling trains for coke oven emissions include a sorbent layer behind the particulate membrane
filter to collect the vapours phase that passes through the membrane filter.

Example 2: Impingers

Practical difficulties associated with the use of impingers (see Section 9.5) have led to the
development of impregnated filters for contaminants such as isocyanates, formaldehyde and
glutaraldehyde.

In the case of the spraying of “two pack” isocyanate-based paints, isocyanates may be present
both as mist and as a vapour. In order to ensure that both phases of the isocyanate exposure are
collected a sampling train comprising of an impinger followed by an impregnated filter can be
used – for details see MDHS 25/4 published by the UK Health and Safety Executive
http://www.hse.gov.uk/pubns/mdhs/pdfs/mdhs25-4.pdf.

Example 3: Fluorides

Fluorides are commonly found contaminant in aluminum smelters. They may exist as particulates,
as a hydrofluoric acid (HF) mist or as hydrofluoric acid gas. They need to be sampled as described
in HSE MDHS 35/2. This method entails a Teflon filter mounted on a sodium carbonate
impregnated paper pad mounted in an inhalable sampler. The Teflon filter removes the particulate
fluorides, whilst the sodium carbonate impregnated pad collects the hydrogen fluoride.
Hydrofluoric acid mist is not retained on the Teflon filter and is collected on the sodium carbonate
impregnated pad.

6.7 Liquid Sample Media


Absorption (or solvation) is the technique whereby the gas or vapours is collected by dissolution
into a liquid contained in either an impinger, midget impinger (see Figure 6-7 Midget Impingers),
fritted bubbler or gas wash bottle. Some liquid sample collection methods are based on a chemical
reaction between contaminant and sample collection liquid (e.g., derivatization, oxidation,
neutralization). Many of these methods were early occupational hygiene developments and have
been superseded by methods that involve specially treated or impregnated filters.

Measurement of Hazardous Substance Page 103


Chapter 6 Gases and Vapours
Collection Figure 6-8 Typical Passive Samplers
efficiencies for liquid
sample collection
rely on surface area

Source: 3M Australia – Reproduced with permission


produced during
sampling (i.e., the
size and number of
bubbles), liquid
volume, sampling
flow rate and
reaction rate.
Sometimes bubblers
may be connected in
series to increase
efficiencies and to
collect any liquid
carryover.

The use liquid sample collection media requires careful handling to avoid spills, or introducing
liquid into the pump, and loss of sample volume through evapoursation. The need to keep sample
collection devices upright to avoid spills and the fragility of equipment limits practical use of this
methodology for personal sampling. There are alternative methods that do not involve liquid
sample collection media for many substances (e.g., isocyanates). These alternate methods
typically involve specially treated or impregnated filters, so the sampling is essentially a variation
of particulate air sampling.

6.8 Air Sampling: Diffusion Methods


Figure 6-7 Midget Impingers
Passive or diffusion sampling is the passive
collection of airborne gases and vapours on to
sorbent beds, usually mounted badges or tubes
(see Figure 6-8). They are light, simple and easy to
use and do not require the use of sampling
pumps, tubing, and batteries or air flow
calibration. They can be simply clipped on to the
Source: University of Wollongong

collar of the worker (see Figure 6-9) for personal


sampling (TWA or STEL) or can be used for area
monitoring as long as there is sufficient airflow at
the location sampled. The sampling process
generally consists of exposing the badge for a
known period of time, and then re-sealing the
badge for subsequent lab analysis.

Measurement of Hazardous Substance Page 104


Chapter 6 Gases and Vapours
Air sample collection rates are based on principles of gaseous diffusion across a permeable
membrane (Australian Standard AS 2986), based on Fick's Law. Fick’s first law of diffusion can be
applied to the mass uptake rate:

𝑚/𝑡 = (𝐴 ∗ 𝐷)/𝐿 ∗ (𝐶 − 𝐶_0) …Equation 6-1


Where

m mass of adsorbate collected in grams

t sampling time in seconds (s)

A cross sectional area of the diffusion path in cm².

D diffusion coefficient for the adsorbate in air in cm²/s– available from manufacturer
of the sampler for a given chemical

L length of the diffusion path in cm (from porous membrane to sampler)

C concentration of contaminant in ambient air in g/cm³.

C0 concentration of contaminant just above the adsorbent surface in g/cm³.

From Equation 6-1 above, if Co is zero (i.e., the collection medium is effective), then mass transfer
or collection rate is proportional to the ambient concentration C.

Sample rates using passive samplers depend on the diffusion coefficient of the contaminant and
the geometry of the monitor. Some monitors such as 3M, SKC monitors and Dräger ORSA monitors
have a diffusion path axial to the sorbent whereas others such as the Radiello badge have a
diffusion path to that is radial to the sorbent surface.

Sample rates remain constant as long as the sorbent media does not reach its capacity (i.e., does
not become saturated) and as long as adequate airflow is maintained across the face of the
monitor. These rates are available from monitor manufacturers.

Organic vapours diffusion monitors typically contain Figure 6-9 3M Diffusion Monitor
activated charcoal so that volatile contaminants
Source: 3M Australia – Reproduced with permission

that can be sampled with a charcoal tube-based


sampling train can instead be sampled with a
diffusion monitor.

Activated charcoal and other sorbents can be


impregnated with certain substances to allow
sampling for materials that might otherwise have
poor capture, retention and recovery from the
sorbent. For example, a solid sorbent can be treated
with 2-(hydroxymethyl) piperidine to collect
formaldehyde, or activated charcoal can be treated
with a bromine compound to collect ethylene oxide.

Measurement of Hazardous Substance Page 105


Chapter 6 Gases and Vapours
There are also diffusion monitors for inorganic mercury and for amines.

Diffusion monitors meet or exceed an accuracy of ± 25% at 95% confidence for many workplace
contaminants. Diffusion monitors can also be used for area monitoring provided there is sufficient
airflow, defined as at least 25 ft/min or 0.13 m/sec in any orientation. Care needs to be taken not
to place diffusion area monitors away from corners and or other dead air spaces.

Although passive badges offer a number of advantages (e.g., ease of use and relatively
inexpensive), some of their disadvantages are as follows:

• Cannot sample low vapours pressure organics such as glutaraldehyde, or reactive


compounds such as phenols and aldehydes.

• Charcoal based diffusion monitors have the same moisture and recovery issues
associated with the use of active sampling tubes.

• With some diffusive samplers inaccuracies can occur at wind speeds >2.5 m/s,
depending on their design.

• “Sampling rates” are supplied by the manufacturer and differ for each compound.

• It can be difficult to know if breakthrough (see Section 6.4.2) has occurred, especially for
the more volatile compounds such as methylene chloride, as some diffusion monitors do
not have a back-up section.

6.9 Grab Sampling Basics


This method collects air into either a rigid evacuated container or canister, or into a flexible bag.
The latter requires an air sampling pump to draw into the bag. This approach is also sometimes
referred to as "whole air sampling" or "grab sampling". In both cases, the container/bag has to be
analysed in a lab within a specified time after use (referred to sometimes as hold times).

Contaminant recovery during analysis depends on relative humidity, reactivity of contaminants of


interest and inertness of the container, which need to be considered before sample collection to
minimize sample losses due to interaction of the contaminant with the container. As a general
rule, grab sampling should be used for chemically stable target compounds that have vapours
pressures greater than 0.1 torr (or 0.1 mm Hg) at NTP (i.e., 760 mm Hg atmospheric pressure and
25°C).

Grab sampling is often used for sampling unknowns, for evaluating contaminant sources, where
the air contaminant concentration is known to be constant, or where peak concentrations are of
interest.

Sampling periods are short and generally last from a few seconds to a few minutes. However, in
the case of an evacuated container, it is possible to install specific flow controllers to regulate air
flow into the container over known periods of time.

Note that grab sampling is generally not a suitable method for personal air sampling.

Measurement of Hazardous Substance Page 106


Chapter 6 Gases and Vapours
6.9.1 Canisters
Grab sampling canisters are typically made from stainless steel and are usually spherical or
cylindrical. Their use does not require a sampling pump. Canisters range in size from 1 to 10 L.

SUMMA canisters have internal surfaces specially treated using a process (also known as summa
process) that combines electro polishing with chemical deactivation to produce nearly chemically
inert interior surfaces to maximize recoveries of air contaminants from the container in the lab.

Canisters are generally furnished from the lab that will analyse the sample(s) where they are
cleaned before use. It's important to review desired limits of detection with the lab to ensure that
canisters that have been suitably cleaned are provided.

Canisters are provided under vacuum, so sample collection involves simply opening the valve to fill
the container. This takes from a few seconds to a few minutes (depending on container size),
unless flow controllers (usually supplied by the lab) are used to sample over a longer specified
time (e.g., 1- 8 hours).

Grab sampling using canisters can yield limits of detections that are in the ppb (or µg/m³) range.
When used to sample for unknowns, the contents are analysed by gas chromatography/mass
spectrometry (GC/MS). While it can yield useful information, SUMMA canister sampling can be
expensive.

6.9.2 Grab Sampling Bags


Gas sampling bags are made of Figure 6-10 Use of Air Sampling Pump to Fill Grab Bag
different materials such as
polyester, polyvinylene chloride,
Teflon (polytetrafluoroethylene

Source: SKC-Reproduced with Permission


or PTFE), and Tedlar (polyvinyl
fluoride). They are often
laminated with aluminum to
reduce contaminant permeation
through the walls. Sample loss
and adsorption on to the bag
material can be significant
concerns so samples should be
analysed as soon as possible after
collection.

Grab sampling bags are relatively inexpensive, can be carried to site in a brief case, filled in
seconds and shipped easily to the laboratory for analysis. See Figure 6-10, although they come in
different sizes (up to 250 L), bags used for occupational hygiene sampling purposes bags are
typically between 5 and 15 litres. Pump flow rates of 1 L/min are typically used to fill these bags.
Keep in mind that overfilling gas bags in low temperatures can create leakage and or damage
when moving bags to warmer temperatures, and that insufficient filling at warmer temperatures
can reduce sample volumes if analysed in lower temperatures.

Measurement of Hazardous Substance Page 107


Chapter 6 Gases and Vapours
6.9.3 Colorimetric Tubes
Colorimetric tubes can also be used to collect grab (short-term) samples although technically they
provide a direct result rather than a sample for lab analysis. See Section 6.13 for more details.

6.10 Sample Analysis


Samples for gases, vapours and mists are analysed in a variety of ways discussed in Chapter 7.
Organic vapours samples are most commonly based on chromatography (see Section 7.2.2).

6.11 Example Calculations of Results


Calculation of results requires calculating volume of air sampled (i.e., how much air flowed
through the sampling media) and later calculating the concentration of air contaminant of
interest.

6.11.1 Air Volume Calculation


This requires calculating the average air flow rate based on pre- and post-sampling flow rates,
which is then multiplied by the sample duration. Consider the following sampling data shown in
Table 6-2 Sampling Flow Rates:

Table 6-2 Sampling Flow Rates

Start End

Flow Rate (L/m) 1.00 0.96 0.98 Average flow (L/m)

Sample Time 0730 1500 420 Sample period (min)

Thus, the volume of air sampled (V, in litres) would be as follows:

𝑉 = 0.98 𝐿/𝑚𝑖𝑛 ∗ 420𝑚𝑖𝑛 …Equation 6-2


𝑉 = 411.6 Litres or 0.412 m³ (since 1 m³ = 1000 litres)

Note that post sampling flow rate was within 5% of initial flow rate, and so is acceptable.

Now, say that the lab reports a total 6.3 mg of toluene in the sample represented by the above air
sampling data. The lab report also shows that there were 5.6 mg in the front section and 0.7 mg in
the back section, and that desorption efficiency was 90%.

Since only 90% of toluene was recovered from the charcoal tube, the corrected amount collected
in the tube would be 6.3/(90%) or 7 mg.

Therefore, the air sample concentration would be (7 mg)/(0.412 m³ ) or 17.0 mg/m³.

This is equivalent to 17.0/24.45 ∗ 92.14 or 1.45 parts per million (ppm) by volume where 24.45
represents the molar volume of gas at NTP, and 92.14 is toluene's molecular weight.

Measurement of Hazardous Substance Page 108


Chapter 6 Gases and Vapours
The ratio of back results to front results is 0.7/5.6, or 12.5%. This is less than 20%, so sample
breakthrough did not occur.

Note that labs will usually report air concentrations in either in mg/m³ or ppm, provided sample
volumes were submitted with samples.

6.11.1.1 Diffusion Sampling Calculations


Sampling period duration, the contaminant weight determined by the laboratory, the recovery
coefficient and the calculation constant either A or B are required to calculate air concentrations
when using diffusion samplers. A constant “A” is used to calculate results in milligrams per cubic
metre (mg/ m³) whereas a constant “B” is used to calculate results in parts per million (ppm).
These constants, which are specific to each brand of monitor and specific for each contaminant,
are supplied by the diffusion monitor manufacturer.

Air temperatures influence diffusion monitor sampling rates, as exemplified in Table 6-3 3M
Diffusion Monitor Temperature Correction Factors. Atmospheric pressure variations do not
require correction factors.

Table 6-3 3M Diffusion Monitor Temperature Correction Factors

Source: 3M – Reproduced
Celsius (oC) -8 -3 2 7 13 19 25 31 37 44

with permission
Fahrenheit (oF) 18 27 36 45 55 66 77 88 99 111

Correction Factor 1.06 1.05 1.04 1.03 1.02 1.01 1 0.99 0.98 0.97

Note that for temperatures between 13°C and 37 °C (i.e., 55°F and 99 °F), correction factors are
quite small (2%).

6.11.1.2 Diffusion Monitor Calculation Example


The time weighted average (TWA) concentration of contaminant in mg/m3 can be

𝐶 = (W (µg) ∗ A)/(𝑟 ∗ 𝑡 (𝑚𝑖𝑛𝑢𝑡𝑒𝑠) ) …Equation 6-3

Where W = weight of contaminant in sample, based on lab analysis.

A = a manufacturer supplied constant for a specific contaminant for calculating


results in mg/m³.

r = the recovery coefficient as reported by the lab.

t = time that the diffusion monitor was exposed.

The TWA concentration of contaminant in ppm can be calculated from the following expression:

𝐶 = (W (µg) ∗ B)/(𝑟 ∗ 𝑡 (𝑚𝑖𝑛𝑢𝑡𝑒𝑠) ) …Equation 6-4

Measurement of Hazardous Substance Page 109


Chapter 6 Gases and Vapours
Where W = weight of contaminant in sample, based on lab analysis.

B = a manufacturer supplied constant for a specific contaminant calculating results


in ppm.

r = the recovery coefficient as reported by the lab.

t = time that the diffusion monitor was exposed.

