Anal. Chem. 1987, 59, 1695-1700
matography system as long as the qualifying conditions (see
introductory section) are satisfied. In other words, in any
system of column chromatography and for any volume of the
sample charge, the sensitivity of analyte-mass determination
should range between the “extreme” values given by eq 9 and
16 (or by curves 3 and 4 in Figure 2). Although the reducing
parameters u, and v,,,,,~ cannot be determined exactly, fair
approximations to these may be obtained from a chromatogram of the smallest possible sample charge. Once the volume
uc is known, the increase in the sensitivity of analyte-mass
determination on concentrating the sample may readily be
calculated. T o do so, eq 9 or eq 13 and 16 are applied to the
volumes of charges of the concentrated and original samples,
respectively. Naturally, the volumes are concerned containing
the same amounts of analyte. For the model to be applicable
directly, the state of aggregation of both concentrated and
original samples should be the same as that of the mobile
phase. The increase required is then given by the ratio of the
two results. The choice between the two column-inlet profiles
depends upon the performance characteristics of the particular
sample-introduction device employed. In principle, relationships analogous to eq 9 and 16 may be derived for any
other column-inlet concentration profile. It may be shown
is
that for large values of a, the sensitivity ratio pmi,ap/pmi,c
nearly equal to (2a)’i2/a regardless of the column-inlet concentration profile. The use of eq 9,13, and 16 may be managed
even with a programmable pocket calculator.
Finally, a brief evaluation should be given of the relative
significance of qualifying conditions (i-vi) (see introductory
section). Obviously, the most severe limitations to the
practical applicability of the model are those imposed by
conditions iv and vi. The adherence of the behavior of a real
instrument to the model described improves on decreasing
the dead volume of the chromatographic system and on de-
1695
creasing the time constants of the detection and registration
system. For very slightly retained compounds and/or for very
quick analyses, condition v may impose significant restriction
to the applicability of the model.
LITERATURE CITED
Kaimanovskii, V. I.; Zhukhovitskii, A. A. J . Chromatogr. 1965, 18,
243-252.
Karger, B. L.; Martin, M.; Guiochon, G Anal. Chem. 1974, 4 6 ,
1640-1647.
Guiochon, G.; Colin, H. “Analytical Techniques in Environmental
Chemistry”; Proceedings of fhe 2nd International Congress, Barcelo
na, Spain, November 1981; Aibaiges, J., Ed.; Pergamon: OxfordNew York-Sydney, 1981; pp 169-176.
Sternberg, J. C. Advances in Chromatography;Giddings, J. C., Keiier,
R. A., Eds.; Marcel Dekker: New York, 1966; Voi. 2, pp 205-270.
McWiiiiam, I . G.; Boiton, H. C. Anal. Chem. 1969, 4 1 , 1755-1762.
Giadney, H. M.; Dowden, B. F.; Swaien, J. D. Anal. Chem. 1969, 4 7 ,
883-888.
Anderson, A. H.; Gibb, T. C.; Littiewood, A. B. J . Chromatogr. Sci.
1970, 8, 840-646.
Grushka, E. Anal. Chem. 1972, 4 4 , 1733-1738.
Pauis, R. E.; Rogers, L. B. Anal. Chem. 1977, 4 9 , 625-628.
Barber, W. E.; Carr, P. W. Anal. Chem. 1961, 53, 1939-1942.
Foiey, J. P.; Dorsey, J. G. Anal. Chem. 1963, 55, 730-737.
Foley, J. P.;Dorsey, J. G. J . Chromatogr. Sci. 1984, 22, 40-46.
Anderson, D. J.; Waiters, R. R. J . Chromatogr. Sci. 1984, 22,
353-359.
Deiiey, R. Chromafographia 1984, 18, 374-382.
Hanggi, D.; Carr, P. W. Anal. Chem. 1985, 57, 2395-2397.
Deiiey, R. Anal. Cbem. 1986, 5 8 , 2344-2346.
Handbook of Mathematical Functions; Abramowitz, M., Stegun, I. A.,
Eds.; National Bureau of Standards: Washington, DC, 1964; Applied
Mathematics Series No. 55, p 932.
van Deemter, J. J.; Zuiderweg, F. J.; Klinkenberg, A. Cbem. Eng. Sci.
1956, 5, 271-289.
Porter, P. E.; Deai, C. H.; Stross, F. H. J . Am. Chem. SOC.1956, 78,
2999-3006.
