PAH (Polycyclic Aromatic Hydrocarbons) in work atmospheres : occurrence and determination

178 Pages·1986·19.39 MB·English

by  Becher

PAH
•
Ill
Work Atmospheres:
Occurrence
and
Determination
Editors
Alf Bj~rseth, Dr. phil.
Director
Petroleum Research Center
Norsk Hydro
Bergen, Norway
Georg Becher, Dr .rer .nat.
Head, Chemical Laboratory of
Toxicology
National Institute of Public Health
Oslo, Norway
Boca Raton London New York
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Library of Congress Cataloging-in-Publication Data
BjØrseth, Alf.
PAH in work atmospheres
Bibliography: p.
Includes index.
1. Polycyclic aromatic hydrocarbons--Toxicology.
2. Polycyclic aromatic hydrocarbons--Environmental
aspects. 3. Polycyclic aromatic hydrocarbons--Metabolism.
4. Polycyclic aromatic hydrocarbons--Measurement.
5. Industrial toxicology. I. Becher, Georg. II. Title.
RA1242.P73B56 1986 616.99’4’071 85-30731
ISBN 0-8493-6064-1
A Library of Congress record exists under LC control number: 85030731
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PREFACE
Polycyclic aromatic hydrocarbons (PAH) are a group of chemical compounds that are
strongly suspected of exhibiting carcinogenic effects in humans. This suspicion is based on
long-term observation, i.e., in animal bioassays, occupational medicine, and epidemiology.
Such observations have been made for a long time. The earliest association of a human
cancer with exposure to an environmental hazard was made more than two centuries ago
by Sir Percivall Pott who reported an increased incidence of scrotal cancer among chimney
sweeps. The coal soot, suspected to be responsible for this scrotal cancer, was not known
until Kennaway and his colleagues reported their work in the 1930s. Since that time, ample
evidence has been generated showing that increased industrialization and man's use of fossil
fuels result in a wide distribution of PAH in the environment. Particularly high levels of
PAH are to be found in occupational environments.
This book deals with the sources, distribution, analytical methods, and monitoring of
PAH in the occupational environment. It is our hope that the publication of this book will
make a contribution to understanding the formation and determination of PAH in work
atmosphere and that it will make a particular contribution to occupational health projects.
Much of the information given in this book has been generated in studies carried out in
cooperation with the Norwegian aluminum industry. The financial contribution to this work
from the Nordic Aluminum Industry's Secretariat for Health, Environment, and Safety is
gratefully acknowledged.
The authors would also like to acknowledge the inspiring working conditions provided
by the colleagues at the Center for Industrial Research in Oslo.
THE EDITORS
AlfBj0rseth, Dr. phil., graduated from the University of Oslo in 1969 with a background
in mathematics, physics, and chemistry with particular emphasis on physical chemistry. He
finished his doctorate in 1979 in Environmental Chemistry.
Dr. Bj0rseth is currently Director of Norsk Hydro's Petroleum Research Center in Bergen,
Norway. His previous engagements include Research Manager in the Chemistry Division
of the Central Institute for Industrial Research in Oslo, Norway and Associate Section
Manager at Battelle Columbus Laboratories in Columbus, Ohio. He is also co-founder of
the Scandinavian Center for Advanced Technology (SCATEC). Dr. Bj0rseth's research
interests include studies of polycyclic aromatic hydrocarbons and their transformation prod
ucts - with emphasis on the application of high resolution gas and liquid chromatographic
techniques. Dr. Bj0rseth has published over 60 papers in these areas, authored and edited
several books, given a number of lectures in the U.S. and Europe, and chaired international
symposia devoted to polycyclic aromatic hydrocarbons.
He is a member of the Norwegian Chemical Society and Norwegian Petroleum Society
where he is currently serving as President of the Bergen Division.