Consider the following data for benzene sampled with a diffusion monitor:

Table 6-4 Diffusion Monitor Data

Sampling time 420 minutes

Temperature 75 °F

Calculation Constant A 28.2

Calculation Constant B 8.82

Contaminant weight in monitor (W) 27.2 µg

Recovery coefficient (r) 0.97

The corresponding air concentration C (in mg/m3) would be derived using the first equation above,
using A:

So, 𝐶 = (27.2 ∗ 28.2)/(0.97 ∗ 420) or 1.88 mg/m3 …Equation 6-5

Similarly, the concentration of benzene in ppm can be derived from application of Equation 3-1
(Chapter 3).

So, 𝐶 = (27.2 ∗ 8.82)/(0.97 ∗ 420) or 0.59 ppm …Equation 6-6

Note that no temperature correction was required for the sample since it was collected at 75 °F.

Note also that labs will usually provide results in terms of either in mg/m³ or ppm, so it's not
common to have to calculate air sample concentrations from lab data.

6.12 Direct Reading Instruments: General


Early direct reading instruments were bulky and impractical for personal monitoring. They were
generally used for area (i.e., static) monitoring. However, these instruments have evolved over the
years so that there are now available a variety of sophisticated battery powered direct reading
instruments, many with real-time data logging capabilities, suitable for personal air sampling.
Continued technology evolution has allowed the deployment of remote sensing devices linked via
telemetry to a central location. While these features can indeed be very useful, it also means it is

Measurement of Hazardous Substance Page 110


Chapter 6 Gases and Vapours
more critical than ever before to be familiar with manufacturer's instructions to obtain best
results, and minimize time lost through operator error.

The biggest advantage of direct reading instruments is obtaining real time data that can be
compared to relevant exposure criteria. The advent of data logging technology now allows analysis
of instantaneous (seconds), short term 15-minute STEL concentrations and 8-hour TWA
concentrations for certain contaminants.

Although many direct reading devices are intended to measure specific contaminants (e.g., carbon
monoxide or hydrogen sulphide), some can monitor simultaneously multiple gases and vapours
(e.g., confined space entry monitors). Others (e.g., flame ionization detectors [FIDs] and photo
ionization detectors [PIDs]) are not able to differentiate between the different gases and vapours
that may be present and instead report a "composite" single result that may require careful
interpretation.

Direct reading instruments are useful for the following activities:

• To obtain real time data (employee concerns, leaks, emergency response, confined
space entry).

• To develop and or prioritize air sampling programmes.

• To evaluate effectiveness of controls in real time.

• To evaluate intraday variability in exposures.

• To obtain information about peaks in exposure levels that traditional air sampling is
unable to measure.

• For stationary installations to record area exposure levels and as well as to sound an
alarm should concentrations of concern be detected.

• For respirator fit testing.

Table 6-5 lists some commonly used direct reading instruments. Some will be discussed during the
practical session.

Measurement of Hazardous Substance Page 111


Chapter 6 Gases and Vapours
6.12.1 Direct Reading Instrument Limitations
Although direct reading instruments offer many advantages as stated above, they have some
limitations that need to be considered:

• Often costly to purchase though they may be available for rent in some countries.

• Need for regular calibration and associated records.

• Sensors are generally substance specific, have a finite life and may have limited range.
May not always be user replaceable.

• Cross sensitivity (see Section 6.12.2).

• Need for intrinsically safe instruments in situations where it is possible for a potentially
flammable atmosphere to be present.

6.12.2 Direct Reading Instrument Cross Sensitivity


Cross sensitivity means that an instrument sensor can give an erroneous reading from the
presence of an air contaminant it was not designed to measure.

Consider a carbon monoxide electrochemical sensor, often found as a feature of confined space
entry monitors. These sensors are responsive to gases other than carbon monoxide, and can give
either false positive results or false negative results that manufacturers address by using a sensor
filter. The following data from one particular supplier illustrates results obtained when applying
100 ppm of the listed gas to the CO sensor:

Table 6-5 Direct Reading Instrument Cross Sensitivity

CO read out (no filter) CO read out (with filter)

Hydrogen Sulphide (H2S)  315 ppm < 10 ppm

Sulphur Dioxide (SO2)  50 ppm < 5 ppm

Nitric Oxide (NO)  30 ppm < 10 ppm

Nitrogen Dioxide (NO2)  - 55 ppm - 15 ppm

Chlorine (Cl2)  - 30 ppm < -5 ppm

Hydrogen (H2) < 40 ppm < 40 ppm

Hydrogen Cyanide (HCN)  40 ppm < 15 ppm

Ethane  90 ppm < 50 ppm

Measurement of Hazardous Substance Page 112


Chapter 6 Gases and Vapours
So, for example, the presence of Figure 6-11 Dräger Tubes and Bellows Sampling Pump

Source: Dräger Safety – Reproduced with permission


small amounts of ethane (100 ppm
or 0.01% in air) without a sensor
filter might lead one to incorrectly
conclude that 90 ppm of CO was
present.

The operating manual of the direct


reading instrument should provide
information about known cross
sensitivities. Where relevant
information is not provided in the
manual, and if there are
contaminants present other than
the one that the instrument is designed to measure, the supplier should be consulted about the
possibility of cross sensitivity.

6.13 Detector Tubes (Colorimetric Tubes)


Colorimetric tubes are a convenient and inexpensive way to provide an initial evaluation of
potential gas and vapours exposures. However, they are less accurate than other approaches and
results are based on short sample periods (usually a few minutes or less).

Colorimetric tubes are based on a specified colour change of a specific reactant when it comes
into contact with the contaminant of interest. Most tubes contain a solid reactant through which a
known volume of air is drawn through the tube using a manual pump. It's important to operate
the pump correctly and to track the number of strokes to collect the required number as specified
in the tube instructions. The tubes usually have an arrow that should point towards the pump to
ensure the tube is in the correct orientation. Air concentration of the particular contaminant, if
present, are read off directly from gradations on the colorimetric tube (i.e., length of stain, see

Figure 6-12 New (Left) and Used ). In some cases, the result is based on counting the
(Right) Colorimetric Tubes number of strokes required to match colour change in
Source: Dräger Safety – Reproduced with permission

the tube with reference colour provided with the


instructions. So, again, reading manufacturer
instructions before use is critical.

The accuracy of colorimetric tubes is dependent on


factors including sample pump volume, efficiency of
the chemical reaction, humidity, temperature,
manufacturer’s calibration of the graduations and
Read result here
interpretation of the length or colour of the stain.
(off tube
Typically, accuracy is quoted as 10 – 30%, and varies
graduations)
according to tube, presence of interferents and tube
concentration range.

There are various manufacturers of colorimetric tubes


such as Dräger, Kitagawa, Gastech and MSA for grab or short term (seconds to minutes) available

Measurement of Hazardous Substance Page 113


Chapter 6 Gases and Vapours
to measure approximately 300 gases in different concentration ranges. Please note that
colorimetric tubes from one manufacturer CANNOT be used with the pump from another
manufacturer.

There are also direct reading long term colorimetric tubes that use low flow battery operated
pumps or diffusion type badges for long term measurements of 1 to 4 hours.

Some of the advantages of direct reading colorimetric tubes include:

• Relatively inexpensive and cheap to use

• Wide range of gases and vapours

• Immediate results

• No expensive laboratory costs

• Can be used for spot checks

• No need for calibration (tubes are pre calibrated)

• No need for charging or electric power during operation

However, such devices have definite limitations such as:

• Interferences from other contaminants (cross sensitivities)

• Need to select correct tube and correct range of tube

• Results should not be compared to TWA

• Storage requirements limit shelf life. Check before use.

• They cannot be used to measure personal exposures, but they may be useful to provide
an on-the-spot indication of the order of magnitude of exposures, as a preliminary to a
decision on which exposures would warrant the collection of personal exposures.

It is very important to read the particular manufactures’ instructions for any colorimetric tube
before use to select the correct tube and to use it correctly, noting the effect of any potential
interferent, some of which can give false positive or false negative results.

6.13.1 Maintenance and Calibration


Readings from direct reading instruments are only as good as the maintenance and calibration of
the equipment. An approach used in the mining industry that has also found use in general
industry is to set out the requirements and responsibilities for the examination and calibration of
different classes of equipment based on their use. These classes are as follows:

Measurement of Hazardous Substance Page 114


Chapter 6 Gases and Vapours
Table 6-6 Calibration Classes

Group I Hand held or portable equipment


Ia – provides scaled indication of actual gas concentration.
Ib – provides alarm indication of actual gas concentration

Group II Equipment that used in severe conditions e.g., mounted on operating equipment,
where it could be exposed to vibration, high levels of dust and humidity.

Group III Equipment installed at a fixed location for appreciable periods of time with a local read
out of concentration.

Group IV Equipment permanently installed with remote readout of concentration.

The mining industry approach also sets out the requirements for a Certificate of Compliance,
recordkeeping, accuracy requirements and the minimum competencies for persons and accredited
authorities engaged in the examination, maintenance and testing of equipment covered.

The mining industry approach also provides advice for techniques and equipment to carry out
span and zero tests on gas detecting equipment. Span test is the test of response to certified test
gas(es). Zero test is test of response to zero gas conditions.

Test equipment for single point span checks consists of a cylinder containing the certified test gas
fitted with either a calibrated flow meter with a precision regulator or a flow restrictor and
pressure gauge.

For equipment in which the external atmosphere reaches the sensor or detector by diffusion, the
test procedure usually involves dispensing the certified test gas to the sensor via tubing and
suitable calibration cup. Calibration cups should conform to equipment manufacturer
requirements.

For sample-draw equipment containing an integral pump or hand-held aspirator, the sample inlet
is connected via tubing to grab sample bag that has been pre-flushed and filled with the certified
test gas.

Measurement of Hazardous Substance Page 115


Chapter 6 Gases and Vapours
Table 6-7 Suggested Maintenance Schedule Based on Instrument Use

Group Group Type Suggested Maintenance Schedule*

Ia Handheld/portable Shift / or before use


Weekly Calibration
6 Monthly Service

Ib Handheld/ portable with alarms Shift / or before use


Weekly Calibration
6 Monthly Service

II Machine mounted Shift / or before use


Zero – Weekly
Calibration – Weekly
Alarm - Weekly
Switching – Weekly
6 Monthly Service
Overhaul - 4 Yearly

III Underground fixed Status – Daily


System – Daily
After relocation
Switching – Monthly
Yearly Service

IVa Surface fixed Status - Daily


System – Monthly
Yearly Service

IVb, IVc Surface fixed Status – Daily


System – Monthly
Line Integrity – Monthly
Yearly Service
* Daily – typically by user
Weekly – typically by maintenance person / department
Monthly – typically by maintenance person / department
Yearly – typically by external authority

6.13.2 A Primer on Explosion Safe Equipment


The International Electrotechnical Commission Scheme for standards for equipment that may be
used in explosive atmospheres is known as IECEx. This scheme has gained worldwide acceptance
in countries that include Europe, United Kingdom, South Africa, USA, Canada, Asia and Australia
and New Zealand. The 60079 Series for Gases and Vapours and the 61241 Series for dusts has
been widely accepted. Intrinsically safe instruments refer to instruments that are incapable of
acting as ignition sources for flammable gases or vapours. To be so designated, instruments must
comply with IECEx guidelines for design and operation.

The modern automation of equipment has led to its increased use in Explosive or Ex areas. Such
equipment is termed “Ex equipment” and is found in areas such as:

Measurement of Hazardous Substance Page 116


Chapter 6 Gases and Vapours
• Automotive refueling stations or petrol stations

• Oil refineries, rigs and processing plants

• Chemical processing plants

• Printing industries, paper and textiles

• Hospital operating theatres

• Aircraft refueling and hangars

• Surface coating industries

• Underground coalmines

• Sewerage treatment plants

• Gas pipelines and distribution centres

• Grain handling and storage

• Woodworking areas

• Sugar refineries

• Metal surface grinding, especially aluminum dusts and particles

Explosions require the presence of three conditions:

• A flammable gas or vapours in concentrations within a specified flammable range, or the


presence of suspended dust in combustible concentrations

• Oxygen

• An ignition source

6.13.2.1 Explosive Zone Classification Scheme


Potentially explosive atmospheres may be defined into zones as follows:

Table 6-8 Explosive Zone Classifications


Reproduced with permission

Gases, Vapours, Mists Dusts Explosive Atmosphere is Present

Zone 0 Zone 20 Most of the time


Source: TestSafe –

Zone 1 Zone 21 Some time

Zone 2 Zone 22 Seldom or short term

Measurement of Hazardous Substance Page 117


Chapter 6 Gases and Vapours
6.13.2.2 Explosive Proof Classification Scheme
Equipment that is explosion proof is classified as follows:

Table 6-9 Explosion Proof Classification

Group I Equipment that is used in underground mines where it could be subjected to methane
and coal dust

Group II Equipment used in industries other than mining with the following subgroups

IIA - Where least readily ignited gases such as propane and benzene may be present

IIB - Where more readily ignited gases such as ethylene and diethyl ether may be
present

IIC - Where most readily ignited gases such as hydrogen and acetylene may be
present

6.13.2.3 Explosive Proof Surface Temperature Classification Scheme


Equipment that is to be used within potentially flammable atmospheres may be rated based on
surface temperature. The concept is to ensure that operating temperatures do not exceed ignition
temperatures of gases and or vapours that may be present.

Group I temperature designation requires that the temperature of the components and surfaces
exposed to dust and methane to be less than 150°C. Where components and surfaces are
protected from the ingress of dust, the maximum temperature of such must be less than 450°C.

For Group II designation, the maximum surface temperature must not exceed values shown Table
6-10 Maximum Surface Temperature / Ignition Temperature which corresponds to the
temperature class of the equipment. For convenience, a temperature class may be assigned to a
gas or vapours based on its ignition temperature.

Table 6-10 Maximum Surface Temperature / Ignition Temperature

Temp Class Maximum Permissible Surface Temp(°C)


Source: TestSafe – Reproduced with

T1 450

T2 300

T3 200

T4 135
permission

T5 100

T6 85

Measurement of Hazardous Substance Page 118


Chapter 6 Gases and Vapours
6.13.2.4 Intrinsically Safe Equipment and Zones
Intrinsic Safety has 3 levels of protection:

• “ia” – means that the type of protection ‘intrinsic safety” (no release of spark energy or
thermal energy that can cause ignition) is maintained with up to two faults.

• “ib” – means intrinsic safety is maintained with up to one fault.

• “ic” – means intrinsic safety is maintained, but no requirement to apply faults.