Gradshtein, I. S.; Ryzhik, I. M. fablitsy Integralov, Summ, Ryadov i
Proizvedenii (fables of Integrals, Summations, Series, and Products),
4th ed.; Fizmatgiz: Moscow, 1982; p 321, formula 3.322.
-
RECEIVED
for review October 10, 1986. Accepted March 3,
1987.
Identification of Mutagenic Methylbenz[ a ]anthracene and
Methylchrysene Isomers in Natural Samples by Liquid
Chromatography and Shpol’skii Spectrometry
Philippe Garrigues,*’Marie-Pierre Marniesse,’ Stephen A. Wise: Jacqueline Bellocq,’ and Marc Ewald’
Groupe d’OcCanographie Physico-chimique, LA 348 C N R S , Universitd de Bordeaux I , 33405 Talence Cedex, France, and
Organic Analytical Research Division, National Bureau of Standards, Gaithersburg, Maryland 20899
Chromatographic extracts of natural samples (rock and air
partlculate matter) have been examlned by high-resolution
Shpoi’skll spectrometry (HRS) at 15 K In n-alkane polycrystalline frozen solutlons for the ldentificatlon of the 12
methylbenr[a ]anthracenes (MBA) and the six methylchrysenes (MC). This Is the flrst report on the unamblguous
identlflcation of each MBA Isomer in real samples which wlll
provide a better understanding of carcinogenic potency and
further quantlflcation of these compounds in tetraaromatic
fractlons.
Polycyclic aromatic hydrocarbons (PAH) and their alkylated derivatives are well recognized as ubiquitous contamiUniversitB de Bordeaux.
2 N a t i o n a l Bureau of Standards.
nants of the environment. The major analytical problem in
the determination of PAH in complex natural mixtures is the
separation and the identification of individual components
in the presence of the numerous other isomeric parent and
alkyl-substituted PAH. Since the biological activity of aromatic compounds is isomer specific, the identification of each
compound in an alkylated aromatic series is a vital part of
understanding the carcinogenic activity of PAH mixtures.
Methylbenz[a]anthracenes (MBA) and methylchrysenes
(MC) are among the most biologically active alkylated aromatic series found in man’s environment (Figure 1) (1-6).
There are 12 possible isomers in the MBA series which vary
significantly with respect to carcinogenicity(Figure 1). 7-MEiA
has been recognized as the most tumorigenic compound,
followed by 6-, 8-, and 12-MBA, which are of equal carcinogenicity, while 9- and 11-MBA are the next most carcinogenic
compounds. The low tumorigenicity of the 1-,2-, 3-, and
4-MBA has been generally cited in support of the bay region
0003-2700/87/0359-1695$01.50/0 0 1987 American Chemical Society
1696
ANALYTICAL CHEMISTRY, VOL. 59,
NO.
13, JULY 1, 1987
I/
--3 MBA
I
1
.
Figure 1. Relative carcinogenic activity of methylbenz[a ]anthracene
(MBA) and methylchrysene (MC) isomers on a scale of zero to AAA.
I
d
Wavelength (nr?)
theory of PAH carcinogenesis (7-11). In the methylchrysene
series, 5-MC is one of the most carcinogenic compounds while
2-, 3-, 4-, and 6-MC are moderately active ( I , 12). However,
identification of methyl tetraaromatic compounds is particularly difficult because of their similar behavior in chromatographic techniques (liquid or capillary gas chromatography)
(13, 14). Capillary gas chromatography on conventional
nonpolar phases (e.g., SE-54) and liquid chromatography are
unsuccessful in the separation of all MBA and MC isomers
(12,13). Recent reports on liquid crystalline stationary phases
in capillary gas chromatography demonstrated improved
separation of these isomers (15);however, several isomers were
still unresolved. Whereas the identification of MC isomers
in natural extracts has been realized (12, 14, 16) only one
tentative identification of MBA isomers was reported previously by 'H NMR (3, 14).
One way to overcome the limitation of classical analytical
techniques in the differentiation of isomeric compounds is to
use high-resolution spectrometry (HRS) in n-alkane matrices
(Shpol'skii effect) which has been shown to be adequate for
solving such problems (16-18). This technique takes advantage of the sharpening of the fluorescence emission spectra
when aromatics are incorporated into an appropriate n-alkane
matrix a t low temperature (19). During the past decade,
Shpol'skii spectrometry has attracted the attention of analytical chemists considering the numerous publications recently reviewed (20).
