Chemistry and Analysis of Volatile Organic Compounds in ...978-94-011-2152...Chemistry and analysis of volatile organic compounds in the environment / edited by H.l. Th. Blocmen and

Chemistry and Analysis of Volatile Organic Compounds

in the Environment

Chemistry and Analysis of Volatile Organic Compounds

in the Environment

Edited by

H.J. Th. BLOEMEN Research Scientist, Air Quality

and

J. BURN Science Associate, International Air Quality

Dutch Institute of Public Health and Environmental Protection (RIVM) The Netherlands

SPRINGER-SCIENCE+BUSINESS MEDIA, B.V.

Firsl edirion 1993 Reprinled 1995

@ 1993 Springer Science+Business Media Dordrecht Origînally publishcd by Chapman & Hali in 1993 Softcovcr reprinl of Ihc hardcovcr isI cditiOll 1993

Typeset in 1O/12pt Times by Thomson Press (India) Led, New Delhi

ISBN 978-94-010-4953-5

Apan from any fair dealing for the purposes of research ar private slUdy, or criricism or review, as permitted under the UK Copyright Designs and Paten!.!; Act, 1988, this pubJica.tion may nOI be reproduced, store

The publîsher makes no rcprcsentation, exprcss or implied, with regard ro the accuracy of the information contained in this book and cannot accept any legal rcsponsibility or liabmty for any errors or omissions that may be roade.

A Caulogue fC(:ord for this book is available from the British Library

Ubrary of Congress Cataioging-In-PubUcation Data

Chemistry and analysis of volatile organic compounds in the environment / edited by H.l. Th. Blocmen and 1. Bum.-tst ed.

p. cm. lncludes bibliogl1lphical rcfercnces and index. ISBN 978-94-010-4953-5 ISBN 978-94-011-2152-1 (eBook) DOI 10.1007/978-94-011-2152-1 1. Volarile organic compounds-Environrnental aspects. 2. Volatile

organic compounds·Analysis. 3. Volatile organic compounds -Health aspects. 1. Blocmen, H.l. Th.(Henkl.Th) n. Bum, 1. (James) TDI96.073C48 1993 93·9751

t§l Printed on ackHrec text paper, manufacrured in auordance with ANSIJNISO Z39.48-1992 (Permanence of Paper).

CIP

Contributors

Dr H.J.Th. Bloemen Air Quality Laboratory (LLO), Dutch National Institute of Public Health and Environmental Protection (RIVM), PO Box I-NL 3720 BA, Bilthoven, The Netherlands

Mr J. Burn Air Quality Laboratory (LLO), Dutch National Institute of Public Health and Environmental Protection (RIVM), PO Box 1-NL 3720 BA, Bilthoven, The Netherlands

Dr P. Ciccioli Instituto sull' Inquinamento Atmospherico del CNR, Area della Ricerca di Roma, Via Salaria km. 29,300, CPlO, 00016 Monterotondo Scalo, Italy

Dr J.J.G. Kliest Research Coordination Environmental Incidents, Dutch National Institute of Public Health and Environmental Protection (RIVM), PO Box 1-NL 3720 BA, Bilthoven, The Netherlands

Dr D. Kotzias Commision of the European Communities, Joint Research Centre, Ispra Environment Institute, 21020 Ispra (V A), Italy

Dr W.A. McClenny US Environmental Protection Agency, Research Triangle Park, North Carolina 27711, USA

Dr.Ir G. de Mik Substances and Risks Division, Dutch National Institute of Public Health and Environmental Protection (RIVM), PO Box 1-NL 3720 BA, Bilthoven, The Netherlands

Dr C. Sparta Commission of the European Communities, Joint Research Centre, Ispra Environment Institute, 21020 Ispra (VA), Italy

Dr G.J.A. Speijers Laboratory of Toxicology, Dutch National Institute of Public Health and Environmental Protection (RIVM), PO Box 1-NL 3720 BA, Bilthoven, The Netherlands

Dr L.A. Wallace US Environmental Protection Agency, Building 166 Bicher Raod, Vint Hill Farms Station, Warrenton, VA 22091, USA.

