Spectral Atlas of Polycyclic Aromatic Compounds: Including Data on Physico-Chemical Properties, Occurrence and Biological Activity

869 Pages·1988·14.93 MB·English

by  W. Karcher (auth.)

SPECTRAL ATLAS
of
POLYCYCLIC AROMATIC
COMPOUNDS
Vol. 2
SPECTRAL ATLAS
of
POLYCYCLIC AROMATIC
COMPOUNDS
Vol. 2
including data on physico-chemical properties,
occurrence and biological activity
Edited by
W. Karcher, Joint Research Centre
(Ispra Establishment, Italy)
Commission of the European Communities
with contributions from
S. Ellison, (Laboratory of the Government Chemist, UK)
M. Ewald, P. Garrigues
(Laboratory of Molecular Photophysics and Photochemistry VA 348 CNRS, F)
E. Gevers, (TNO, Technology for Society, Zeist, NL)
J. Jacob, (Biochem. Institut fur Umweltcarcinogene, FRG)
KLUWER ACADEMIC PUBLISHERS
DORDRECHT / BOSTON / LONDON
for the
Commission of the European Communities
Library of Congress Cataloging in Publication Data
ISBN-13: 978-94-010-7061-4 e-I SBN-13: 978-94-009-1263-2
001: 10.1007/978-94-009-1263-2
Publication arrangements by
Commission of the European Communities
Directorate-General Telecommunications, Information Industries and Innovation, Scientific and
Technical Communications Service, Luxembourg
Lay-out: Reproduction service J.R.C. PEDEN
Design frontcover: Reproduction service J.R.C. ISPRA
EUR 11050
© 1988 ECSC, EEC, EAEC, Brussels and Luxembourg
Softcover reprint of the hardcover 1s t edition 1988
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Table of contents
Preface vi
1. Introduction 1
2. Information for Users 4
A. Physicochemical Properties 4
B. Crystallography 5
C. Occurrence 5
D. Biological Activity 5
E. Spectral Measurements 6
3. Acknowledgements 15
4. Data Presentation 16
A. Physicochemical Properties 16
B. Crystallography 26
C. Occurrence 31
D. Biological Activity 45
E. Spectra 56
5. References 830
6. Index 846
7. Glossary 864
Preface
Polycyclic Aromatic Compounds (PAC) are a broad class of compounds whose wide
distribution in the environment results from incomplete combustion processes of fossil
fuels in power generator, industrial plant and domestic heating, from car exhaust
gas and from tobacco smoke.
Many PACs are biologically active and in particular many of the PACs with three
or more fused rings are carcinogenic.
Currently there is concern of the occurrence of these pollutants at ppb (ug.kg-1) le
vel. However the predicted 2 to 3% annual increase in the rate of their release into
the environment could lead to ppm (ug.g-1) levels in the next century. The move to
wards stricter control of these pollutants brings with it the need for accurate monito
ring of their environmental occurrence.
Reliable identification and quantification of these compounds in complex environ
mental samples depends greatly on the availability of reference values for their phy
sicochemical and biochemical properties.
This second volume results from a close collaboration within the General Directorate
for Science, Research and Development of the Commission of the European
Communities between the Joint Research Centre, Ispra Establishment, the
Community Bureau of Reference and expert laboratories of the Member States.
It extends the work of the first volume to a further 45 PACs and a broader range
of properties and will be of assistance to all those engaged in research on the physi
cal, chemical and biological behaviour of this important class of chemicals whose
occurrence extends from the human environment to interstellar matter.
P. Fasella
Director General
General Directorate for Science,
Research and Development
vi
1 . Introduction
As by-products of the combustion of fossil fuels, polycyclic aromatic compounds (PAC)
are ubiquitous in the human environment. Because of their carcinogenic or mutage
nic properties, their identification and control in air, water, soils and food is warran
ted to protect human health and implement environmental quality standards.
Ideally, pure samples of each individual compound needing identification and quan
titation should be available to the analyst for comparison and instrumental calibra
tion. However, due to the enormous number of compounds which are encountered,
this situation is unlikely to be attained in the foreseeable future. Instead, the wide
spread availability of high quality molecular spectra and related data represents a
more realistic and practical alternative. For instance, UV and fluorescence spectra
can facilitate determination by HPLC and low temperature fluorescence spectra can
sometimes be used in Shpol'skii matrices to identify and determine certain isomers
without prior separation. Mass spectra are of course extremely valuable for the com
bination of GC with MS, although isomer differentiation is not usually possible with
this technique. For the unambigous identification of isomers and metabolites NMR
spectra are very useful and IR spectra are traditionally valuable for "finger printing".
In order to obtain a data collection based on identical materials, all spectra were
newly determined using samples of well defined purity. Table 1 gives an inventory
of the materials studied in the order of presentation in this volume. Care was taken
wherever possible to employ standard conditions for the measurement of the spec
tra. The range of solvents used was minimised and the concentrations and other
operating conditions were kept approximately constant within a technique.
The present collection is the second volume published in the form of a "Spectral
Atlas of PAC" and contains the spectra of about 45 new compounds, ·i.e.