In this paper, we report the low-temperature emission
properties of MBA and their identification in rock and air
particulate samples which also contained MC. Such studies
will lead to the quantification of individual MBA and MC
isomers, which is of particular interest in environmental
chemistry and organic geochemistry (21).
EXPERIMENTAL SECTION
Chemicals and Samples. The MBA were purchased from
the chemical repository of the National Cancer Institute
(Bethesda, MD). The purity of each MBA was reported as greater
than 96%. The six MC were purchased from the Community
Bureau of Reference (BCR, Commission of the European Community, Brussels, Belgium). The purity of each MC was certified
to be greater than 99.6%.
All the solvents (spectroscopic grade from Fluka and Merck)
used for HPLC fractionation and Shpol'skii analysis were purified
by distillation and then dried and kept over molecular sieves.
Residual fluorescence emission of solvents was verified by roomtemperature spectrofluorometry.
The sedimentary rock sample came from a well in an Indonesian
petroleum field (21)and was provided by J. L. Oudin (TOTALCFP, Pessac, France). The tetraaromatic fractions from a
Philadelphia, PA, air particulate sample and from a Washington,
DC, air particulate sample (Standard Reference Material, SRM
1649, Urban Dust/Organics) were obtained according to the
analytical procedure reported previously (22, 23).
Figure 2. Fluorescence emission spectra of some individual reference
MBA in n-octane at 15 K (c = lo-' M). Excitation was at 294 nm.
Note the important diffuse base for the 3-MBA.
Isolation of Monomethyl Tetraaromatic Isomers. The
fractionation procedure of aromatics, proposed by Wise et al. (24)
has been modified and used as applied previously to the isolation
of alkylated PAH (16, 18, 21). Briefly, the first normal-phase
high-performance liquid chromatography (HPLC) step on an
aminosilane column separates the aromatics into ring classes. A
two-step reversed-phase LC fractionation procedure then utilizes
the differences in selectivity between monomeric and polymeric
CIS columns to isolate fractions suitable for HRS analysis. The
separation on a monomeric reversed-phasec18 allows the collection
of the methyl tetraaromatic fraction. This fraction is then s e p
arated on a polymeric reversed-phase c18 column which has high
selectivity for the separation of PAH isomers (Supelcosil, type
LC-PAH) (13,18,25,26). A mixture of 70% acetonitrile in water
was used as the mobile phase to yield fractions of one to four
methyl tetraaromatic isomers that were amenable to identification
by HRS.
High Resolution Shpol'skii Spectrometry (HRS). Lowtemperature luminescence experiments were performed with a
homemade spectrofluorometer described previously (16). Fused
silica tubes containing the solutions were attached to the cold head
of a closed cycle cryogenerator (CTI, Cryodyne 21 SC) operating
at 15 K. Excitation was provided by a xenon lamp (450 W).
Emission spectra were recorded and stored on a hard disk of a
microcomputer (IBM/XT). Processing of the spectra gives
emission peak wavelengths with a precision of 0.1 nm.
R E S U L T S A N D DISCUSSION
Low-Temperature Spectrofluorometry of MBA Reference Compounds. Some previous studies have already
reported the Shpol'skii emission spectra of some MBA isomers
(27-30). The site multiplet structure for the 0-0 transition
of the 12 MBA in n-octane a t 15 K covers a spectral region
of about 10 nm (Table I and Figure 2). Each compound
exhibits sharp fluorescence emission spectra with a multiplet
structure containing up to four quasi-line emission peaks
arising from several different orientations of the MBA guest
molecules in the frozen n-octane host (29,31). The maximum
long-wavelength displacement relative to the emission peak
of the parent compound (benz[a]anthracene, BA) is observed
when the methyl group is introduced a t position 7 or 12,
whereas 1-, 2-, 3-, 4-, 5-, 6-, lo-, and 11-methyl derivatives
exhibited a shift of about 2-3.5 nm. The 9-MBA exhibits a
slight short-wavelength displacement while the 8-MBA gives
rise to a quasi-line structure in the same spectral area as the
BA. All these observations are in good agreement with previous studies (27, 28).