For M onique and Ingrid

Contents

Editorial introduction

1 VOCs and the environment and public health-exposure L.A. WALLACE

1.1 Introduction 1.2 Measurement methods

1.2.1 Air 1.2.2 Water 1.2.3 Body fluids

1.3 Human exposure 1.3.1 Air 1.3.2 Drinking water 1.3.3 Food and beverages 1.3.4 Dust and soil 1.3.5 Dermal absorption

1.4 Body burden 1.4.1 Breath 1.4.2 Blood 1.4.3 Mother's milk

1.5 Human health effects 1.5.1 Acute effects (sick building syndrome) 1.5.2 Chronic effects (cancer)

1.6 Summary References

2 VOCs and the environment and public health-health effects a.J.A. SPEIJERS

2.1 General introduction 2.2 Toxicokinetics and biotransformation

2.2.1 Introduction 2.2.2 Conditions influencing the toxicokinetic behaviour 2.2.3 Toxicokinetic behaviour of styrene 2.2.4 Toxicokinetic behaviour of toluene 2.2.5 Toxicokinetic behaviour of phenol 2.2.6 Toxicokinetic behaviour of chlorophenols 2.2.7 Toxicokinetic behaviour of benzene 2.2.8 Toxicokinetic behaviour of chloroform 2.2.9 Toxicokinetic behaviour of methylene chloride 2.2.10 Toxicokinetic behaviQur of volatile chlorobenzenes 2.2.11 Toxicokinetic behaviour of ethylene and propylene oxide

2.3 Introduction to toxicological studies 2.3.1 Acute toxicity in animals 2.3.2 Short-term toxicity 2.3.3 Long-term toxicity and carcinogenicity 2.3.4 Genotoxicity and mutagenicity

xi

1

1 1 1 4 4 4 4

10 11 11 11 12 12 13 13 13 13 15 17 17

25

25 25 25 26 30 32 33 35 35 37 37 39 40 41 41 45 51 55

viii CONTENTS

2.3.5 Reproductive toxicological effects and teratogenicity S8 2.3.6 Effects on the nervous system 61 2.3.7 Effects on the immune system 64 2.3.8 Effects on the cardiovascular system 65 2.3.9 Effects on the endocrine system 66 2.3.10 Interaction of VOCs in cases of combined exposure 67 2.3.11 Effects in humans: differences from observations in animals 69 2.3.12 Effects in humans: risk groups 70 2.3.13 Risk assessment and the use of mathematical models 71

References 74

3 VOCs and air pollution 92 P. CICCIOLI

3.1 Introduction 92 3.2 VOC emission 93

3.2.1 VOC sources and source categories: estimates and spatial distributon 96

3.2.2 Future trends in the evaluation of VOC emission 103 3.3 VOC effects 105

3.3.1 VOCs as air toxics 107 3.3.2 VOCs as precursors of photochemical smog and acid deposition 110 3.3.3 VOCs as a source of stratospheric ozone depletion 120 3.3.4 VOCs in a changing climate 123

3.4 VOC measurement 124 3.4.1 Evaluation of VOCs in emission sources 124 3.4.2 Evaluation of VOCs in the atmosphere 131

3.5 Methods for VOC determination 153 3.5.1 Total and non-methane VOC content 153 3.5.2 Determination of individual VOCs 154

3.6 Conclusions 164 References 165

4 VOCs and water pollution 175 D. KOTZIAS and C. SPARTA

4.1 Introduction 175 4.2 Definition 176 4.3 Distribution in air, water and soil 176

4.3.1 Henry's law constant (H) 176 4.3.2 n-Octanolfwater partition coefficient (Kow) 178 4.3.3 Water/soil or sediment partition coefficient (Ko.) 178

4.4 Occurrence 178 4.4.1 Seawater 178 4.4.2 River, lake, ground and tap water 180

4.5 Sources 184 4.6 Behaviour and fate of VOCs in aquatic systems 185

4.6.1 Volatilization 185 4.6.2 Biodegradation 186 4.6.3 Adsorption 188 4.6.4 Photo-induced degradation 188 4.6.5 Oil in seawater 189

4.7 Environmental aspects of selected organohalogen compounds 189 4.8 Sampling of VOCs in water 192

4.8.1 Sampling procedure 192 4.8.2 Methods for sampling enrichment 192

4.9 Analysis of VOCs in water 195

CONTENTS

4.9.1 Factors influencing VOC analysis 4.9.2 Sum parameters (TOX, POX) 4.9.3 Description of a practical procedure for the analysis of