Table 6-11 Level of Explosion Protection and Explosion Zones

Level of Protection Suitable For…

Source: TestSafe –
“ia” Zones 0, 20

Reproduced with
permission
“ib” Zones 1, 21

“ic” Zones 2, 22

What's In A Label? Table 6-11 Level of Explosion


Protection and Explosion
Only appropriate certified and marked electrical equipment Zones links intrinsic safety
may be used in hazardous areas. Users of electrical equipment classifications with explosion
must ensure that the equipment complies with the relevant zone.
regulations and local standards.
Safety factors are applied and
Equipment for use in hazardous atmospheres has to be labelled the equipment evaluated for
with the name of the manufacturer, model number, Ex code spark and thermal ignition
and certificate number. This information, which will be in short energy after the application
hand, has to be attached to the equipment. of faults.
Consider the following equipment label example: Only explosive protected
equipment can be used in
areas where explosive
atmospheres may occur.

What does it mean? Explosive protective


equipment can be
Ex indicates the equipment may be used in potentially manufactured to IEC
explosive atmosphere. protection type levels which
“ia” indicates equipment is suitable for zone 0 application. are subject to the
requirements of their own
IIC the equipment is suitable for Groups IIA, IIB, IIC.
specific standards. Intrinsic
T4 the equipment is suitable for gases with auto ignition safety, Flameproof, Increased
temperature greater than 135°C Safety, Encapsulation etc. are

Measurement of Hazardous Substance Page 119


Chapter 6 Gases and Vapours
some of the common types of protection used for explosion protected electrical equipment.

Further and much more detailed information for the use of gas detection equipment in potentially
explosive atmospheres including the Classification of Zones, Explosion Groups, Temperature
Classes, the Types of Protection provided by equipment, the requirements for Certification and
Marking is available from the different National Standards and Certification bodies.

6.13.2.5 Explosion Control Basics


Eliminating or controlling one will usually control potential explosive hazards. The currently
accepted hierarchy for control of these hazards is as follows:

• Reduce or avoid the use of flammable substances

• Do not allow any releases of flammable substances to form potentially explosive


atmospheres

• Remove sources of ignition from the potentially explosive atmosphere

• Use adequately designed equipment that reduces the probability of causing an explosion
(i.e., Ex equipment)

• Provide measure to reduce the effects of explosions

Measurement of Hazardous Substance Page 120


Chapter 6 Gases and Vapours
Chapter 7 Sample Analysis

This section provides an overview of occupational hygiene sample analysis. Occupational


hygienists are expected to have a general understanding of the principles and applications of
these methods

7.1 Introduction
Analysis of occupational hygiene samples may be done on the job using some form of direct
reading device or instrument. Alternatively, a sample is often collected at the workplace and sent
to a laboratory for analysis. This analysis could vary from a relatively simple weighing of the
contaminant on a filter to the determination of a metal using an inductively coupled plasma (ICP)
spectrometer or the use of a gas chromatograph linked to a mass spectrometer (MS) for the
determination of an organic solvent.

In most cases the hygienist does not perform the laboratory analysis, but an understanding of
some of the basics is required to:

• Select an appropriate monitoring and analytical method

• Communicate with the analytical laboratory

• Understand the principles of the direct reading instrument

• Make an assessment of the reliability of the results

7.2 Analytical Methods


Most modern methods of occupational hygiene sample use instruments rather than the classical
“wet chemical methods” common before the 1960s.

The types of analysis can typically be divided into the following main types

• Spectroscopy

• Atomic

• Molecular

• Chromatography

7.2.1 Spectroscopy
The basic underlying principle of spectroscopy is that all elements or chemical compounds absorb
or emit electromagnetic radiation at specific frequencies. If a sample is radiated at a specific
frequency for a particular element, if that element is present the amount of radiation absorbed or
emitted is proportional to the concentration of that element in the sample.

Measurement of Hazardous Substance Page 121


Chapter 7 Sample Analysis
7.2.1.1 Atomic Spectrometry
Typically used for the analysis of the metallic elements. Samples usually collected using
conventional sampling methods on to filters, impingement into liquids or adsorption on to a solid.
Samples then prepared by appropriate method for subsequent analysis.

Figure 7-1 Schematic of an Atomic-Absorption Spectrometer

Source: BP International
7.2.1.1.1 Flame Atomic Absorption Spectrometry (AAS)
The sample in solution is atomized by flame and the absorption of a specific wavelength of light
from the hollow cathode lamp in the flame is measured to quantify the element. This technique
typically used for the analysis of approximately 60 metals.
Figure 7-2 Atomic Absorption
7.2.1.1.2 Hydride Generation
Spectrometer
Arsenic and selenium have poor sensitivity using
conventional Flame AAS because their spectral lines
are in the far UV. Hydride generation overcomes this
issue. As and Se are converted to their respective
hydrides AsH3 and H2Se. When these hydrides are
swept through the flame or a through a heated quartz
cell a larger proportion of the element reaches the
light path resulting in increased sensitivity.
Source: University of Wollongong

7.2.1.2 Flameless Atomic Absorption


AAS is not sensitive enough for analysis of low
concentration of metals in biological samples such as
blood. During AAS there is a high flow rate of sample
through the flame and a more sensitive method
where less material is used is required.

Measurement of Hazardous Substance Page 122


Chapter 7 Sample Analysis
7.2.1.2.1 Graphite Furnace
Atomization of elements without the use of a flame can be achieved with the use of electricity
(electrothermal atomization). The sample is placed inside a hollow graphite tube and rapid heating
of the tube using a high electric current causes the sample to atomize.

7.2.1.2.2 Cold Vapours Generation


This technique is used for the analysis of mercury because of the volatility of mercury at room
temperature. Mercury compounds are reduced to metallic mercury and the mercury vapours is
transported to the absorption cell by a stream of gas for determination.

7.2.1.3 Atomic Emission Spectrometry


This technique is also based on the flame excitation of an element, but is looking at the emission
of energy when the excited element is returned to its ground state.

7.2.1.3.1 Flame Emission


Atomic absorption spectrometers can be operated in the emission mode or a separate instrument,
a flame photometer can be used. Typically, the elements where this technique is used are the
alkali and some alkaline earth metals e.g., Sodium and Potassium.

7.2.1.3.2 Inductively Coupled Plasma Spectrometry


An extension of atomic emission spectrometry is inductively coupled plasma spectrometry (ICP).
By using gas plasma temperatures up to 10,000°C can be obtained resulting in a large increase in
excited atoms and hence sensitivity. Plasma is a cloud of highly ionized gas comprising ions,
electrons and neutral particles. In
Figure 7-3 Graphite Furnace
ICP the gas used is usually argon
because it is easily ionized with radio
frequency electromagnetic fields.

Since all elements in a sample emit


their characteristic wavelengths
simultaneously it is possible to
measure a large number of
elements, up to 60, simultaneously
or sequentially.
Source: University of Wollongong

The scanning ICP has a distinct


advantage over AAS in that a
separate lamp for each specific
element is used in AAS but up to 60
elements can be analysed by ICP on
the same sample.

Measurement of Hazardous Substance Page 123


Chapter 7 Sample Analysis
7.2.1.4 Molecular Spectrophotometry

7.2.1.4.1 UV-Visible Spectrophotometry


This technique is used for metals or organic compounds. Samples are collected by conventional
sampling methods on to filters or by impingement into solutions.

The principle of the method is based on the absorption of ultraviolet and visible radiation by the
excitation of bonding electrons in molecules.

Figure 7-4 Schematic of a Single Beam UV-Vis Spectrophotometer

Source: BP International
Most chemicals species absorb UV or Visible radiation and thus can be quantified, e.g., oil. For
non-absorbing compounds a reaction with a colour producing reagent (a chromophore) may allow
its quantification.

E.g., the reaction of hexavalent chromium with s-diphenyl carbazide to produce a red complex
with an absorption peak at 540 nm.

7.2.1.5 IR Spectrometry
Infra-red (IR) spectrometry provides a way of identifying pure species as each molecular species
has its own unique absorption spectrum, i.e., fingerprint.

Absorption or emission of infra-red radiation results in the change in vibration or rotation of a


molecule. The number of ways a molecule can absorb energy is related to the number of

atoms and the number of bonds it contains. IR is particularly applicable to organics and covalently
bonded metal complexes.

The IR spectrum for quartz is provided in

. Note the distinctive quartz “doublet” at 798 and 779 cm-1 wavenumbers.

Measurement of Hazardous Substance Page 124


Chapter 7 Sample Analysis
The main application of infra-red
Figure 7-5 IR Spectrum for Quartz
spectrophotometry is identification of
compounds and in occupational hygiene is
also used for direct gas and vapours
monitoring using portable instruments and
for the measurement of quartz in dust.

7.2.1.6 Molecular Fluorescence


Fluorescence is one of the ways a molecule
returns to its ground state after excitation. It
involves the emission of radiation at
characteristic wavelengths of the molecule
and different from the exciting wavelengths.
Fluorescence can be used to measure
compound which fluoresce such as aromatic
Source: University of Wollongong
hydrocarbons.

7.2.2 Chromatography
Chromatography is a separating method that
relies on differences in partitioning behavior
between a flowing mobile phase and a
stationary phase to separate the
components in a mixture.

A column or other support holds the stationary phase and the mobile phase carries the sample
through it. Sample components that partition strongly into the stationary phase spend a greater
amount of time in the column and are separated from components that stay predominantly in the
mobile phase and pass through the column faster.

There are a number of Figure 7-6 Gas Chromatograph


different chromatography
techniques and include:
Source: University of Wollongong

Measurement of Hazardous Substance Page 125


Chapter 7 Sample Analysis
• Gas chromatography (GC): Figure 7-7 Gas Chromatograph Mass Spectrometer
Applied to volatile organic
compounds. The mobile
phase is a gas and the
stationary phase is usually a
liquid on a solid support or
sometimes a solid
adsorbent.

Source: University of Wollongong


• High-performance liquid
chromatography (HPLC): A
variation of liquid
chromatography that
utilizes high-pressure pumps
to increase the efficiency of
the separation.

As the components elute from the column they can be quantified by a detector and or collected
for further analysis. An analytical instrument can be coupled with a separation method for on line
analysis and includes gas and liquid chromatography with mass spectrometry.

7.2.3 Other Analytical Techniques

7.2.3.1 X-Ray Diffraction


X-Ray diffraction (XRD) can help identify and quantify crystalline substances. However, it cannot
give information on the elements present in the sample. An example where XRD is used is in the
analysis of materials containing silicon and oxygen:

• Quartz (SiO2) has a TLV of 0.1 mg/m³ (respirable)

• Kaolin is a hydrated aluminum silicate Al2Si2O5(OH4) has a TLV of 10 mg/m³ (inhalable)

• Amorphous Silica has a TLV of 10 mg/m³

Conventional analysis only showing the amounts of silica and oxygen is not helpful in this
situation; we need to know the form that the silica and oxygen is in. XRD is able to both identify
and quantify the different crystalline phases that have quite different potential health effects.

7.2.3.2 X-Ray Fluorescence


X-ray fluorescence (XRF) is widely used for the identification of elements. The absorption of x-rays
produces an excited atom that returns to its ground state via a series of electronic transitions.
These transitions are accompanied by an emission (fluorescence) of X radiation which is
characteristic of the element.

Multi-channel instruments permit up to 24 elements to be analysed simultaneously for samples


such as ashes, ores, minerals, ceramics, alloys and metals.

Measurement of Hazardous Substance Page 126


Chapter 7 Sample Analysis
7.2.3.3 Mass Spectroscopy
This technique is based on the conversion of a sample into gaseous ions and their separation on
the basis of charge to mass ratios. This provides both qualitative and quantitative information. The
spectra obtained are relatively easy to interpret since they provide information based on the mass
of structural components and the total molecular weight of the compound.

7.2.4 Detection Limits, Sensitivity, Chemical Interferences

7.2.4.1 Detection Limits


As discussed in Section 4.9, the analytical detection limit can have an impact on whether it is
possible to collect a sample of sufficient volume to yield a measurable result.

7.2.4.2 Method Sensitivity


Does the analytical method cover the concentration range of interest? Some analytical methods
may not have sufficiently low limits of detection to measure short term exposures. Is there
another method that could be used to get better sensitivity e.g., the use of ICP rather than AAS for
the analysis of metals.

7.2.4.3 Chemical Interferences


What other substances are likely to be present in the sample and are they likely to interfere with
the proposed analytical method?

For example, if a welder is being sampled for “welding fumes” the gravimetric determination, i.e.,
the filter weighing, will be adversely affected if “grinding dusts” have also been sampled during
the fume collection period.

An example of chemical interference is calcium in the presence of phosphate as it forms the stable
compound calcium phosphate, which can reduce the absorbance of calcium.

Chemical interferences can be especially a problem if chemical speciation of individual


contaminants is required.

7.2.5 Sources of Analytical Methods


There are a number of recognized sources of standard and recognized methods that are used for
occupational hygiene analysis. These include:

• NIOSH Manual of Analytical Methods (NMAM) – a collection of over 1,700 methods for
sampling and analysis of contaminants in workplace air, and in the blood. Available on
line at: www.cdc.gov/niosh.nmam.

• UK HSE Methods for the determination of hazardous substances (MDHS Series) more
than 100 methods available on line at: www.hse.gov/uk/pubns/mdhsindex.htm.

Measurement of Hazardous Substance Page 127


Chapter 7 Sample Analysis
• OSHA – Standard methods for sampling www.osha.gov/dts/osta/otm/otm_toc.html.

• ISO – Standard methods for sampling and analysis


www.iso.org/iso/en/ISOOnline.frontpage.

• National Standard – A number of standards including the sampling for respirable and
inspirable dust, welding fumes and organic vapours are available through the National
Standards organisations of a number of countries.

• SKC Inc Comprehensive Catalog and Sampling Guide – annual publication and also on
their website www.skcinc.com provides references to the method, sampling parameter,
analysis and equipment for over 2,500 specific compounds.

• Although mainly aimed at measuring contaminant concentrations that are emitted from
a workplace rather contaminant concentrations within a workplace, methods published
by the Environmental Protection Agency (EPA) in the USA may also be worth
considering.

7.3 Laboratory Balances


While weighing is often considered the simplest of the analytical tools, there are a number of
sources of error that must be considered.

The analyst is often weighing sub milligram quantities of material and greater care has to be taken
during both filter/sample head preparation and filter reweighing after sampling.

Insufficient sampling time may mean not enough material is collected and cannot be detected
unless an appropriate laboratory balance is used.

Calibration of the microbalance is a key aspect and the following extract from AS3640 can be used
as a guide to what is required.

“The accuracy of the microbalance used in the gravimetric measurements shall be checked in the
following manner:

1. Repeatability: Every 6 monthly, an appropriate repeatability test shall be conducted on


the microbalance.

2. Before every weighing session: Before weighing the filters:

i) Check the balance with a reference weight at or near to full electrical


capacity; and

ii) Check the linearity of the balance inside or near to the working range.

3. During every weighing session: When weighing filters:

i) Conduct a zero check after each sample/blank filter weight determination;


and

Measurement of Hazardous Substance Page 128


Chapter 7 Sample Analysis
ii) Verify that electrostatic effects are insignificant by repeat sample weighing.

4. After every weighing session: Check the calibration of the balance with a reference
weight at or near to full electrical capacity.