When the low-temperature fluorescence emission spectra
on the complete series of the 12 MBA are obtained, some
interesting observations can be made. Some isomers (1-,2-,
ANALYTICAL CHEMISTRY, VOL. 59,
Table I. Characteristic Shpol'skii Fluorescence Emission
Peaks of MBA and MC Isomers in n -Octane at T = 15 K"
compound
fluorescence emission peak,
nm
AA, nm
benz[a]anthracene(BA) 384.0 (+++), 384.3 (+++)
1-MBA
2-MBA
3-MBA
4-MBA
5-MBA
6-MBA
7-MBA
8-MBA
9-MBA
10-MBA
11-MBA
12-MBA
chrysene (C)
1-MC
2-MC
3-MC
4-MC
5-MC
6-MC
386.7 (+++), 387.0
386.7 (+++I, 387.0 (+++),
387.9 (+)
385.3 (+++), 385.8 (+++)
386.2 (+++), 388.5 (+++),
387.3 (+++)
387.6 (+++), 387.9 (+),
388.1 (++I, 388.5 (+)
385.0 (++), 386.3 (++),
386.5 (+++I, 386.8 (+)
389.2 (+++), 390.9 (+)
384.1 (+++), 384.3 (++),
385.0 (++), 385.4 (++)
383.1 (+), 384.0 (+++),
384.5 (+)
386.1 (+), 387.0 (+++),
387.1 (++), 387.4 (+)
384.3 (+), 385.6 (+++),
385.9 (++), 386.7 (++)
390.6 (+++I, 390.8 (+++),
391.4 (++), 392.1 (+)
360.5 (+++), 361.1 (+++),
362.2 (++)
361.3 (++), 361.9 (++),
362.2 (++), 362.5 (+++)
361.2 (+++), 361.5 (+++)
362.0 (+++), 362.2 (++),
362.6 (++), 363.1 (+)
365.4 (+++), 366.0 (+),
366.9 (++)
367.2 (+++), 367.6 (++),
367.9 (+)
362.6 (+), 363.3 (+++),
364.6 (++)
2.7; 2.4
2.7; 2.4
1.3; 1.0
2.2; 2.9
3.6; 3.3
2.5; 2.2
5.2; 4.9
0.1; 0.2
-0.9; -1.2
2.1; 1.8
1.6; 1.3
6.6; 6.3
0.8; 0.2
0.7; 0.1
1.5; 0.9
4.9; 4.0
6.7; 5.8
1.9; 1.3
"Excitation at 294 nm for MBA and at 274 nm for MC. AA
represents the peak shifts (in nm) of the major fluorescence peak
of each methylated derivatives relative to the two major fluorescence peaks of the respective parent compound. Intensity scale is
from zero to +++.
NO. 13, JULY 1, 1987
1697
3-, lo-,and 12-MBA) exhibit quasi-linear emission peaks that
emerge from a broad diffuse base (Figure 2) which could be
attributed to a strong interaction between aromatic molecules
and the n-octane chains. Such interaction could be due to
the position of the methyl group which leads to a nonplanar
character for some MBA molecules (32), e.g., the sterically
hindered MBA with substituents in position 1 and 12. The
presence of this diffuse base is also observed for MBA molecules for which the substituted carbon is bonded to carbon
atoms not engaged in ring structure (2-, 3-, and 10-MBA). On
the contrary, very nearly planar structures such as 4- and
11-MBA (32) do not exhibit such a diffuse base.
As shown in Table I, the multiplets of the MBA are subject
to spectral interferences in the emission region of the 0-0
transition. Particularly 1-and 2-MBA exhibit major emission
a t the same wavelengths. However, as presented in Figure
3, the most carcinogenic compounds (6-, 7-, 8-, and 12-MBA)
are easily identified in the synthetic mixture of the 12 isomers.
The other MBA isomers could be identified tentitatively by
two different analytical approaches: (a) by using selective
excitation with a laser (29)or (b) by HRS analysis of fractions
collected with a highly selective reversed-phase column (18).
This second approach has been developed for the identification of MBA and MC as described in this paper.