VOCs in water samples 4.10 Conclusions References

5 VOCs and soil pollution J.J.G. KLIEST

ix

197 197

198 199 199

202

5.1 Introduction 202 5.1.1 The soil as part of the environment 202 5.1.2 VOCs and soil pollution 203

5.2 Sources of soil contamination with VOCs: relationship with other environmental compartments 204 5.2.1 Sources of soil contamination 204 5.2.2 Fate of VOCs in the environment: the fugacity concept 204

5.3 Partitioning of VOCs in the soil 205 5.3.1 Introduction 205 5.3.2 Adsorption and desorption to the solid phase 206 5.3.3 Partitioning between the liquid phase and the gas phase 207 5.3.4 Calculation of partitioning for non-polar compounds 209 5.3.5 The kinetics of adsorption 209

5.4 Transport of VOCs in the soil 210 5.4.1 Introduction 210 5.4.2 Diffusion in the soil under steady-state conditions 211 5.4.3 Diffusion under non-steady conditions: Fick's second law 212 5.4.4 Applications of Fick's second law 212 5.4.5 Other methods for calculation of diffusional transport 217 5.4.6 Convection with the liquid phase 218

5.5 The assessment of concentrations of VOCs in the soil 218 5.5.1 Introduction 218 5.5.2 Sampling and analysis of the solid phase of the soil 219 5.5.3 Sampling and analysis of the liquid phase of the soil 223 5.5.4 Sampling of soil air 225

5.6 Soil pollution with VOCs: human health risks 226 5.6.1 Introduction 226 5.6.2 Calculation of human toxicologically based C-standard values 229 5.6.3 Potential and actual risk 230 5.6.4 Validation of exposure modelling and discussion 230

References 235

6 Future monitoring techniques for VOCs W.A. McCLENNY

237

6.1 Automated gas chromatographs (autoGCs) 237 6.1.1 What are autoGCs and why are they being developed? 237 6.1.2 Applications for autoGCs 240 6.1.3 Treatment of water vapor 244 6.1.4 Data processing to improve the retention time variability

and quantitation of VOCs 245 6.1.5 Future directions for autoGCs 245

6.2 Open path monitoring of VOCs 246 6.2.1 The fundamentals of open path monitoring 246 6.2.2 Systems based on differential optical absorption spectroscopy (DO AS) 248 6.2.3 Systems based on infrared absorption 249

6.3 Real-time and near real-time monitoring of VOCs 252

x CONTENTS

6.3.1 Analyzers equipped with diffusion scrubbers, gas denuders or nebulization/reflux concentrators

6.3.2 Fast gas chromatography and portable GCs 6.4 Passive sampling devices (PSDs) for VOCs

6.4.1 New developments in PSDs 6.4.2 Typical applications for PSDs

6.5 Sample containment and transport 6.5.1 Whole air sample containers and solid absorbents 6.5.2 The question of storage stability

6.6 Other important VOC monitoring method developments 6.6.1 Direct sampling inlets for GC-MS systems 6.6.2 Multi-dimensional gas chromatography 6.6.3 Time-of-flight mass spectrometry (TOFMS) 6.6.4 Direct sampling MS-MS 6.6.5 Microsensor arrays and gas chromatographs

6.7 Conclusions Equipment manufacturers References

7 VOCs and occupational health G. de MIK

7.1 Introduction 7.2 Sources

7.2.1 Importance 7.2.2 Applications 7.2.3 Multiple exposure

7.3 Exposure 7.3.1 Differences from the general population

7.4 Sampling 7.5 Health-based recommended exposure limits

7.5.1 Introduction 7.5.2 Threshold limit values 7.5.3 Other occupational exposure limits

7.6 Biological exposure limits 7.6.1 Introduction

7.7 Combined exposure to chemicals 7.7.1 Introduction 7.7.2 Interactions in the exposure phase 7.7.3 Toxicokinetic interactions 7.7.4 Toxicodynamic interactions 7.7.5 Consequences of interactions

References

Index

252 254 255 255 257 258 258 259 261 261 261 261 262 263 263 264 264

268

268 268 268 268 270 270 270 271 272 272 274 276 276 276 278 278 278 278 279 279 279