5. Long weighing sessions

If a series of filters is being weighed the microbalance accuracy shall be checked at appropriate
intervals during the procedure.”

7.4 Microscopy
Polarized light microscopy (PLM) together with dispersion staining is the technique that is used for
the identification of types of asbestos fibre, and phase contrast microscopy (PCM) is used for the
counting of fibres.

Fibres are particles that have a needle-like or thread-like appearance with a specific length to
width ratio. Some examples of fibres include asbestos, fiberglass, rockwool and ceramic fibres.

Monitoring for asbestos fibres is carried out following the appropriate Standards methods such as:

• Determination of Airborne Fibre Number Concentrations: A recommended method by


phase contrast optical microscopy (membrane filter method) published by the WHO
(1997)
Figure 7-8 Sampling Head for Asbestos Fibres
• NIOSH Method 7400
Asbestos and other fibres by
PCM

• HSG 248 Asbestos: The


analysts’ guide for sampling,
analysis and clearance
procedures – Appendix 1:
Fibres in air: Sampling and Source: University of Wollongong
evaluation by Phase
Contrast Microscopy (UK)

• NOHSC Code Asbestos:


Code of Practice and
Guidance Note or the
Membrane Filter Method
for Estimating Airborne Asbestos Dust (Australia)

Microscopy should only be performed by a trained and certified person. Typically, such persons
routinely participate in an inter laboratory system to maintain their skills and validate their
consistency with international standards.

Measurement of Hazardous Substance Page 129


Chapter 7 Sample Analysis
The principle of the method is air samples are collected on a gridded mixed cellulose ester or
cellulose nitrate filter mounted in a cowled asbestos sampling head.

Figure 7-9 Phase Contrast Microscopy – Amosite After sampling the filters are
Fibres & Synthetic Mineral Fibres mounted on a microscope slide by
collapsing the membrane using

Source: A Rogers – Reproduced with permission


acetone vapours making it
transparent. Glyceryl triacetate is
added to the slide to provide a
suitable medium for seeing the
fibres.

The fibres are then counted using


phase contrast microscopy following
standard fibre counting rules. Results
are expressed as numbers of
fibres/ml of air.

The other area of analysis in regard


to asbestos fibres is that of identification in bulk materials. This involves the suspension of fibres in
liquids of known refractive indices and observation of the colours displayed under polarized light
at different orientations of the fibres. A variety of microscope configurations can be used,
including dispersion staining and crossed polars with first order red compensator plate. This
technique is both rapid and sensitive in the hands of a trained operator.

Figure 7-10 Chrysotile

Source: A Rogers – Reproduced with permission

Measurement of Hazardous Substance Page 130


Chapter 7 Sample Analysis
Figure 7-11 Amosite (1st Order Red Retardation)

Source: A Rogers – Reproduced with permission


7.5 Quality Assurance of Analysis

7.5.1 Internal Quality Control


The internal quality control process is the set of procedures adopted by a laboratory to assess
whether the results from each set of tests are consistent. Occupational hygiene samples can often
pose quality control concerns including the very low levels being measured, matrix effects from
the sampling medium, interfering substances, incomplete recoveries, degradation in storage or
transport etc. The procedures typically used include method validation, the use of standards,
blanks and controls, recoveries and quality control charts.

7.5.1.1 Method Validation


Before use an analytical method must be validated to ensure it is sufficiently accurate and precise.

Its accuracy may be tested by analysing known concentrations of the analyte. For example, by
adding known amounts of solvent to charcoal tubes, desorbing it and analysing it by gas
chromatography; or by spiking blood or urine samples with lead for example and analysing by
atomic absorption. The recovery of the analyte is the percentage of added analyte recovered, i.e.,
measured in the analysis.

Precision is determined by analysing enough replicate samples to enable the calculation of the
standard deviation or coefficient of variation. Several different concentrations over the range
should be selected.

The measurement range is a guide as to the usual operating range of the method. At the lower
end this involves an estimate of the limit of detection (LOD) and the limit of quantitation (LOQ).

Measurement of Hazardous Substance Page 131


Chapter 7 Sample Analysis
Other factors to be evaluated include:

• Interfering substances

• Capacity of the collection media (e.g., breakthrough volume for sorbent tubes)

• Stability of samples

• Critical steps in the analysis where special care must be taken

There are well established and validated methods for many common chemicals.

7.5.1.2 Standards
Standard reagents: are chemicals of known purity and composition. These materials are often
available from external agencies e.g., Standard Reference Materials from the US National Bureau
of Standards.

Calibration standards: these are reference standards against which all test and control samples are
compared.

Where standard calibration curves are prepared at least 5 points should be used and appropriate
regression analysis should be undertaken to ensure the viability of the calibration curve.

7.5.1.3 Blanks
Field sampling blanks should be submitted with field samples to determine if there has been
contamination during sample handling and storage. The blank is treated in the same manner as
the field sample but with no air being drawn through it.

Reagent blanks are used in the laboratory to correct for any contribution made by the laboratory
reagents used in the analysis.

7.5.1.4 Control Materials


These have been previously analysed and are analysed with the test samples so that a comparison
between actual and expected result can be made.

7.5.1.5 Recoveries
Recoveries should be assessed both as part of the method validation process, but also on an
ongoing basis as part of the quality control process.

7.5.1.6 Duplicates
Duplicate samples, i.e., from the field are more useful in assessing the reproducibility of the
sampling or analysis than are duplicate analysis, i.e., two chromatograph injection from the one air
sample.

Measurement of Hazardous Substance Page 132


Chapter 7 Sample Analysis
7.5.1.7 Quality Control Charts
These can provide a means of showing the reliability of each method and to identify trends or
cyclical changes in laboratory performance.

7.5.2 External Quality Assurance

7.5.2.1 Proficiency Testing Schemes


Many countries run inter-laboratory testing schemes and some of these are International:

• NIOSH - Proficiency Analytical Testing (PAT) – solvents on charcoal, asbestos, silica and
metals on filters

• UK HSE – Workplace Analysis Scheme for Proficiency (WASP) – solvents on charcoal,


metals on filters

They involve the distribution of control samples to laboratories by an outside agency. The material
is analysed and the results returned to the coordinating body for statistical analysis.

7.5.2.2 Laboratory Accreditation


The purpose of accreditation is to ensure a laboratory’s results are reliable. A laboratory applying
for accreditation is visited by assessors, who examine all aspects of the laboratory’s operations
including the qualifications and experience of staff, quality, calibration and maintenance of
instruments, accommodation, laboratory practice including sample handling, quality control,
recording and reporting, and the test methods used. If satisfied, the appropriate approval to
undertake the type of analysis being sought is granted.

Measurement of Hazardous Substance Page 133


Chapter 7 Sample Analysis
Chapter 8 Other Sampling Tools

This chapter describes and discusses other types of sampling occupational hygienists may be
called upon to do. These include
✓ Bulk Samples

✓ Surface Contamination

✓ Dermal Exposure

✓ Confined Space Sampling

✓ Compressed Air Quality

8.1 Bulk Sampling


In many instances it will be necessary to collect some bulk samples to identify which contaminants
are likely to be present in the workplace. This is commonly the case in regard to asbestos
identification where bulk samples are collected and the presence and type of asbestos identified
by dispersion staining or other confirmatory techniques.

The same principles can be applied to other unknown substances found in workplaces. Before
developing a monitoring programme, bulk samples of an unknown material can be sent to a
laboratory for analysis to check on the specific contaminants present and to check for any
contaminants which may interfere with some sampling methods.

The results will guide what type of monitoring strategy is required and thus it is very useful in the
overall process.

8.2 Surface Contamination Measurements


If a comprehensive risk assessment for exposure to contaminants in the workplace is to be
developed, it is essential that any contribution from surfaces be evaluated. This will always be
dependent on the toxicological properties of the substance and is common practice in the nuclear
industry.

There are various methods used for evaluating surface contamination, such as micro vacuuming,
disposable paper towels and manual wipe methods. The manual wipe method (also called smear
and wipe) is the most commonly used and involves a filter paper being drawn over a known area
of contaminated surface and then being analysed to produce an assessment of the level and
nature of the deposit.

Another method which has shown good results in laboratory trials (Wheeler & Stancliffe 1998) is
the use of adhesive tape, more specifically forensic tape. Such tapes are constructed of a clear
plastic top coat, a sticky middle layer and a base layer. By removing the clear plastic top coat, the
sticky layer can be pressed into a surface thus collecting what contaminants are present. In
general samples (both wipe and adhesive tape) are treated with acid to dissolve any contaminants

Measurement of Hazardous Substance Page 134


Chapter 8 Other Sampling Tools
present, followed by atomic absorption spectrophotometry, or the samples can be analysed
without any acid digestion by X-ray fluorescence spectrometry (XRF).

Other approaches to assessing contaminated surfaces involve the use of pH sticks or colorimetric
pads (acids and alkalis) or instrumentation such as mercury sniffers (the high vapours pressure of
mercury makes this a particularly effective technique).

The question as to why you would undertake surface contamination invariably arises. Such
sampling (especially during evaluation of contaminated waste sites) improves the characterization
of what hazards may be present and allows for better decision-making.

Surface contamination samples can indicate sources of leakage and help to track the spread of
contamination. They can give an indication of how and where skin contact might occur. However,
they are not a direct measure of exposure and cannot readily be compared with any exposure
limits.

8.3 In-Situ XRF Metal Analysis


An XRF spectrometer uses primary radiation from an X-ray tube to excite secondary emission from
a sample. The radiation emerging from the sample includes the characteristic X-ray peaks of major
and trace elements present in the sample. Dispersion of these secondary X-rays into a spectrum,
usually by X-ray diffraction, allows identification of the elements present. The height of each
characteristic X-ray peak relates to the concentration of the corresponding element in the sample,
allowing quantitative analysis of samples for most elements in the concentration range 1 ppm to
100%.

In recent years small hand-held XRF analysers have been developed which are extremely useful for
measurements of samples within the field. One such application is their use to measure elements
in contaminated soils and unknown bulk materials. This is particularly useful for metal analysis.

It should be noted that particle size and surface preparation can influence results. Improved
analysis can be achieved if the sample is dried, sieved, ground or pressed.

Dost (1996) evaluated a field XRF unit in relation to the measurement of dusts from surfaces in
workplaces and commented on the ease with which the elemental nature and level of
contamination in the workplace could be determined. Dost also concluded that the XRF technique
had a distinct advantage over the traditional wipe method where the contaminant material was
on a rough and porous surface (e.g., concrete). Conversely, it was not suitable on surfaces such as
steel as it picked up the elements of this surface as well as the overlaying contaminant material.

A common use for XRF instruments is in the evaluation of coatings for the likely presence of
significant amounts of lead.

8.4 Skin Exposure


Dermal exposure can present a significant pathway for some contaminants to enter the body. This
is especially the case with pesticides, but other compounds can be absorbed this way.

Measurement of Hazardous Substance Page 135


Chapter 8 Other Sampling Tools
Dermal exposure evaluation methods have been broadly categorized into direct and indirect
methods.

8.4.1 Direct
Direct means assessing what is deposited on to the skin; indirect means estimating dermal dose
either as attributable to some biologic indicator that is actually measured or that which could
potentially result from a contaminant measured on an accessible surface.

The most common direct method is the use of dermal dosimeters in the form of patches. Other
direct evaluation methods include skin washes and wipes, and the video detection of fluorescent
tracers.

8.4.2 Indirect
Indirect methods refer primarily to measuring a biologic response such as cholinesterase activity in
blood or urinary excretion, but also include measuring surface contamination.

In comparison to air sampling and even biological monitoring, dermal dosimetry is not a simple or
routine procedure.

An individual applying dermal dosimeters should be thoroughly trained regarding the placement
and retrieval of the dosimeters and recording of observations and other information about the
activity.

In addition to objective parameters, observed work practices can also have statistically significant
important influences on dermal exposure.

Each patch dosimeter is a sandwich holding a passive matrix (like a cotton gauze sponge) flat and
to protect it from skin perspiration. Either one or two sets of patch dermal dosimeters can be
used. The most important is the set placed against the skin under the clothing. It is believed that
errors will result from using patch dosimeters attached to the inside of clothing that is free to
move relative to the skin; such dosimeters will neither collect contaminants reaching the skin via
penetration through openings (such as the neck, sleeves, or cuffs) nor be affected by the air
motion carrying contaminant through the weave of the fabric. A second set of dosimeters may be
placed outside of any clothing; it is also important that no inner dosimeter is placed beneath an
outer dosimeter.

After dosimeters have been in place throughout an activity involving exposure, they are carefully
removed, prepared for extraction (the quantitative removal of the chemical from the collection
matrix), and the extract is analysed for the mass of chemical.

Whole body dosimeters are typically a set of long cotton underwear that minimizes the effect of
non-uniform depositions within a body part, but suffers from the lack of a barrier between the
skin and dosimeter and may add heat stress to the wearer. After use, the whole-body dosimeter
may still be dissected into portions covering individual body parts.

Measurement of Hazardous Substance Page 136


Chapter 8 Other Sampling Tools
As with all other approaches to assessing dermal exposures, there are limitations to the use of
dermal dosimeters. Among the most important of these limitations (not restricted to dermal
dosimeters) is the difficulty in accurately collecting depositions of volatile chemicals.

Biological monitoring to assess dermal exposure is a common technique (e.g., cholinesterase


activity in blood for pesticides); however, it may be invasive and unless correct sample collection
techniques are observed may grossly underestimate exposure. In such cases dermal dosimetry
(patches) may be a good alternative.

In other cases, such as chromium VI, Styrene or (Tetraethyl lead) where skin absorption can be a
significant route of exposure, a combination of environmental monitoring and biological
monitoring may give the most accurate picture of employee exposure.

Irrespective of the circumstances, dermal monitoring should only be undertaken by persons


trained and experienced in the appropriate monitoring techniques.

8.4.2.1 Tool Kit for Dermal Risk Assessment and Management -


RISKOFDERM
The European Research Project RISKOFDERM – Risk Assessment of Occupational Dermal Exposure
– has developed a conceptual model for dermal risk assessment and a simple to use tool kit for
assessment and management of health risks from dermal exposures and is currently undergoing
final evaluation. The tool kit can be downloaded at:

http://www.eurofins.com/research- development/occupational hygiene/risofderm.asp

The tool kit was constructed by analysing the major determinants of dermal hazard and control
exposure. The results were combined in the form of a decision tree. The tool kit does not show all
the details behind the assessment, but asks the user a series of questions that are translated by
the system into hazard and exposure categories that lead to an estimate of health risk from
dermal exposure together with suggested control strategies.

8.4.2.2 Hazard
The user is asked to enter the identification of the chemical and the risk phrases and any
additional information such as pH and the physical state of the chemical.

The information is translated into two hazard categories – one concerning local effects, the other
systemic effects after uptake through the skin. The hazards are rated – negligible, low, moderate
high, very high or extreme.