Georg Becher, Dr .rer .nat., is Head of the Chemical Laboratory in the Department of
Toxicology at the National Institute of Public Health in Oslo, Norway. Dr. Becher obtained
his M.S. and Ph.D. degrees in 1970 and 1974, respectively, from the Department of Organic
Chemistry, University of Gottingen, West Germany. He did his postdoctoral work at the
Department of Chemistry, University of Oslo, Norway and served as an Assistant Professor
at the Department of Chemistry, University of Regensburg, West Germany. In 1979, he
joined the Environmental Chemistry Department at the Central Institute for Industrial Re
search in Oslo as a research scientist. Since 1983, Dr. Becher is in his present assignment
at the National Institute of Public Health in Oslo.
Dr. Becher has been a recipient of the postgraduate fellowship of the Funds of Chemical
Industry, West Germany and is a member of the German and the Norwegian Chemical
Society. Dr. Becher is currently engaged in the analyses of trace quantities of potentially
hazardous compounds in environmental samples. Among others, he is interested in the
development of new methods for determination of human exposure to PAH.
TABLE OF CONTENTS
Chapter I
PAH as Occupational Carcinogens .................................................... .
I. Historical Review ................................................................. 1
II. Epidemiological Evidences for Cancer Risk from PAH ........................... 2
A. Chimney Sweeps .......................................................... 2
B. Aluminum Workers ....................................................... 4
C. Coke Oven and Steel Workers ............................................ 6
D. Iron and Steel Foundry Workers .......................................... 9
E. Asphalt and Tar Workers ................................................. 10
III. Summary and Conclusion ........................................................ 11
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Chapter 2
Mode of PAH Formation .............................................................. 15
References ............................................................................... 18
Chapter 3
Physical and Chemical Properties of PAH ............................................ 21
I. Chemical Structure and Nomenclature ........................................... 21
II. Physical Properties ............................................................... 23
III. Atmospheric Forms of PAH ..................................................... 28
IV. Chemical Reactivity ............................................................. 29
A. Oxidation Reactions ...................................................... 30
B. Reactions with Oxides of Nitrogen and Sulfur ........................... 30
V. Summary and Conclusion ........................................................ 31
References ............................................................................... 32
Chapter 4
Sources and Exposure .................................................................. 35
I. Sources of P AH in the Work Environment ...................................... 35
A. Coke Production .......................................................... 35
1. Historical Perspectives ............................................ 35
2. Coal Characteristics ............................................... 35
3. Structure and Operation of a Coke Plant. ......................... 35
4. Major By-Products ................................................ 37
5. Personnel ......................................................... 37
B. Aluminum Production .................................................... 38
1. Introduction ....................................................... 38
2. Electrolytic Reduction ............................................ 38
a. Pre bake Anode Process .................................... 38
b. Soderberg Anode Process ................................. 40
C. Iron and Steel Works ..................................................... 41
1. Iron Production ................................................... 41
2. Steel Production .................................................. 41
D. Iron and Steel Founding .................................................. 42
E. Petroleum Processing ..................................................... 43
F. Coal Conversion .......................................................... 43
1. Coal Gasification ................................................. 45
a. Historical Perspectives .................................... 45
b. Modem Coal Gasification Processes ....................... 45
c. Commercial Gasifiers ..................................... 46
d. Experimental Gasifiers .................................... 46
2. Coal Liquefaction ................................................. 47
G. Shale Oil Production ..................................................... 47
H. Asphalt Production and Use .............................................. 48
I. Carbon Black Production ................................................. 50
J. Combustion Engines ...................................................... 53
K. Lubricants ................................................................ 53
II. Pathways of Exposure ........................................................... 54
III. Summary and Conclusion ........................................................ 55
References ............................................................................... 55
Chapter 5
Sampling of PAH in Work Atmospheres .............................................. 57
I. Filter Sampling .................................................................. 57
II. Sampling by Filter and Back-Up ................................................. 58
III. Sampling Modes ................................................................. 59
A. Stationary Sampling ...................................................... 59
B. Personal Sampling ........................................................ 60
IV. Storage and Shipment. ........................................................... 61
V. Summary and Conclusions ....................................................... 61
References ............................................................................... 62
Chapter 6
Analytical Methods for Airborne PAH ................................................ 63
I. Real-Time Techniques ........................................................... 63
II. Fast and Inexpensive Group- or Compound-Specific Methods ................... 66
III. Detailed Analysis ................................................................ 71
A. Desorption ................................................................ 72
B. Isolation .................................................................. 74
1. Liquid-Liquid Partition ............................................ 74
2. Column Chromatography ......................................... 76
3. High-Performance Liquid Chromatography (HPLC) .............. 77