281

Editorial introduction

Volatile organic compounds (VOCs) and their reaction products are increas-ingly regarded as posing unacceptable risks to public and occupational health, as well as to biological and physical environments. VOCs may be identified and measured in all compartments of the environment and on all scales ranging from the individual to the global. Their ubiquity reflects partly their volatility-a vapour pressure greater than 0.13 kPa is conventionally used to distinguish them from less volatile organics I-and partly their involvement in comparably ubiquitous living processes-some VOCs may be referred to as biogenic. However, the key role of VOCs in the industries and economies of today's fossil fuel-based societies, together with the quantities of VOCs involved, are the prime contributing factors. Anthropogenic VOCs have now also appeared in abundance.

While some biogenic VOCs perform various biophysical and biochemical functions within living cells and mircoorganisms, others are released by living organisms-sometimes in great quantities-into the surroundings. Dimethyl sulphide is emitted into seawater and thence to the atmosphere by marine microorganisms throughout the world; isoprene and terpenes are released into the air by vegetation as diverse as the woodlands of Central Europe and the prairies of North America, and, during the rice-growing season, vast amounts of methane are produced and released into the atmosphere from Asian paddy fields. This methane may be biogenic in origin, but its occurrence and quantity are anthropogenically determined, being dependent both on rice-growing and on specific paddy cultivation techniques. Similarly, most of the VOCs referred to as anthropogenic are, or are believed to be, of biological origin, but their presence, especially at current quantities, is the result of social, economic and industrial activities.

In pre-industrial societies sources of VOCs such as wood and 'natural' oils, tars and waxes were exploited largely as fuels, primarily on a domestic scale. When the Industrial Revolution gained momentum in the 19th century, emissions of organic compounds increased exponentially. In pre-war Germany the chemical industry manufactured numerous compounds, among them novel VOCs. In this emerging industry, still based on coal, VOCs were usually formed after processing the heavier starting material. Exploration of the vast

1 Subdivisions of the group, excluding certaift species or distinguishing classes according to criteria other than volatility, may be encountered if indicated by the application.

xu EDITORIAL INTRODUCTION

oil fields in the USA and the Middle East transformed pre-war communities into oil-based societies. Nowadays, light oil products, obtained from crude oil directly or after cracking heavy fractions, make up the essential ingredients of modern transportation, energy generation and the petrochemical industries. The seemingly unlimited capacity of the chemical industry has created a wide range of new and sometimes exotic compounds. Ever-expanding product applications are accompanied by seemingly inevitable spills. Only in a few cases are VOCs not released into the environment; in most cases they are flushed into aquatic systems, evaporated into the air or dumped in the soil. In addition to 'regular' spills (the end result of malcontrolled chemical or physical processes), accidental releases (e.g. uncontrolled emissions from industrial plants or wrecked tankers at sea) contribute to the increasing levels of a wide range of compounds. This happens not only near industrial and urban areas, but also in remote areas such as the Arctic stratosphere, where stable organic compounds are found in elevated concentrations.

The mere presence of VOCs in the environment, even in large quantities, would simply be a scientifically interesting phenomenon, were it not for the range of adverse effects known, or suspected, to be associated with them. The exposure of the environment and living organisms to VOCs has altered the delicate balance of ecosystems and has caused adverse health effects. The relationship between these health effects and exposure to VOCs was first recognized in the chemical industry, where high concentrations of a limited number of compounds existed. Toxicological research revealed that many VOCs have various reversible and irreversible effects on the human body, ranging from acute anaesthesia to long-term effects such as induction of carcinomas. Ecotoxicological research has indicated effects on the environ-ment; these range from changes in the population of terrestrial and aquatic ecosystems to the extinction of vulnerable species. All of these effects can be considered to be directly due to VOCs, although the active agent may be one or more metabolites produced by the target species.

A current, extremely relevant, indirect effect of VOCs was recognized in the 1950s. Heavy air pollution in the Los Angeles basin was found to be created by the photo-oxidation of VOCs in the presence of nitrogen oxides. The main constituent of this type of smog was found to be ozone, now known to have reversible and irreversible effects on the lungs. Furthermore, the effects are not limited to humans and animals; crops have also been proven to be damaged after exposure to this type of air pollution. Recent research has revealed that this 'urban soup' also contains a multitude of other reactive compounds, a number of which are suspected to be biologically and ecolog-ically active.