- 18 polycyclic aromatic hydrocarbons (PAH) (fluorene, benzofluorenes dibenzopy
renes, dibenzofluoranthenes, etc.)
- 10 N-heterocyles (acridines, benz- and dibenz-acridines, dibenzocarbazoles)
- 17 methylated PAH (methylanthracenes and methylbenz(a)anthracenes, methyl-
cholanthrene.
As in the first volume, the Atlas presents the following spectra, determined largely
under standardised experimental conditions:
- UV-spectra
- Fluorescence (emission and excitation spectra at room temperature)
- Fluorescence and Phosphorescence Shpol'skii spectra at 15K
- Mass spectra (magnetic and quadrupole spectra)
- NMR spectra (proton- and carbon-13 spectra)
- IR-spectra (taken in solution and in KBr-pellets).
As before, we have chosen to group all the spectra for each compound on consecu
tive pages, rather than keeping all spectra of the same type together as is common
in data collections. We hope, thereby, to make the task of the user that much easier
when seeking the available data on a particular compound.
Table 1: Inventory of compounds
Chem. Mass m.p. Purity SCR -
Compound CAS Nr.
Formula number (0C) (gig) RM-Nr.
Naphthalene ClOHS 128 81 0.999 91-20-3
Acenaphthylene C12HS 152 92-93 0.998 208-96-8
Acenaphthene C12HlO 154 95 0.997 83-32-9
9H-Fluorene C13HlO 166 115-116 0.994 86-73-7
Acridine C13HgN 179 110 0.996 260-94-6
2-Methylanthracene C15H12 192 203 0.999 2498-76-2
9-Methylanthracene C15H12 192 79 0.999 2381-16-D
11 H-8enzo(b )fluorene C17H12 216 213.5 0.994 243-17-4
7H -8enzo( c) fluorene C17H12 216 126.5 0.91 205-12-9
Triphenylene C1sH12 228 199 0.998 217-59-4 270
Naphthacene C1sH12 228 357 0.999 92-24-0
8enz(a)acridine C17H11N 229 131 0.998 225-11-6 157
8enz(c)acridine C17H11N 229 107.4 0.998 225-51-4 158
1-Methylbenz(a)anthracene C1gH14 242 138.6 0.993 2498-77-3 93
2-Methylbenz(a)anthracene C1gH14 242 146-147 0.982 2498-76-2
3-Methylbenz(a)anthracene C1gH14 242 159-161 0.972 2498-75-1
4-Methylbenz(a)anthracene C1gH14 242 193 0.985 316-4g..4
5-Methylbenz(a)anthracene C1gH14 242 154 0.992 2319-96-2
6-Methylbenz(a)anthracene C1gH14 242 125 0.991 316-14-3
7- Methylbenz(a)anth racene C1gH14 242 134 0.987 2541-69-7
8-Methylbenz(a)anthracene C1gH14 242 158 0.999 2381-31-9
9-Methylbenz(a)anthracene C1gH14 242 151 0.992 2381-16-D
10-Methylbenz(a)anthracene C1gH14 242 139 0.994 2381-15-9
11-Methylbenz(a)anthracene C1gH14 242 117.5 0.995 6111-78-D
12-Methylbenz(a)anthracene C1gH14 242 138 0.990 2422-79-9
Perylene C2oH12 252 277.5 0.998 198-55-0
3, 9-Dimethylbenz(a)anthracene C2oH16 256 186 0.988 316-51-8
6, 8-Dimethylbenz(a)anthracene C2oH16 256 143 0.990 317-64-6
7,12-Dimethylbenz(a)anthracene C2oH16 256 122 0.989 57-97-6
13H-Dibenzo(a, i) carbazole C2oH13N 267 221 0.995 239-64-5
7H-Dibenzo (c,g) carbazole C2oH13N 267 158 0.997 194-59-2 266
3-Methylcholanthrene C21H16 268 179 0.993 56-49-5
Dibenzo (k, mno) fluoranthene C22H12 276 150 0.992 203-25-8
Indeno (1, 2, 3-cd) fluoranthene C22H12 276 262 0.998 193-43-1 267
Picene C22H14 278 364 0.998 213-46-7 168
Pentacene C22H14 278 300 (dec.) 0.99 135-48-8
Dibenz (a, c) acridine C21H13N 279 203.4 0.999 215-62-3 155
Dibenz (a, h) acridine C21H13N 279 226.1 0.999 226-36-8 153
Dibenz (a, i) acridine C21H13N 279 207.5 0.998 226-92-6 152
Dibenz (a, j) acridine C21H13N 279 217 0.998 224-42-D 154
Dibenz (c, h) acridine C21 H13N 279 190.6 0994 224-53-3 156
Coronene C24H12 300 439 0.998 191-D7-1 272
Dibenzo (a, e) fluoranthene C24H14 302 232 0.998 5385-75-1 265
Dibenzo (a, k) fluoranthene C24H14 302 229 0.993 84030-79-5
Dibenzo (a, h) pyrene C24H14 302 317 0.992 189-64-D 159
Dibenzo (a, i) pyrene C24H14 302 282 0.997 18g..55-9 268
Naphtho (2, 3-k) fluoranthene C24H14 302 299-300 0.992 207-18-1
2
Occasionally, for technical or practical reasons, a particular spectrum is not illustra
ted and where appropriate, this is indicated and explained in the experimental sec
tion below, under the respective methods.