4. Thin-Layer Chromatography (TLC) ............................... 77
5. Selected Analytical Schemes ...................................... 78
C. Identification and Quantification ......................................... 79
I. TLC .............................................................. 79
2. HPLC ............................................................. 81
3. GC ................................................................ 85
IV. Quality Control of the Analytical Method ........................................ 90
A. Use of Internal Standards ................................................. 90
B. Intra- and Interlaboratory Control of PAH Analyses ...................... 90
V. Summary and Conclusion ........................................................ 94
References ............................................................................... 95
Chapter 7
Biological Monitoring of P AH Exposure ............................................. I 03
I. Intake, Distribution, and Excretion of PAH ..................................... I 03
II. Metabolism and Activation of PAH ............................................. 105
III. Effects of Particulate P AH ...................................................... 107
IV. Analysis of PAH in Urine ...................................................... I 08
V. Analysis of P AH in Blood Samples ............................................. Ill
VI. Summary and Conclusion ....................................................... 113
References .............................................................................. 114
Chapter 8
PAH in Different Workplace Atmospheres .......................................... 117
I. Threshold Limit Values for PAH ............................................... 117
II. Gas Works and Coke Ovens .................................................... 118
Ill. Aluminum Plants ............................................................... 122
IV. Iron and Steel Works ........................................................... 125
V. Foundries ....................................................................... 126
VI. Manufacturing of Carbon Electrodes ............................................ 128
VII. Roofing, Paving, and Insulating ................................................ 129
VIII. Coal Conversion Plants ......................................................... 131
A. Coal Gasification Plants ................................................. 131
B. Coal Liquefaction Plants ................................................ 132
IX. Chimney Sweeping ............................................................. 133
X. Exposure to Exhaust from Combustion Engines ................................ 135
XI. Summary and Conclusion ....................................................... 136
References .............................................................................. 13 7
Chapter 9
PAH Profiles and Proxy Methods .................................................... 141
References .............................................................................. 144
Chapter 10
Methods of Analysis ................................................................... 147
I. Introduction ..................................................................... 147
II. Cyclohexane-Soluble Fraction of Total Particulate Matter ...................... 147
A. Scope and Field of the Application ...................................... 147
B. Principle ................................................................. 147
C. Apparatus ............................................................... 14 7
D. Reagents ................................................................. 148
E. Procedure ................................................................ 148
F. Calculations ............................................................. 148
G. Repeatability and Reproducibility ....................................... 149
H. Schematic Presentation of Procedure .................................... 149
I. Advantages and Disadvantages .......................................... 149
Ill. Analysis of BaP ................................................................. 149
A. Scope and Field of Application .......................................... 149
B. Principle ................................................................. 149
C. Apparatus ............................................................... 150
D. Reagents ................................................................. 151
E. Procedure ................................................................ 151
F. Calculation .............................................................. 152
G. Repeatability and Reproducibility ....................................... 152
H. Schematic Presentation of the Procedure ................................ 152
I. Advantages and Disadvantages .......................................... 152
IV. Gas Chromatographic Profile Analysis of PAH ................................. 152
A. Scope and Field of Application .......................................... 152
B. Principle ................................................................. 153
C. Apparatus ............................................................... 153
D. Reagents ................................................................. 153
E. Procedure ................................................................ 153
F. Calculation .............................................................. 155
G. Repeatability and Reproducibility ....................................... 156
H. Schematic Representative of the Procedure .............................. 157
I. Advantages and Disadvantages .......................................... 157
V. HPLC Determination of P AH ................................................... 157
A. Scope and Field of Application .......................................... 157
B. Principle ................................................................. 157
C. Apparatus ............................................................... 157
D. Reagents ................................................................. 158
E. Procedure ................................................................ 158
F. Calculations ............................................................. 159
G. Repeatability and Reproducibility ....................................... 159
H. Schematic Representation of the Procedure .............................. 160
I. Advantages and Disadvantages .......................................... 160
References .............................................................................. 160
Index ................................................................................... 163
1
Chapter I
PAH AS OCCUPATIONAL CARCINOGENS
I. HISTORICAL REVIEW
The history of the detection, synthesis, and biological study of polycyclic aromatic hy
drocarbons (PAH) is closely related to the establishment of the carcinogenicity of coal tar.