8.4.2.3 Exposure
User asked to enter information to identify the workplace or process that is assessed and which
one of the Dermal Exposure Operational units’ best fits with the sub category of exposure to solid
or liquid:

• Handling of contaminated objects – solid or liquid

Measurement of Hazardous Substance Page 137


Chapter 8 Other Sampling Tools
• Manual dispersion – solid or liquid

• Hand tool dispersion – solid or liquid

• Spray dispersion – solid or liquid

• Immersion – solid or liquid

• Mechanical treatment – solid or liquid

From the information the tool kit will apply default exposure rates, take into account duration and
the exposed body areas and the actual exposure score from local effects and the internal exposure
score from systemic effects are then calculated separately and ranked as health risk scores with
suggested controls ranging from no action required up to substitute in either case and stop
working.

The toolkit is an attempt to adapt elements of exact science to a situation where the necessary
input data are of limited quality and are only estimates. The purpose is to enable the user to
estimate the order of magnitude of hazard, exposure and risk and to encourage the user to deal
with issues of dermal hazard, exposure and control.

The RISKOFDERM project has been the subject of significant controversy and more detail can be
found in an overview by Oppl et al (2003).

8.5 Confined Spaces

8.5.1 Identification and Nature of Hazards


Confined spaces have various legal definitions in different parts of the world and while a full list of
such definitions is not appropriate for this course, all contain the same (or similar) key elements.
These include:

• They are enclosed or partially enclosed spaces at atmospheric pressure during


occupancy.

• May have a deficiency or an excess of oxygen.

• May have an atmosphere which has potentially harmful levels of contaminants.

• May contain a product which could cause engulfment.

• Could have restricted means of entry and exit.

Please be sure to understand the definition of a confined space in your jurisdiction, as definitions
and air monitoring requirements may vary.

Examples of confined spaces include:

• Storage tanks, boilers, silos, pressure vessels, etc.

Measurement of Hazardous Substance Page 138


Chapter 8 Other Sampling Tools
• Pits, pipes, sewers, ducts, etc.

A confined space is determined in part by the hazards associated with entry into such a space and
not just work performed in a physically restrictive location.

The presence of chemical agents (alone or in combination) may present a risk to personnel in a
confined space that would not otherwise occur in the general atmosphere.

Some of the hazards that may be associated with work in confined spaces are:

• Hazardous Substances: This includes the use of chemicals, previously stored substances
or their by-products (e.g., H2S from decomposing plant material), fumes from welding,
painting, etc.

• Flammable Atmospheres: This includes gases, vapours and dusts which are present in
the explosive range.

• Unsafe Oxygen Level: This includes oxygen deficient atmospheres as a result of


oxidation, combustion, displacement, absorption, consumption by some process and,
excess oxygen as a result of a leaking oxygen supply fitting, oxy-propane cutting, oxygen
injection and the use of chemicals that liberate oxygen (e.g., hydrogen peroxide).

• Engulfment: Asphyxiation caused by a stored supply of material immersing workers


within the confined space.

• Physical and Other Factors: This includes manual handling, ignition hazards, electrical
hazards, mechanical hazards, noise, radiation, biological hazards and heat stress.

8.5.2 Monitoring in Confined Spaces


The human senses should never be trusted to determine if the atmosphere within a confined
space is safe. Many toxic gases and vapours (such as carbon monoxide) cannot be seen or smelt,
nor can the level of oxygen be established accurately without appropriate instrumentation.

As permit to enter procedures for confined spaces invariably involve a risk assessment, this
process should ensure that appropriate arrangements are put in place to test the atmosphere
within the confined space.

Where appropriate the atmosphere should be tested for:

• Oxygen content; and/or

• Airborne concentration of flammable contaminants; and/or

• Airborne concentration of potential harmful contaminants.

The common means of sampling the air to assess the risk of adverse health effects is to test for
specific materials with a suitable portable analyser. There are many different kinds of analysers
available but the results are only as good as the operator’s skill and the state of analyser

Measurement of Hazardous Substance Page 139


Chapter 8 Other Sampling Tools
maintenance. An explosimeter, used for measuring the percent Lower Explosive Limit (LEL) in a
confined space, should be tested against a known standard gas, both before and after a test for
vessel entry, to ensure that an accurate reading is obtained. It should be noted that a reading
below the LEL could still mean that hundreds or even thousands of ppm of contaminants are
present in the atmosphere.

Instruments used for testing the atmosphere in a confined space should be selected for their
ability to measure hazardous concentrations and should be calibrated in accordance with the
manufacturer’s guidelines or manuals.

If atmospheres that are to be sampled are potentially explosive, intrinsically safe monitoring
equipment will be necessary. Initial monitoring should be performed from outside the confined
space by inserting a sample probe at appropriately selected openings. Telescopic extension probes
or probes attached to a line can be used to reach remote regions.

Some gases or vapours are heavier than air (for example, hydrogen sulphide) and in unventilated
areas will settle to the bottom of a confined space. Also, some gases are lighter than air (for
example, methane) and will be found around the top of the confined space. As it is possible for
contaminants to settle at different levels, the top, middle and bottom of a space should be
sampled. Horizontal spaces should also be sampled at representative intervals along their length.
Sampling should be such as to reflect accurately the conditions within the confined space.

When considering the appropriate time to monitor the atmosphere, it should be understood that
unless monitoring is undertaken immediately prior to entry, the results may not be relevant and
an unsafe condition may potentially exist.

While pre-entry testing indicates whether the atmosphere in the confined space is acceptable for
entry, atmospheric conditions in the confined space can change, therefore the atmosphere should
be re-tested during the work day.

Testing the atmosphere within the confined space while work is in progress will indicate whether
or not the ventilation system is adequate or if the work processes are making the atmosphere
unsafe.

Continuous monitors provide constant surveillance of atmospheric conditions in a confined space.


Personal direct reading monitors can be used to initially test the space, and then can be worn by
an employee during work to detect atmospheric changes during entry. These monitors should be
fitted with visual and audible alarms to warn employees of the hazard and the need for further
action as set out in the entry procedure and permit.

Re-testing and continuous monitoring of the atmosphere may be necessary:

• If determined under the risk assessment;

• As indicated from the initial testing of the atmosphere;

• Because of the potential for later release or disturbance of hazardous material. Such
material includes sludge, scale or other deposits, brickwork and liquid traps. The
hazardous material may be released if disturbed or if heat is applied. Where harmful

Measurement of Hazardous Substance Page 140


Chapter 8 Other Sampling Tools
contaminants are released, control measures should be based on the assumption that
any further disturbance of the sludge will release more vapours; or

• Because of the work undertaken in the space. For example, heat or fumes from
processes such as welding can build up rapidly in a confined space.

No matter what type of instrumentation is used to assess a confined space (or any other
workplace), it is important that the operator clearly understands the limitations of that
equipment. For example, an explosimeter exhibits different sensitivities towards different
flammable gases or vapours and thus to give accurate results it should be calibrated with known
concentrations of the gas or vapours likely to be present in the atmosphere being assessed.

Moreover, most chemical sensors used for the measurement of contaminant gases are fitted with
filters to minimize cross sensitivity from other contaminants. These filters need to be replaced
according to the manufacturer’s instructions and the potential problems of cross sensitivity well
understood by the instrument operator.

It should also be noted that monitoring is never a substitute for the systematic and verified
isolation of the confined space from any outside source of hazardous material.

8.5.3 Breathing Air Quality


Air supplied or self-contained breathing apparatus (SCBA) relies on the use of air generated by air
compressors to provide the air source. It is important to ensure that the quality of this air is
assessed at regular intervals to check for contaminants such as carbon monoxide and oil mist,
which may have been inadvertently generated by the compressor. If significant pipework is used
to direct the breathing air around a plant, it is not uncommon for condensation to occur in the
pipes, leading to corrosion. Under some circumstances such corrosion can give rise to an
astringent taste in the air.

In most commercial systems filters are installed to control moisture, oil mist and carbon
monoxide, but these have a finite life and need to be changed when expended.

There are varying approaches to monitoring these contaminants in the air but the advent of direct
reading devices has made the inline analysis of carbon monoxide on site relatively easy.

In modern systems continuous monitoring instrumentation for carbon monoxide and built-in
filtration are common. For older systems it may be necessary to sample the breathing air using
external procedures. In such cases air is drawn into a gas sampling bag from which it is extracted
and presented to the instrument (carbon monoxide monitor or indicator tube) for measurement.
Oil mist is usually sampled by passing a known volume of air through a small pore size filter. The
collect oil is either analysed gravimetrically or more accurately by infra-red or gas
chromatographic means.

Measurement of Hazardous Substance Page 141


Chapter 8 Other Sampling Tools
Chapter 9 Presentation of Results

This chapter addresses the basics of how to analyse and present the results of occupational
exposure measurements

9.1 Background
Accurate reporting of data is as important as sample collection as they provide a record of what
was done, where, when, why and by whom. It is therefore important to be clear on the objectives
of exposure monitoring effort, and to keep careful and detailed field notes in a consistent fashion.
Besides reporting findings made, reports should address the meaning of the data and should
include recommendations (including whether further sampling is necessary) as appropriate. Note
that in some jurisdictions such as the US, an exposure evaluation report is considered an exposure
record for which there are specific requirement regarding how long an employer is required to
retain the report.

Preparing an exposure monitoring report requires identifying the intended audience and affected
stakeholders such as:

• Management or person/group requesting the survey.

• Statutory authorities – if involved in the exercise.

• Workforce representatives (unions) – if involved in the process.

• Persons monitored– It stands to reason that individuals who participate in exposure


monitoring be informed of the results and what they mean. This is best done in person
by someone familiar with their interpretation so that concerns can be addressed.

The BOHS also published a guidance document for clear and concise report writing (see
https://www.bohs.org/information-guidance/bohs-resources/ ), which builds on previous
documents prepared by AIOH 2006. This guidance is the basis for BOHS assessment of reports as
part of personal learning portfolios (PLPs) for BOHS certificate and or diploma candidates.

There are also two national standards that address occupational exposure assessment report
structure and content: British Standard BSEN689 and Australian Standard AS 2985 (see text
boxes).

9.2 General Report Content


A well-based occupational hygiene report should be written in easy-to-read language, address all
questions raised in the original scope of work and be able to satisfy an experienced occupational
hygienist that the work was properly conducted and appropriate conclusions drawn. It may take
many forms depending on the objectives of the survey. However, they should generally address
the following:

• Introduction - What the objectives of the survey were. Who did the work and where.
What were the limitations?

Measurement of Hazardous Substance Page 142


Chapter 9 Presentation of Results
• Methods and Materials - How were the samples collected? When did the work take
place? What equipment was used? How was it calibrated? Who analysed the samples?
Attach the lab report to sample report.

• Results and Discussion - What was the process investigated? What did the lab report?
Calculate 8h-TWAs as needed. What do the results mean? What was observed on site
that could explain the results?

• Recommendations - What should be done about the findings? Is additional sampling


needed? Are there regulatory consequences?

• Conclusions - What did the study find?

It’s always a good idea to have a colleague review your report before sending it out. The checklist
provided in the current BOHS guidance is very useful.

BSEN689: Guidance for Assessment of Exposure by Inhalation to Chemical Agents

“Reports shall be written of the occupational exposure assessment and of any periodic
measurement. Each report should give reasons for the procedures adopted in the particular
workplace.
• The report has to contain:

• The name of the person(s) or institutions undertaking the assessment and the
measurements;

• The name the substances considered;

• Name and address of company;

• The description of the workplace factors including the working conditions during the
measurements;

• The purpose of the measurement procedure;

• The measuring procedure;

• The time schedule (date, beginning and end of sampling);

• The occupational exposure concentrations;

• All events or factors liable to influence appreciably the results;

• Details of quality assurance if any;

• Results of the comparison with the limit value (OEL).”

Measurement of Hazardous Substance Page 143


Chapter 9 Presentation of Results
AS2985 Workplace Atmospheres: Method for Sampling and Gravimetric Determination of
Dust for requires test reports to include:

• Identification of sample either as name of person wearing sample or sampler


location.

• Activities being conducted during sampling.

• Any personal protective equipment worn.

• Name of laboratory or authority which performed the test.

• Date on which the test was carried out and sampling duration.

• If uncertainties are not formally derived, for sampling periods greater than 60
minutes the concentration should be reported to two decimal places and three
significant figures for six place microbalances, and to one decimal place and two
significant figures for five-place microbalances.

• Net weight of dust on filter.

• The identity of any reference material used to assist in the validation of the test
results.

• Any observation, in relation to either the test sample or the performance of the test,
which may assist in the correct interpretation of the test results.

• References to the test method used.”

9.3 Notes on Process Description


Where a survey of an area, plant or process is conducted, the following should be described:

• Area/plant/process surveyed, e.g.,” a survey of the area known as cold press or CP was
conducted”.

• Conditions at the time (i.e., personnel, process conditions, risk controls in place) e.g.,
“usual operator unavailable”, “shutdown”, “worst case situation, with no controls”, “as
normal, believed to be a representative working day”, “only Blender No.2 was
operating”, “protective equipment worn other than overalls”.

• Identify any items examined, e.g., “Toolmaster serial number 123”, “machine called the
hot block curer”.

• Number of employees, duration of work shift(s) and task frequency and duration, e.g.,
“9 employees work an 8-hour day, 5-day week with 2 hours overtime worked
infrequently”, “it takes about 30 minutes for 5 bags to be opened and poured daily”.

Measurement of Hazardous Substance Page 144


Chapter 9 Presentation of Results
Diagrams and photographs are useful for clarifying sampling locations and conditions.

9.4 Notes on Results and Discussion


• Results may be presented in the body of the report or as appendices. The level of
information, considering the complexity of the processes, tasks and risks, should satisfy
the technical reader but not unnecessarily complicate the report. Results should be
traceable to the original field notes to enable verification of supporting data (e.g.,
identity of equipment used, calibration, etc.) should this be needed.

• Results of personal sampling should be compared with the relevant exposure standard.
If there is no relevant exposure standard, it will be necessary to either modify or adapt
an existing guideline or develop a guideline. The rationale justifying the guideline used
should be provided.

• Time weighted average (TWA) and short-term excursions limits (STEL), or

• TWA and general excursions limits (if no STEL is set), or

• Peak/ceiling limits.

• Results should be compared with any previous surveys at the premises and data from
similar premises if available, e.g., “The process produced results that are similar to other
coating operations”. An explanation of general trends and unusual high or low trends
should be included.

• The level of risk should be determined (preferably quantitatively) to allow for the
adequacy of controls to be assessed and the prioritization of control options.

9.5 Notes on Conclusions and Recommendations


Conclusions should be drawn about whether or not the relevant exposure standard(s) have been
exceeded and if the work could harm employee health, e.g., “Exposure is likely to approach and
may exceed the exposure standard and there is a significant risk”, “It is believed that exposures
are unlikely to approach the exposure standard and the risk is not significant”, “The risk is
uncertain due to the state of knowledge (or level of exposure)”.