In the 1980s two further major indirect effects of VOCs on a global scale were discovered. First, after sophisticated satellite measurement of the Antarctic ozone column and through examination and re-evaluation of the data obtained, it was shown that inert VOCs, until then thought to be

EDITORIAL INTRODUCTION xiii

harmless, were related to dramatic ozone depletion in the stratosphere above the Antarctic. A second indirect effect is global climatic change. The presence of, again, relatively unreactive compounds in the upper atmosphere is thought to be responsible for trapping surplus solar radiation. Although the process is not completely understood, current evidence indicates changes for some global regions that are dramatic enough to warrant strong recommendations of dramatic measures.

The presence of VOCs in the indoor environment also poses a threat to public health. Modern building materials and household products are sources of many different VOCs. The increasing effort to reduce heat loss from buildings has initiated nationwide programmes for insulating walls and windows and recirculating air in air-conditioned buildings. This has led to a reduction of forced and natural ventilation and so to the build-up of concentrations of compounds emitted by indoor sources. It is clear that VOCs have increasingly affected the world we live in and that a better understanding of their occurrence and behaviour is of eminent importance to counteract their effects.

Scientific and public awareness of the threat that VOCs pose to humans and the environment has alerted regulatory bodies. Many initiatives have been launched to reduce the emission of VOCs or to reduce their adverse impact on humans and the environment, especially in the industrial nations where local and regional levels and effects are most pronounced. The intrinsic conflict arising from the basic role of VOCs in modern society and the need to prevent the environment from becoming hostile has complicated and delayed, but not obstructed, the ratification of various agreements on reduction of VOCs. Wherever possible, the air toxic, benzene, is banned from industrial processes and solvents. The Montreal Protocol to limit the use of and, ultimately, to ban chlorofluorocarbons is ratified by many countries. The ECE VOC Protocol to reduce ozone levels by the reduction of VOC emission is already having some effect. The amendments to the US Clean Air Act deal with the reduction of VOCs from industrial and mobile sources. These are some major illustrations of the intention to preserve the delicate balances so important to life.

All of these initiatives are based on the work of researchers from several disciplines in many institutions worldwide. Their research is quite diverse, jncluding public health, studies on the physics and chemistry in the upper stratosphere, and research on ecosystems at the bottom of the sea. As in many other fields, communication between researchers of various disciplines on the one hand, and between researchers, policy makers, research programme officers and the public on the other, although essential, is hampered by the complexity and limited knowledge of the issues.

This book can be seen as a contribution to improving communication between the various participants in the search for solutions to the many problems created by the presence of VOCs. Scientists from the main fields

xiv EDITORIAL INTRODUCTION

of VOC investigation highlight aspects relevant to the impact assessment ofVOCs. In addition to the biochemistry ofVOCs in the human body, and the chemistry and physics of VOCs in environmental compartments, special attention is given to both analytical and modelling techniques, for defining identities and assessing levels of VOCs. Distinction is made between direct effects on human health, and mainly ecological, but also some indirect human health effects encountered in environmental compartments. The first aspect is dealt with in chapters 1 and 2. In chapters 3, 4 and 5 the main compartments of the environment -air, water and soil, are explored. Assessing the occurrence of VOCs by means of analytical techniques is considered to be one of the driving forces in this area of research, therefore chapter 6 is devoted to future developments in monitoring techniques for VOCs. Finally, chapter 7 deals solely with occupational health, probably the most developed research area.

The compilation offacts presented in this book cannot, and is not intended to be complete but will certainly paint a broad picture of what is happening in the many institutes concerned with increasing our knowledge of the role VOCs. The aim of the book is to enable researchers, policy makers and programme officers concerned with public health and environmental quality to familiarize themselves with the insights and approaches presented, and so to improve their understanding of the uncertainties and the scope of current knowledge. This may prove to be essential for progress between disciplines.

We would like to express our gratitude to the individual contributors presenting so many facts, insights and approaches from the day-to-day work done in their particular fields. Compiling this book, in which such a wide area of research has been covered, has only been possible through their valuable contributions. Finally, we thank the Board of Directors of the National Institute of Public Health and Environmental Protection in Bilthoven for the facilities necessary to complete this book.

Henk 1.Th. Bloemen lames Burn