Already in 1775, the British surgeon Sir Percivall Pott published studies which indicated
increased incidences of scrotal cancer among chimney sweeps in England, resulting from
prolonged contact of the skin with coal soot. 1 These chimney sweeps were, as children,
forced to climb the narrow English chimneys and remove soot from the inside of the chimney
flue. Dr. Pott assumed that the cause of the cancer development was soot and tar. It is, in
retrospect, interesting to note that Dr. Pott did not regard scrotal cancer as a serious problem,
since it could be removed without the least inconvenience. This part of Dr. Pott's observations
is probably not valid today.
About 100 years later, high incidences of skin cancer were reported among workers in
the paraffin refining/ shale oil,1 and coal tar industries.'' However, early attempts to produce
cancer in experimental animals with the raw materials of these industries were unsuccessful.
It was not until 1915 that the Japanese pathologist Yamagiwa and his colleagues at the
Imperial University of Tokyo' succeeded in inducing tumors with coal tar. Professor Ya
magiwa and his assistant Ichikawa showed5 that if they repeatedly painted the inside of the
cars of rabbits (two to three times a week), malignant tumors developed at the site of the
skin painting after 3 months, and these later proved to be cancer tumors which grew over
the whole ear. This was the first time that cancer tumors were produced experimentally by
means of chemicals. It is interesting to note that Yamagiwa and Ichikawa made a very good
choice by painting the cars of rabbits, since these show very high sensitivity toward exper
imental carcinogens. If they had painted the skin of dogs or guinea pigs instead of rabbits,
they probably would not have found any tumor development. Soon thereafter, Tsutsui"
obtained malignant skin tumors in mice also by painting them with coal tar. This was the
first experiment with a design that later should prove to be one of the most-used animal
models for studies of carcinogenic compounds: skin painting on mice. Following Tsutsui's
observation, other scientists showed that soot could be extracted and that these extracts also
produced skin cancer on mice. Therefore, by 1925 it was well established that coal, tar,
and soot contained material that was carcinogenic both to animals and to man.
In the 19th century, a discovery was also made which was of basic importance to the
chemical understanding of PAH. The recognition in 1865 that carbon atoms could be linked
in closed rings was one of the great conceptual advances of chemistry. The discovery was
made by August Kekule. 7 It is said that he solved the riddle of the structure of the benzene
molecule after having a dream in which dancing snakes bit their own tails. From the
understanding of the structure of the benzene molecule it was only a short step to the
recognition that the naphthalene molecule has two fused benzene rings. The structure of the
multiple-ring, or polycyclic compounds will be discussed below.
Soon after Kekule's discovery, the classical paper of Berthelot was published" in which
he showed that the heating of acetylene formed a tar which contained benzene and other
aromatic hydrocarbons. A likely source of the PAH was therefore recognized.
After the animal studies had demonstrated the presence of carcinogenic compounds in
coal tar, studies were undertaken to attempt to characterize the carcinogens in this material.
All that was known then was that the carcinogenic compounds were concentrated in the
high-bOiling fractions of the tar. Kennaway and his group at the (then) Research Institute