Conclusions should also be drawn about adequacy of control and any further practical actions to
eliminate or reduce the assessed risk so far as is practicable, e.g., “existing controls adequate if
maintained”,” existing controls not adequate and need to be upgraded”.

Recommendations should be selected using the hierarchy of control approach (personal


protective equipment being the last resort) and guidance on an appropriate implementation time
frame (e.g., urgent, short, medium or long term) should be provided. e.g., “Temporarily cease
work on No.123 process until corrective actions (see below) have been implemented”, “Personal
protection is a short-term interim control. In the longer-term engineering controls…”, “A
preventive maintenance programme should be implemented as soon as practicable”, “Periodic
reviews to determine if control measures need to be modified should occur at least once a year”.

Measurement of Hazardous Substance Page 145


Chapter 9 Presentation of Results
Recommendations arising from regulatory requirements or similar guidelines should reference the
relevant source document(s), e.g., “The xxx Occupational Health and Safety (Noise) Regulations
1992 require that…”, “xxx Standard 4114 Spray Painting Booths states that a minimum velocity of
…”. ”

What is fundamental in all cases is that the information collected and evaluated is communicated
to all the stakeholders involved in the exercise in a manner and format that meets their needs or
expectations. In almost all cases this will be different for each of the stakeholders.

9.6 Statistical Analysis Primer


Occupational hygienists may be called upon to use evaluate air sampling measurements, typically
to determine whether measured exposures exceed an OEL, or in some cases, other internal
criteria (often half of a recognized OEL). As suggested in Chapter 4, a collection of results
represent a population of data, and the issue becomes how to evaluate it collectively rather than
value by value. In the case of a prescribed standard, there may be specific approaches and
requirements for data collection and analysis but this is not usually the case.

This primer is intended to provide a brief overview of statistics and statistical tools in the context
of occupational hygiene data. OHTA 501 Students are expected to be familiar with the general
concepts but will not be required to apply them as part of this course. However, competence and
board certifications in occupational hygiene will require a deeper understanding and application of
these and other concepts.

The following is suggested for further reading: Milz S, and J Mulhausen (2015) “Appendix IV:
Descriptive Statistics, Inferential Statistics, and Goodness of Fit” In A Strategy for Assessing and
Managing Occupational Exposures, 4th edition, AIHA, Fairfax, VA.

A 2021 BOHS Webinar on YouTube also provides further information (see


https://www.youtube.com/watch?v=THWxgHoJwU0). Search for BOHS statistics if link does not
work.

In the absence of prescribed approaches, occupational hygienists have used professional


judgement to evaluate air sample results. For example, if all measured exposures are well below
an exposure criterion (half of the OEL is used by many hygienists), the process would be
considered under reasonable control and the results would be judged to be acceptable. This does
not mean that exposures could not exceed the criterion, however if they did, this would be due to
unusual circumstances (e.g., maintenance). Results that approximate the criterion would require
further evaluation and potentially the introduction of better controls since it is more likely to
exceed the desired criterion. A process would be considered out of control if exposures exceeded
the criterion. This should prompt an exposure mitigation program, including temporary use of
respiratory protection until process emissions can be better controlled.

Note that statistical analysis assumes random sample collection, which may not always be the
case in occupational hygiene work. Often, processes vary, or anomalies may occur on the day of
sampling. Moreover, Nonetheless, statistical analysis provides useful insight.

Measurement of Hazardous Substance Page 146


Chapter 9 Presentation of Results
9.6.1 Statistical Distribution
According to parametric statistical theory, most data sets (i.e., measurements) represent a
universe of values that conform to some form of definable distribution. For occupational hygiene
work, we are mostly interested in normal and log normal distribution of data. The latter is where
the data is equally distributed around a central mean, which yields a bell-shaped curve. However,
data distribution becomes skewed when there cannot be negative results, as occurs with air
sampling data. This type of data distribution is known as a log normal distribution, because
plotting log values of the data yields a normal distribution. Figure 9-1 illustrates the difference
between these two types of distribution.

When examining occupational hygiene data, it is reasonable to assume lognormal distribution


unless there is a compelling reason to believe otherwise. This should be verified through online
data analysis tools (e.g., AIHA’s IH Stat) or can be determined by plotting data on log probability
paper (see below).

Figure 9-1 Normal and Lognormal Distributions

permission of the American Industrial


(Source: AIHA 1998 – Used with the

Hygiene Association 2007)


9.6.2 Mean and Standard Deviation
A collection of data can be defined by their mean values, as well as standard deviation. Normal
and lognormal distributions each have their own versions as shown in

Table 9-1. The equations shown below can be used to calculate those values, although most
spreadsheet programs calculate parameters such as mean and standard deviations easily, as does
the AIHA’s IHSTAT spreadsheet (see https://www.aiha.org/public-resources/consumer-
resources/topics-of-interest/ih-apps-tools).

Table 9-1 Normal vs Log Normal Parameters

Normal Log Normal

Arithmetic Mean (AM) Geometric Mean (GM)

Standard Deviation (SDev) Geometric Standard Deviation (GSD)

Measurement of Hazardous Substance Page 147


Chapter 9 Presentation of Results
The equations for these parameters are shown below

Arithmetic Mean (AM)

1
𝑥̅ = ∑𝑥
𝑛 …Equation 9-1
Where x = result
n = number of sampler
𝑥̅ = arithmetic mean

Standard Deviation (SDev)

∑(𝑥 − 𝑥̅ )2 …Equation 9-2


𝑆𝐷𝑒𝑣 = √
𝑛−1

Where SDev = standard deviation

Geometric Mean (GM)

1
ln(𝐺𝑀) = ∑ ln 𝑥
𝑛
1
𝐺𝑀 = 𝑒 𝑛 ∑ 𝑙𝑛(𝑥) …Equation 9-3

Where GM = geometric mean

Measurement of Hazardous Substance Page 148


Chapter 9 Presentation of Results
Geometric Standard Deviation (GSD)

1
ln 𝐺𝑆𝐷 = ∑(ln(𝑥) − ln(𝑥̅ ))2
𝑛−1
1 2 …Equation 9-4
𝐺𝑆𝐷 = 𝑒 𝑛−1 ∑(𝑙𝑛(𝑥)−ln(𝑥̅ ))

Where GSD = geometric standard deviation

Care needs to be taken when analysing data that contains some results reported as less than a
specified quantity (i.e., results are reported as non-detect, ND, or < LOD). Non detect results
represent neither zero nor a value just less that the limit of detection so should necessarily be
discarded when evaluating a collection of data. The University of Montreal has created an online
tool to address this issue (https://espum.umontreal.ca/lespum/departement-de-sante-
environnementale-et-sante-au-travail/production-scientifique/utilitaires/ndexpo/).

The Arithmetic means (AM and GM) scan be compared to OELs directly but are not informative as
to how likely it is that the criterion might be exceeded. Examination of Figure 9-1 indicates that it
is hypothetically possible to exceed any given value, so it is of value to get a sense of how likely
that might be. Standard deviations (SDev) and geometric standard deviations (GSD) provide some
insight into this.

Standard deviations essentially indicate how widely spread the underlying data is. Geometric
standard deviation values also can provide an insight into the nature of the underlying data as
shown on Table 9-2.
Table 9-2 Rules of Thumb GSD Values

GSD Value Comment

1.0 No variability

1.5-2.0 All data are same values-why?

2.0-3.5 Very little variability

> 3.5 Moderate variability

Nowadays, these means and standard deviations (normal and log normal) are easily calculated in
most spread sheet applications. Online tools such as AIHA’s IHSTAT (https://www.aiha.org/public-
resources/consumer-resources/topics-of-interest/ih-apps-tools) simplify statistical calculations
and encourage the application of statistical concepts for evaluating data.

Knowledge of AM and SDev, as well as GM, and GSD, allow inferential analysis of the underlying
data by estimating various parameters such as confidence levels, and MVUE.

Measurement of Hazardous Substance Page 149


Chapter 9 Presentation of Results
9.6.3 Confidence Levels
Means and standard deviations allow an estimation of likely values within the populations they
define. For example, it possible to derive a point estimate below which one could expect 95% of
measurements. This would be termed a 95% upper confidence limit (95% UCL).

In some instances, estimated 95% UCL values are compared to exposure criteria to determine
whether a process is adequately controlled, particularly where the process involves substances
that exhibit acute toxicity.

It is easier to use spreadsheets or online tools such as AIHA’s IHSTA to estimate confidence limits.
However, they can also be estimated using log probability plots of data

9.6.4 Minimum Variance Unbiased Estimate (MVUE)


Minimum variance unbiased estimate (MVUE) is especially useful in those cases when the data is
heavily influenced by high results. The MVUE provides an unbiased estimate of the true arithmetic
mean of a lognormal dataset. When the data has little variability (GSD <2.0) the GM and MVUE
(AM) will be close together, however as variability increases (GSD 2.0 – 3.5) the MVUE (AM) will
give a better estimate of the central point of the exposure profile (Figure 9-2).

Figure 9-2 AM and GM of Lognormal Distributions

permission of the American Industrial Hygiene


(Source: AIHA 1998 – Used with the

Association 2007)

MVUE values are difficult to calculate because of the iterative nature of its calculation.

Measurement of Hazardous Substance Page 150


Chapter 9 Presentation of Results
9.6.5 Log Probability Plots
Log probability can be sued to evaluate whether a data set is log normally distributed.

The plot can be done manually by ranking the results, 1 being used for the lowest value,
determining their plotting position as follow:

𝑅𝑎𝑛𝑘
𝑃𝑙𝑜𝑡𝑡𝑖𝑛𝑔 𝑃𝑜𝑠𝑖𝑡𝑖𝑜𝑛 (%) = 𝑥 100%
𝑛+1
…Equation 9-5
Where Rank is rank of result with lowest = 1

and, n = number of results

The resulting data can then be plotted on log normal paper, with % position on the y-axis, and
corresponding result on the x-axis. A linear plot indicates the data is log normally distributed. See

Figure 9.2 below:

Figure 9.2: Example of Log Probability Plot


Cumulative %

The GM can be found by reading off the concentration at the 50th percentile, so in the above
case, it would be 0.06 ppm (assuming the plot data is in ppm).

Measurement of Hazardous Substance Page 151


Chapter 9 Presentation of Results
Deriving the GSD requires either dividing the concentration at the 84th percentile by that of the
50th percentile, or by that of the 50th percentile by the 16th percentile. Results may not always
be symmetrical due to calculations to plot best fit line. In the above example, GSD is around 4. This
indicates a fair amount of variability. Perhaps there are outliers, or perhaps the group sampled is
not as homogeneous as anticipated.

The 95th percentile (used as a measure of compliance by some organisations) can also be read off
the graph (around 0.40 ppm in the example above)

Log probability plots are easily done on software available on line such as AIHA’s IH Stat
(https://bit.ly/3SVKEfQ). They can also be done on linear plots on Excel, though you may need to
work with log converted concentrations, and will need to convert back when trying to derive
actual values (e.g., GM, 95%-ile) off the chart.

Measurement of Hazardous Substance Page 152


Chapter 9 Presentation of Results
Chapter 10 Biological Monitoring

10.1 Fundamentals of Biological Monitoring


Biological exposure monitoring, or biological testing, is a way of determining how much of a
particular contaminant has actually entered, and has been taken up by, the body from all routes of
exposure. A number of substances can be measured in this way. It can also provide information on
cumulative exposures experienced over a long period of time or environments where air sampling
presents challenges such as due to equipment limitations or scheduling difficulties (e.g., firefighter
exposures during live fire response). The advantages of such an approach include:

• It provides additional information where there is a respiratory hazard

• It can be used where the main route of exposure is not inhalation

• It can highlight deficiencies in the wearing of personal protective equipment, i.e.,


respirators and gloves and/or clothing

• It provides evidence for medical assessment

In contrast, workplace air monitoring and comparison of the results with exposure standards
provides information about the probable exposure of workers to inhalation hazards. It does not
provide information about the other exposure routes of skin absorption, ingestion, nor
information about any non-work-related exposures.

Biological monitoring is one of the three tools used in the prevention of disease from hazardous
substances in the work environment, the other two being occupational hygiene or environmental
monitoring and health surveillance.

Biological monitoring means the assessment of exposure to chemicals (substances) that are
present in the workplace, through the measurement of appropriate determinants in biological
specimens from exposed workers. In most cases, the specimen used for biological monitoring is
urine, blood or exhaled air.

The risks associated with the obtaining and handling of bodily fluids, in terms of potential
exposure to possible pathogens, i.e., HIV, Hepatitis, viruses etc. have to be considered.

In many countries only a qualified doctor or nurse can obtain such samples. Local advice must be
sought before such work is to be carried out.

Biological monitoring can be divided into:

• Direct biological monitoring also referred to as biological monitoring of exposure

• Biological effect monitoring

Measurement of Hazardous Substance Page 153


Chapter 10 Biological Monitoring
10.2 Direct Biological Monitoring
The purpose of direct monitoring is to assess the health risk through the evaluation of internal
dose of the chemical in question with the aim of ensuring the exposure does not reach levels that
can cause adverse effects.

The direct analysis of the contaminant is undertaken in the specimen:

• Blood – e.g., for lead and mercury

• Urine – e.g., for cadmium and MOCA (methylene bis-orthochloroaniline)

• Hair and nails - e.g., for arsenic

• Breast milk– e.g., for pesticides and Polychlorinated Biphenyls (PCBs)

• Expired air – e.g., for carbon monoxide and organic solvents – e.g., benzene or analysis
of its metabolites

• Blood – carboxyhemoglobin from carbon monoxide

• Urine – mandelic acid from styrene

10.3 Biological Effect Monitoring


Biological effect monitoring is aimed at identifying early and reversible biochemical changes
resulting from exposures, i.e., no detrimental effect has occurred but one or more measurable
biochemical changes has occurred. The degree of change is less than that which leads to injury and
is not associated with a known irreversible pathological effect.

Some examples of biological effect monitoring are:

• Zinc protoporphyrin in blood – these levels increase with exposure to lead, because lead
inhibits the biosynthesis of heme.

• Cholinesterase activity in red blood cells and plasma – exposure to organophosphate


pesticides depresses cholinesterase activities.

Biological effect monitoring is not health surveillance through which individuals with early signs of
adverse health effects are identified.

10.4 General Considerations


The extent and rate of absorption of a chemical after exposure depend on the properties of the
chemical, especially its solubility in lipids and water, and the route of exposure. It is also important
to select the appropriate specimen for the determinant of interest. For example, blood may be
more appropriate than urine for a determinant with a biological half-life of many months, while
breath may be more appropriate for volatile determinants.