Further, as the sources, distribution and biological effects of these ubiquitous pollu
tants are of considerable importance in the assessment of their total impact on health,
a representative selection of the available data (up to the end of 1986) on occurren
ce and mutagenic or carcinogenic activity are summarised in tabular form for each
of the compounds.
In view of the increasing use of basic physicochemical properties, such as water
solubility, octanol/water distribution coefficient, vapour pressure etc. for assessing
environmental fate and distribution and human and ecological exposure risks, the
corresponding data section has been significantly extended.
It is the intention, to continue and expand the present data collection. A third volume
of the "Spectral Atlas on PAC" is in preparation, focusing mainly on nitro-, oxygen
and sulphur derivatives of PAC and some matabolites.
W. Karcher
JRC Ispra
May 1988
3
2. Information for Users
A. Physicochemical Properties
The melting points given in Table 1 for BCR certified reference materials and
repeated with the spectra were determined by Differential Scanning Calorimetry
using the same materials as were used for the spectra measurements. The
melting points of indium (0.999999 gIg) and lead (0.99999 gIg), were used as
references for calibration and the values shown are the means of at least six
individual measurements. For the other compounds the melting points were
determined using coventional melting point apparatus.
For methylderivatives, most melting and boiling points in table 2A were col
lected from literature (6, 21).
Besides melting and boiling points, tables 2 and 2A also give information an
heat of vaporization, molecular connectivity, which can be used for estimating
boiling points and related thermodynamic properties, retention indices and
length/breadth ratio (UB). The GC retention indices are based on standard
= = =
reference values (naphthalene 200, phenanthrene 300, chrysene 400,
picene = 500), introduced by Lee and co-workers (13). LC retention values were
determined for a polymeric C18 column (Wise and co-workers, ref. 22).
Table 3 presents an overview on vapour pressures, enthalpies of sublimation
and fusion, sublimation entropies, where available, and on Henry constants.
In tables 4-4b, data on water solubility, octanol/water and soil/water distribu
tion coefficients are collected in view of their importance for assessing the
distribution and fate of organic pollutants in the biosphere.
These distribution coefficients are defined as follows:
= concentration in oetanol phase
(i) Kow
concentration in aqueous phase
(i i) Kp = concentration in soil or sediment
concentration in aqueous phase
=
(ii i) Koc Kp for organic soil/sediment fraction
Vowles (20) has developed some simple equations for deriving Kp and Koc from
Kow values of PAH:
(iv) log Kp = 1.15 log Kow - 2.53
(v) log Koc = 1.20 log Kow - 1.13 (parent PAH)
(vi) log Koc = 0.774 log Kow + 0.37 (for alkylnaphthalenes)
In addition, tables 4-4b present some values for molar/molecular volume and
surface area, which can be used in solubility estimations (14, 16, 18).
Finally, table 4c shows bioaccumulation and degradation factors for some
selected PAH (4, 260).
4
B. Crystallography
For photophysical applications, structure-activity studies, and more general
theoretical considerations, crystallographic parameters and C -C bond lengths
may also be of interest. Therefore, tables 5 to 5c list the crystal parameters
of PAH, methylderivatives, heterocycles and other derivatives, including crystal
symmetry, lattice parameters and angles, space group and number of
molecules per unit cell. Through the references, further data on C -C distances
and angles are accessible for more detailed structural investigations.
C. Occurrence
As a comprehensive assessment of the health effects of these important
pollutants must be based on both occurrence and on biological hazard effects,
a survey on the major sources and environmental distributions of PAH as well
as an indication of their mutagenic and carCinogenic activities is included for
each of the compounds. This review of the literature is not intended as an ex
haustive survey but should facilitate the overall assessment of occurrence and
of potential health risks. For more detailed information, the user is referred
to the recent relevant monographs (6, 425, 431) and special evaluation studies
(447).
The data are presented in tabulated format for convenience and grouped under
four main headings:
- mobile sources (car exhaust, engine oils, crude oils)
- stationary sources (coal, oil, wood and peat combustion, coke ovens, tars, etc.)
. environmental domains (air, water, soil)
. foodstuffs (smoked meat, fish, vegetables, etc.)
D. Biological Activity
The biological data are also summarised in tables, subdivided into bacterial
mutagenicity data (Ames' tests), mammalian cell tests and animal car
cinogeniCity data (animal studies).
The data presented for the Ames test are based on results obtained with
metabolic activation (5-9 mixture) and when comparing results of different
origin, it should be borne in mind that the purities and experimental condi
tions used in these tests can vary considerably.
The test strains or cell types used for the mutagenicity tests and the animal
species studied for carcinogenicity or toxicity effects are also given. Whenever
5