Measurement of Hazardous Substance Page 154


Chapter 10 Biological Monitoring
Once absorbed, a chemical is distributed and spreads into various tissues depending on the
susceptibility of the tissue due to variations in pH, permeability etc. Very water-soluble chemicals
may be distributed throughout the total body water, while lipophilic (attract non polar organics
such as fats and oils) may concentrate in the body fat, or in other lipid tissues such as the brain.

The loss of chemical from the body or elimination depends on metabolism and excretion.
Chemicals may be eliminated by numerous routes including fecal, urinary, exhalation, perspiration
and lactation.

A chemical may be excreted from the body without metabolism, i.e., the particular chemical can
be measured directly. In other cases, the chemical may be metabolized through oxidation,
reduction, hydrolysis or combination of these followed by often very complex biochemical
reaction in the body. Hence the choice of the indicator of exposure and even the timing of when
to take a sample is critical.

10.5 Biological Half-Life


The biological half-life of a substance is the time required for half of that substance to be removed
from the body by either a physical or a chemical process. The half-lives for different substances
vary significantly and hence the importance of the correct sampling time cannot be over
emphasized.

10.6 Sampling Time


The timing of biological samples can be very important. Substances absorbed into the body are
removed at different excretion rates. The concentration of some determinants can change rapidly,
so in these cases sampling time must be observed and recorded carefully. On the other hand, a
determinant that accumulates slowly may not need a specific sampling time.

An exposure that occurs through the ingestion route typically takes longer to enter the blood
stream than an exposure through the inhalation route. So, it is possible to collect the sample too
soon after the exposure occurs, although this is not usually an issue in relation to workplace
exposures.

Table 10-1 Recommended Sampling Times

Sampling Time Recommended Collection

Prior to shift 16 hours after exposure ceases

During the shift Any time after 2 hours of exposure

End of shift As soon as possible after exposure ceases

End of the work week After 4 or 5 consecutive working days with exposure

Discretionary At any time

Measurement of Hazardous Substance Page 155


Chapter 10 Biological Monitoring
Practical guidance on the interpretation of sampling times is given by the ACGIH (2007). While the
ACGIH provides the recommendations as listed in Table 10-1 Recommended Sampling Times, it is
important to understand that this information is for guidance only and an understanding of the
substance being monitored is critical if accurate and meaningful results are to be achieved.

The UK Health & Safety Executive (HSE) in the Guidance Note EH56 “Biological Monitoring for
Chemical Exposures in the Workplace” (HSE 1992) uses the following Table 10-2 Optimum Time
for Collecting Samples) to provide advice on the timing of sample collection.

Table 10-2 Optimum Time for Collecting Samples

Source: HSE – Reproduced with permission


Half Life Optimum Time for Taking Samples

<2 Hours Concentration changes too fast – not suitable

2 to 10 Hours End of shift or next morning

10 to 100 Hours End of shift at end of week

>100 Hours Random sampling acceptable

10.7 Urine Specimen Acceptability


The concentration of urine can have a marked effect on the results of the analysis of the
contaminant. Sample results can be corrected for urine concentration in one of two ways:

• By adjusting for the specific gravity of the sample; or

• By correcting for the creatinine level in the urine, as creatinine excretion from the body
occurs naturally at a nearly constant rate.

The World Health Organisation has adopted the following guidelines for acceptable limits to assist
in overcoming the issues associated with highly diluted and highly concentrated urine samples:

Creatinine concentration: >0.3 g/L and <3 g/L


or
Specific Gravity: >1.010 and <1.030
Samples outside these guidelines should be discarded and another sample collected.

Some Biological Exposure Indices BEIs® for determinants whose concentrations is dependent on
urine output are expressed as relative to creatinine concentration. For other determinants
correction for urine output is not appropriate.

Measurement of Hazardous Substance Page 156


Chapter 10 Biological Monitoring
10.8 Biological Standards

10.8.1 Biological Exposure Indices


Similar to TLVs®, the results of biological monitoring are compared against Biological Exposure
Indices or BEIs®. The main source of BEIs® is from the ACGIH in their handbook Threshold Limit
Values and for Chemical Substances and Physical Agents and Biological Exposure Indices (ACGIH
2019).

Biological Exposure Indices (BEIs®) are guidance values for assessing biological monitoring results.
BEIs® represent the levels of determinants that are most likely observed in specimens collected
from healthy workers who have been exposed to chemicals to the same extent as workers with
inhalation exposure at the TLV®.

In a similar fashion to TLVs®, BEIs® are to be used as guidelines in the evaluation of occupational
hygiene health hazards. BEIs® do not indicate a sharp distinction between hazardous and
nonhazardous exposures. Due to the often-varied nature of concentration in biological specimens’
great care and caution must be exercised in the interpretation of the results from a single
specimen.

BEIs® apply to 8-hour exposures, 5 days per week. The BEI® Committee does NOT recommend
adjusting or applying a correction factor to the BEIs® for altered or extended shift patterns.

Use of BEIs® should only be done by experienced occupational health professionals in consultation
with the associated documentation for them. The BEI® is a guideline for the control of potential
health hazards for workers and the values are inappropriate for use for the general public and for
non-occupational exposures. In the application of BEIs® reference must be made to the current
edition of the Documentation of the Threshold Limit Values and Biological Indices from the
ACGIH®.

10.8.2 Notations
A notation is a designation that appears as a component of the adopted BEI® value to provide
additional information with respect to the particular chemical:

“B” = Background

The determinant may be present in biological specimens collected from subjects who have
not been occupationally exposed, at a concentration which could affect the interpretation
of the result.

“Nq” = Non-quantitative

Biological monitoring should be considered for this compound based on the review;
however, a specific BEI® could not be determined due to insufficient data.

“Ns” = Non-specific

Measurement of Hazardous Substance Page 157


Chapter 10 Biological Monitoring
The determinant is non-specific, since it is also observed after exposure to other chemicals.

“Sq” = Semi-quantitative

The biological determinant is an indicator of exposure to the chemical, but the quantitative
interpretation of the measurement is ambiguous.

These determinants should be used as a screening test if a quantitative test is not practical or as a
confirmatory test if the quantitative test is not specific and the origin of the determinant is in
question.

10.8.3 UK Limits
In the UK the HSE has established a system of non-statutory biological monitoring guidance values
as an aid in the interpretation of biological monitoring data.

Biological Monitoring Guidance Values (BMGVs) are set where they are likely to be of practical
value, suitable monitoring methods exist and there are sufficient data available. The type of data
that are available will vary between substances and therefore the route taken to deriving the
BMGV will vary between substances. BMGVs are either based on a relationship between biological
concentrations and health effects, between biological concentrations and exposure at the level of
the WEL or are based on data collected from a representative sample of workplaces correctly
applying the principles of good occupational hygiene practice. The technical basis for each BMGV
will be clearly described in supporting documentation such as an EH64 summary or other
guidance.

BMGVs are non-statutory and any biological monitoring undertaken in association with a guidance
value needs to be conducted on a voluntary basis (i.e., with the fully informed consent of all
concerned). BMGVs are intended to be used as tools in meeting the employer’s primary duty to
ensure adequate control under COSHH. Where a BMGV is exceeded, it does not necessarily mean
that any corresponding airborne standard has been exceeded nor that ill health will occur. It is
intended that where they are exceeded this will give an indication that investigation into current
control measures and work practices is necessary.

Of course, that is not necessarily to say that because biological monitoring results are below a
particular guidance value an employer need take no further action to reduce exposure; but it
should be noted that BMGVs are not an alternative or replacement for airborne occupational
exposure limits.

10.9 Confidentiality
There are several ethical and confidentiality issues that must be considered and implemented
before commencing a biological monitoring programme.

• The method should be appropriate for the requirements of the investigation.

• The procedures should not threaten the health of the participant.

Measurement of Hazardous Substance Page 158


Chapter 10 Biological Monitoring
• The risk of using invasive methods must be justified by the benefits.

• The informed consent from the participants is needed. This consent must only be given
when the participant feels no fear of reprisals if their consent is not given.

• Results of the monitoring should be kept confidential and shared only with the
occupational health professional and the participant.

Measurement of Hazardous Substance Page 159


Chapter 10 Biological Monitoring
Appendix A Introduction to Physiology and Toxicology

This section contains a basic review of physiology and toxicology. This subject is covered in
greater detail in student manual of the OHTA module W507 Health Effects of Hazardous
Substances.

A.1 The Human Body


The human body has many different interacting sub-systems. It is important to have some
understanding of the function and features of these systems to appreciate the effects that
exposure to occupational hygiene hazards and in particular exposure to hazardous substances may
have.

A.1.1 Cardiovascular System


The main components of the cardiovascular or circulatory system are the heart, the blood and the
blood vessels. The blood vessels consist of arteries, capillaries and veins.

Arteries bring the oxygenated blood, pumped from the heart, to the tissues and the veins bring
the deoxygenated blood back to the heart. Blood passes from arteries to veins through capillaries,
which are the thinnest and most numerous of the blood vessels.

A.1.2 Digestive System


The digestive system takes in food, digests it to extract energy and nutrients for the body and
expels the remaining waste. It consists of:

• Upper gastrointestinal tract – mouth, esophagus and stomach

• Lower gastrointestinal tract – small and large intestine.

• Related organs including liver, gall bladder and pancreas.

A.1.3 Endocrine System


The endocrine system is a control system of ductless glands that secrete “instant messengers” or
hormones that circulate within the body via the bloodstream to affect distant cells within specific
organs. Endocrine glands secrete their products immediately into the blood or interstitial fluid,
without storage of the chemical.

Hormones act as messengers and are carried by the bloodstream to different cells in the body
which then interpret the message and act on them. Examples include the pituitary gland, the
thyroid gland, adrenal gland and the pancreas and gonads.

A.1.4 Immune System


The immune system protects the body from infection by creating and maintaining barriers that
protect bacteria and viruses from entering the body. If a pathogen breaches the barriers and gets

Measurement of Hazardous Substance Page 160


Appendix A Introduction to Physiology and Toxicology
into the body the innate immune system is equipped with specialized cells that detect, and often
eliminate, the invader before it is able to reproduce, potentially causing serious injury to the host.
A pathogen that successfully invades the innate immune cells faces a second, adaptive immune
system. It is through the adaptive response that the immune system gains the ability to recognize
a pathogen and to mount stronger attacks each time that pathogen is encountered. Examples of
disease that arise from damage or impairment of the immune system are Hepatitis, Ebola,
Acquired Immune Deficiency Syndrome (AIDS), Influenza, Cholera, Typhoid and Malaria.

A.1.5 Integumentary System


The integumentary system comprises of the skin (cutaneous membrane) and its accessory
structures of hair, nails and exocrine glands. There are three layers of skin – epidermis, dermis and
subcutaneous tissue. The cutaneous glands include the sweat glands, oil glands, glands of the ear
and the mammary glands.

Figure 10-1 Diagram of the Layers of the Human Skin

Source: Tranter 1999 – Reproduced with permission

The skin is often known as the largest organ of the body and as the interface with the
surroundings it provides protection against the physical hazards such as heat, radiation and
abrasion, chemicals and bacteria. Its other important functions are insulation and temperature
regulation, sensation and Vitamin D and B synthesis.

A.1.6 Lymphatic System


The lymphatic system is a complex network of lymphoid organs, lymph nodes, lymph ducts and
lymph vessels that produce and transport lymph fluid from tissues to the circulatory system. It is a
major component of the immune system.

Measurement of Hazardous Substance Page 161


Appendix A Introduction to Physiology and Toxicology
The lymphatic system has three interrelated functions:

• Removal of excess fluids from body tissues.

• Absorption of fatty acids and subsequent transport of fat to the circulatory system.

• Production of immune cells (such as lymphocytes, monocytes and antibody producing


cells called plasma cells).

A.1.7 Muscular System


The muscular system is the biological system that allows us to move. It is controlled by the
nervous system, although some muscles (such as the cardiac muscle within the heart) can be
completely autonomous.

In general, the function of muscle is to produce movement, maintain posture, stabilize joints and
to generate heat.

Muscles are attached to bone by tendons and other tissues. They exert force by converting
chemical energy into force. Nerves link the muscles to the central nervous system.

A.1.8 Nervous System


The nervous system is often divided into the central nervous system (CNS) and the peripheral
nervous system (PNS). The CNS consists of the brain and the spinal cord and functions as the
body’s control centre. The PNS consists of all of the other nerves and neurons in the body that do
not lie within the CNS and carry electrical impulses to and from the spinal cord and cranial nerves
that carry electrical impulses to and from the brain.

The peripheral nervous system is divided into the somatic nervous system and the autonomic
nervous system.

The somatic nervous system is responsible for coordinating the body's movements, and also for
receiving external stimuli. It is the system that regulates activities that are under conscious
control.

The autonomic nervous system is then split into the sympathetic division, parasympathetic
division, and enteric division. The sympathetic nervous system responds to impending danger or
stress, and is responsible for the increase of one's heartbeat and blood pressure, among other
physiological changes, along with the sense of excitement one feels due to the increase of
adrenaline in the system. The parasympathetic nervous system, on the other hand, is evident
when a person is resting and feels relaxed, and is responsible for such things as the constriction of
the pupil, the slowing of the heart, the dilation of the blood vessels, and the stimulation of the
digestive and genitourinary systems.

The role of the enteric nervous system is to manage every aspect of digestion, from the esophagus
to the stomach, small intestine and colon.

Measurement of Hazardous Substance Page 162


Appendix A Introduction to Physiology and Toxicology
A.1.9 Reproductive System
The role of male and female reproductive systems is to produce offspring. The male reproductive
organs include the sperm producing region – the testes located inside the scrotum and the duct
system comprising the epididymis, the vas deferens and the urethra.

The female reproductive system consists of the internal organs including the ovaries, fallopian
tubes, uterus, cervix and vagina.

A.1.10 Respiratory System


The respiratory system consists of the airways, the lungs and the respiratory muscles that mediate
the movement of air into and out of the body. Inhaled air passes from the nose and mouth
through the trachea and into the branched structures of the lungs called bronchi.
Figure 10-2 Respiratory System

Source: Tranter 1999 – Reproduced with permission

Air then travels along the bronchioles to its ending (the terminal bronchiole) which is covered in
tiny multi lobed sacs called alveoli where most of the gas exchange occurs.

A.1.11 Skeletal System


The human skeleton is made of 206 individual or joined bones, such as the skull, supported and
supplemented by a structure of ligaments, tendons, muscles, cartilage and other organs.

The most obvious function of bone is to support the body. It is also the site of hematopoiesis, the
manufacture of blood cells that takes place in bone marrow and why bone marrow cancer is very
often a terminal disease. The skeleton is also necessary for the protection of vital organs. Human

Measurement of Hazardous Substance Page 163


Appendix A Introduction to Physiology and Toxicology
movement is dependent on the skeletal muscles which are attached to the skeleton by tendons.
Without the skeleton to give leverage movement would be greatly restricted. Bone also serves as
a storage deposit in which fat and minerals such as calcium and phosphorous can be stored and
retrieved.

A.1.12 Urinary System


The urinary system is the organ system that produces, stores and eliminates urine. In humans it
includes two kidneys, two ureters, the urinary bladder, two sphincter muscles and the urethra.

The kidneys are one of the various organs (together with the lungs, intestine and skin) that
participates in the elimination of the wastes of the organism. The kidneys are bean-shaped organs
about the size of a bar of soap. They are near the middle of the spine, just below the ribcage. They
are situated behind the organs of digestion within the abdominal cavity. Situated on the superior
surface of each kidney is an adrenal gland.

A kidney consists of about 1 million filtering units termed nephrons, each consisting of a
glomerulus, ball-shaped network of capillaries, and a network of tubules. Blood plasma is filtered
by the glomerulus, and the resultant "prourine" passes through the tubular system where water,
and nutrients are reabsorbed under the supervision of hormone activity and the autonomic
nervous system.

Humans produce about 1.5 litres of urine over 24 hours, although this amount may vary according
to circumstances. Increased fluid intake generally increases urine production, while increased
perspiration and respiration may decrease the amount of fluid excreted through the kidneys. A
reduced intake of water will normally result in less urine production as well. Some medications
interfere directly or indirectly with urine production, such as diuretics.

The kidney plays a crucial role in regulating electrolytes in the human blood (e.g., sodium,
potassium, calcium). pH balance is regulated by the removal of excess hydrogen ions (H+) from
blood. In addition, they remove urea, a nitrogenous waste product from the metabolism of
proteins from amino acids. The metabolism process forms ammonia which is transported by blood
to the liver and detoxified to a less harmful byproduct called urea.

A.2 Routes of Entry


There are four primary routes of entry for contaminants into the human body;

Inhalation: The requirements of a man in a normal day are approximately 3.4 kg food and water
(water is obtained in the food we eat and as direct ingestion). For light physical work an average
person breathes in between 1-1.2 m³ of air per hour. This rate would be much higher for heavy
physical exertion.

Therefore, it is easy to understand why inhalation is by far the most common route of entry due to
both the volume of air coming into contact with the large surface area of the lungs and the thin
cell layer in the lungs separating the air from the blood, with skin absorption next (especially
pesticides) and ingestion last. Inhalation is the major route of entry of dusts, fumes, mists, gases
and vapours into the body.

Measurement of Hazardous Substance Page 164


Appendix A Introduction to Physiology and Toxicology
Skin Absorption (includes injection): Skin absorption via direct contact with chemicals especially
organic solvents and organophosphate pesticides is the second most important route of entry to
the body.

Eye: The eye is a relative minor route of entry into the body. It should also be noted that the eye is
also at risk from direct contact with chemicals.

Ingestion: Ingestion is usually a relatively minor route of absorption of chemicals in the workplace.
It is commonly as a result of an accidental ingestion, or from poor personal hygiene e.g., eating
with dirty/contaminated hands. In some workplaces inadvertent ingestion or skin absorption can
result from contact with contaminated surfaces.

It should be noted that insoluble aerosols can end up in the digestive tract from where they can be
absorbed into the body. Additionally, involuntary ingestion as a result of clearance mechanisms in
the upper respiratory tract can also be another route of entry, especially in the case of large
particles of toxic substances.

A.3 Target Organs and Systems


There are numerous target organs for contaminants in the human body such as:

• Heart • Liver • Bones

• Lungs • Brain • Thyroid

• Kidneys • Central Nervous • Blood


System

Target organs are defined as organs in which critical effects are observed as the result of exposure
to a harmful input. There are many identifiable instances of inputs which affect a number of
critical organs. Which they affect depends upon the circumstances of exposure, the interplay of
defense processes and the susceptibility of the individual, as well as the tissues of the target
organ. Thus, in discussing effects it is required that all possible target organs are considered.

The definition of 'target organs' must, necessarily, be wide, and must include, where appropriate,
systems and tissues as well as organs.

For example, the target organ of hydrogen sulphide, which attacks the nerve tissue and causes
respiratory paralysis, might be categorized as the central nervous system.

Crocidolite induces serious disease of the pleura and peritoneum (the tissue lining in the inner
surface of the chest wall, and the lungs or the inner surface of the abdominal cavity and the
abdominal organs). In this instance the pleura and peritoneum are the target organs.

A series of target organs and an outline of their principal functions are given in Table A-3.

Measurement of Hazardous Substance Page 165


Appendix A Introduction to Physiology and Toxicology
Table A-3 Target Organs, With an Outline of Their Principal Functions

Target Organ Principal Functions

Skin Protects against friction, water/fluid loss, entry of harmful inputs; thermal
insulation; self-greasing by means of sebaceous glands; thermoregulatory
by means of sweat glands; receives afferent information.

Respiratory tract Oxygen and carbon dioxide exchange; defense against aerosols; warming
and moistening of incoming air; excretion of gases, vapours.

Blood, plasma, blood- Metabolism: transformation and conjugation.


forming organs:
Chief transport system for oxygen, carbon dioxide nutrients, heat and
circulatory system
fluids.

Kidney, urinary tract Excretion: Water, salts and nitrogenous wastes (includes homeostasis
as well as bio- dumping).

Secretion: Hormones for controlling blood pressure and production of


red blood cells.

Metabolism: Transportation and conjugation.

Liver Secretory: a) Bile - contains waste non-nutrients, aids digestion


b) Heparin - anti-coagulant for blood

Storage: a) Vitamins
b) Iron (for hemoglobin)
c) Glycogen-energy store substance

Metabolism: Transformation and conjugation

Brain and nervous system Information processing and control of bodily activities.

Bone Support framework for movement and protection (certain bones house
blood-forming organs; but those are functionally separate from bone).

Gut Input of nutrients; digestion; excretion of non-nutrients; defensive


processes of gastric-acid barrier.

Lymphoid system and Tissue drainage; filtration; site of defensive processes such as immune
lymphatics response and phagocytosis.

Ductless glands Such as thyroid, parathyroids, adrenals (suprarenal); produce hormones -


substances exercising key control over function and morphology.

A.4 Concept of Dose Response


"No substance is a poison by itself, it is the dose that makes a substance a poison." Paracelsus
1540.

Ideally dose should be defined as the concentration of a substance at the site of effect, regard
being made for the time for which the substance concentration is maintained. For practical

Measurement of Hazardous Substance Page 166


Appendix A Introduction to Physiology and Toxicology
purposes dose refers to the amount of a substance to which a person is exposed and is a
combination of the amount or concentration of exposure and the duration of exposure. Exposure
can arise from inhalation (most common route) or skin absorption (common with some
substances) or via eye absorption (rare).

In simplistic terms dose can be expressed as:

Dose = Concentration of exposure x duration of exposure …Equation A-1

This simplistic equation does not account for the following factors:

• Dose may be less than the amount inhaled if most is exhaled without any absorption
(e.g., many gases).

• Heavy physical workload results in higher breathing rates than light workloads and thus
have higher doses.

• Dose may depend on an individual being a mouth or nose breather.

• Additional exposure may come from non-occupational sources (carbon monoxide from
smoking).

Effect can be any observable, biological change associated with the input concerned, and ideally it
should be quantifiable. It is implicit in dose-effect relations that effect is related to and caused by
the dose.

Effect does not necessarily denote an adverse biological change, but embraces any biological
change. Certain effects can be beneficial and only become adverse if the dose is excessive or
remains for a critical period of time.

Types of toxic effects include acute, chronic, local and systemic.

Acute or immediate effects occur during or immediately after exposure and last for a short period
of time. Examples of acute effects include the immediate eye and respiratory tract response to
exposure to, and inhalation of, chlorine or burns to the skin caused by direct contact with strong
acids or alkalis.

Chronic effects are long lasting and may be, but not necessarily, permanent. Some examples of
chronic exposures are pneumoconiosis from long term exposure to coal dust, silicosis after
exposures to quartz dusts.

Local effects occur at the point of entry to the body of the toxin and systemic effects are
associated with distant target organs (e.g., with lead the main route of entry is by inhalation but
the toxic effect is upon the blood forming process, nervous system, kidneys and reproductive
functions).

Critical organ concentration seems, given the present state of knowledge, to be the parameter of
greatest utility in estimating dose. Whole body concentration provides a less useful criterion,
because the organs in which greatest accumulation occurs may not be critical organs.

Measurement of Hazardous Substance Page 167


Appendix A Introduction to Physiology and Toxicology
Bone, for example, accumulates lead, but the critical organ is bone marrow, which is functionally
separate from the bone which surrounds it.

At some time in the future, it will, no doubt, be possible to estimate dose in terms of critical cell
concentrations - or subcellular concentration - but at present this is impracticable.

There are complexities in the specification of effect, since certain effects, such as death, are of an
all-or-none character, while others are of a graded nature, such as occupational deafness.

Specification is further complicated by the fact that certain all-or-none effects (cancer, for
example) require only a trigger. Once triggered they continue by self-propagation or by the other
processes independent of the dose of the triggering input. On the other hand, many observable
and gradable effects are both trivial and reversible.

However, the complexities do not end here. The specification of dose needs to take account of all
possible modes of input, and the non-occupational as well as the occupational possibilities. For
example, in the case of metals like lead, in most if not in all countries, input by ingestion from the
normal diet is inevitable. Any occupational exposure, probably by inhalation, will be supplemented
by the non-occupational dose. Combination of the two may cause a critical organ concentration to
be reached in the bone marrow or in other organs.

A.4.1 Dose Response


Dose response is that proportion of a human population which experiences a specific effect
following exposure of the total population to specified harmful contaminant. The correlation of
the response with estimates of the dose provides a dose-response relation, which is normally
expressed as a graph, with percentage of population affected on the y axis and estimated dose on
the x axis (Figure 10-3 Dose Response Curve).

A.4.2 No Observed Adverse Effect Level


The “no observed adverse effect level” (NOAEL) is the term used to define that point below which
adverse effects cannot be observed. Effects, particularly adverse effects, are generally
manifestations of the change in an organ and particularly the cells of the organ.

In toxicology, the NOAEL is specifically the highest tested dose or concentration of a substance at
which no adverse effect is found in the exposed test species (usually animals or cells).

This level is commonly used in the process of establishing a dose response relationship, a
fundamental component in most risk assessment strategies.

Another important toxicological concept is “lowest observed adverse effect level” (LOAEL) or the
lowest dose or concentration that causes any observed adverse effect. Thus, by definition the
NOAEL is less than the LOAEL.

As these determinations of exposure and effect have generally been established in species other
than humans, various safety factors or uncertainties are applied before this data is used in the
establishment of workplace exposure standards.

Measurement of Hazardous Substance Page 168


Appendix A Introduction to Physiology and Toxicology
A.4.3 Threshold
The term "threshold" is used in toxicology to describe the dividing line between no-effect and
effect levels of exposure. It may be considered as the maximum quantity of a chemical that
produces no effect or the minimum quantity that does produce an effect. Every change produced
by a chemical, whether it is beneficial, indifferent, or harmful, has a threshold. (Perhaps the word
"change" should be qualified with an adjective such as "biological" or "clinical" to anticipate the
reader with a literal bent who will say that the mere exposure of an organism to a chemical
represents a change and that such a change obviously does not have a threshold).

The precise threshold for a given effect can, and usually does, vary within certain limits with
species, with individuals within a species, and perhaps even with time in the same individual.

For a given population, as illustrated by the dose response relationship (see Figure 10-3 Dose
Response Curve), it is clear that thresholds exist because it can be determined experimentally that
certain low levels of exposure will produce no detectable effect, and that as the dosage is
increased the effect appears.

Since the dose-response relationship is a continuum, somewhere between the experimental no-
effect and effect levels is the turning point known as the threshold.

Dose-response curves typical of those plotted from data obtained in chronic toxicity experiments
exist for a number of contaminants. It is very important to recognize that such a curve is drawn
from only several points, one for each exposure group in the experiment. The greater the number
of exposure groups, the greater the number of points, and hence, the greater the accuracy of the
curve that is drawn. But without an infinite number of points, the precise shape of the dose-
response curve cannot be known.

The curve is interpreted as follows: with chronic exposure of increasing doses up to the threshold,
no effect is detectable because some biochemical or physiologic mechanism, handles the chemical
in a manner that prevents an effect from occurring. At the threshold, the defense mechanism is
saturated, or in some manner
overwhelmed, for the more Figure 10-3 Dose Response Curve
Source: Tranter 1999 – Reproduced with

susceptible individuals and the effect


begins to appear. With increasing
doses, increasing numbers of
individuals show the effect until finally
a dose is reached where all of the
members of the population show the
effect (ceiling level).
permission

The threshold concept is of great


importance to toxicologists because it
permits them to make judgements about the potential hazard, or lack thereof, to humans from
exposure to chemicals.

Another toxicologic question relates to the shape of dose-response curves for carcinogens as they
approach zero dose. The inability of toxicology to answer this question by experiment has given

Measurement of Hazardous Substance Page 169


Appendix A Introduction to Physiology and Toxicology
rise to a scientific controversy concerning whether or not there is a threshold (no-effect level) for
carcinogenic effects. If there is no threshold, extension of the experimentally derived dose-
response curve to zero effect would yield a line that would go through the origin (zero dose). If
there is a threshold, the extended line would meet the abscissa [x axis] at some point greater than
zero dose.

In regard to carcinogens, it is important to note that it is rare to have any data except for high
doses, so the estimate of the shape of the dose response curve below the lowest actual data point
must typically cover many orders of magnitude. Where a threshold cannot be identified, limits are
generally risk based and dependent upon the dynamics of the particular substance.

It is extremely important, as background to all considerations of the threshold, to recognize that


detectable biological effects are not universally adverse.

What should be recognized is that in any group of test subjects there are some susceptible
individuals (hypersensitive) who are affected at low concentrations of the test contaminant and
there are also some highly resistant individuals (hyposensitive) who are not affected at high
concentrations but there are the vast majority of “average” individuals in the middle (Figure 10-4
Variability of Human Exposure to Dose).

Figure 10-4 Variability of Human Exposure to Dose

Source: AIOH 2007 – Reproduced with permission

Consequently exposure standards tend to be based on dose response relationships applicable to


“average” individuals and thus it is important to recognize that some hypersensitive individuals
may be in a work group and that they may suffer adverse health effects at exposures below the
recognized exposure standard.

Measurement of Hazardous Substance Page 170


Appendix A Introduction to Physiology and Toxicology
A.4.4 Threshold of Intoxication
For each substance, no matter how toxic, there exists a dose level called the threshold of
intoxication, which the human body is capable of accepting and detoxifying without injury to itself.
It is this principle that the major exposure standards used within the western world are based
upon.

Measurement of Hazardous Substance Page 171


Appendix A Introduction to Physiology and Toxicology

You might also like