Analysis of MBA and MC in Natural Extracts. Specific
emission and excitation wavelengths of tetraaromatic parent
compounds are listed in Table 11. Despite numerous tetracyclic alkylaromatic derivatives, the selectivity of spectrofluorometry allows the observation of each series (chrysene,
benz[a]anthracene, triphenylene, naphthacene, benzo[c]phenanthrene) without interferences between each other
(Table I and 11) (33). Methyltriphenylenes have also been
observed as minor components of this fraction: indeed triphenylene exhibits fluorescence emission in n-octane at about
350 nm (30) and fluorescence emission peaks corresponding
to possible methyltriphenylenes have been observed at about
355 nm; but without reference standards a true identification
was not possible. Naphthacene (linear) and benzo[c]phenanthrene (sterically hindered) derivatives have not been
detected and are most likely minor contributors according to
Table 11. Characteristic Room-Temperature Fluorescence Properties of Tetraaromatic Parent Compound (31, 33)"
tetraaromatic compounds
benz[a]anthracene
max emission wavelengths, nm
max absorption
wavelengths, nm
385, 405, 430
222, 268.5, 278, 299
chrysene
361, 380, 402
218, 259,269
triphenylene
355, 362,373
284, 273, 258, 249
structure
@&
possible
methyl
derivatives
l2
@ p 6
2
@
@
naphthacene
482.5, 513, 551
294, 275, 265
3
benzo[clphenanthrene
broad band centered at 400
218.5, 222, 272, 283
6
The most intense band is italicized.
-
ANALYTICAL CHEMISTRY, VOL. 59, NO. 13, JULY 1, 1987
1698
T
5 MEA
I
5 MBA
7 MEA
12 MBA
3
4
u
R e t e n t i o n t i m e (mn)
+J
>
.6Y
c
+J
W
v,
c
._
W
0
e
W
6Y
0
Figure 5. Reversed-phase LC analysis of C, tetraaromatic fraction
from Washington urban dust (SRM 1649). Absorption detection was
centered at 288 nm. Compounds have been identified on the basis
of HRS spectra of reference compounds. Note the lack of 1-, 7-, and
12-MBA.
5 MBA
L
W
3
0
-
LL
sedimentary r o c k
C,-tetraarornatics
1
7 MBA
oi
390
Wavelength (nrn)
Figure 3. Fluorescence emission spectra of MBA isomers (excitation
at 294 nm): (a) in an equimolar synthetic mixture of the 12 MBA (each
at c = lo-' M); (b) in a C, tetraaromatic rock extract. Note the lack
of 12-MBA and the presence of the very carcinogenic 7-MBA.
+
fraction 2
I
0
0
i
385
sedimentary r o c k
5 MEA
o 1 1 MBA
X
1 MBA
0
7 MBA
Wavelength (nrn)
Figure 6. Fluorescence spectra of some MBA in subfraction 2 of C,
tetraaromatic fraction from the sedimentary rock. Excitation was at
294 nm.
R e t e n t i o n t i m e (mn)
Figure 4. Reversed-phase LC analysis of C, tetraaromatic fraction
from a sedimentary rock. Absorption detection was centered at 288
nm. Compounds are identified on the basis of HRS spectra of reference compounds. Note the lack of 12-MBA.
the predominance of angular over linear annelated and sterically hindered structures (34). Therefore, the distribution
of monomethyl tetraaromatics is dominated by the methylbenz[a]anthracenes and methylchrysenes.
The total C, tetraaromatic fraction of the sedimentary rock
which was isolated by reversed-phase LC on the monomeric
C18 column was analyzed by HRS for MBA determination.
Despite MBA emission interferences, HRS allows a partial
identification of selected MBA isomers (Figure 3). In particular, it is possible to observe the lack of 12-MBA and the
presence of 7-MBA in the C1 tetraaromatic rock extract which
are two of the most carcinogenic compounds of the series.
The C1 tetraaromatic fractions from the sedimentary rock
and air particulate samples were submitted to an HPLC step
on the highly selective polymeric CIS column (Figures 4 and
5 ) . As indicated by Wise et al. (13) and in Table 111, only
part of the methyl tetraaromatic isomers could be cleanly
separated from each other. The identification of MBA and
MC isomers in HPLC subfractions is demonstrated in Figures
6-8. Indeed, despite the use of an observation centered at
an absorption of 288 nm that favors MBA detection, MC
ANALYTICAL CHEMISTRY, VOL. 59, NO. 13, JULY 1, 1987
1699
Table 111. LC Retention Index (log I , ref 13) of MBA and MC and Their Identification in Natural Sample Fractions (See
Figures 4 and 5)
Philadelphia air
particulate
compound
retention index (log I)
sedimentary rock
Washington urban dust
matter
2-MBA
12-MBA
6-MBA
11-MBA
1-MBA
5-MC
6-MC
7-MBA
4-MC
8-MBA
10-MBA
5-MBA
3-MC
4-MBA
3-MBA
9-MBA
1-MC
2-MC
4.09
4.10
4.10
4.13
4.14
4.14
4.14
4.14
4.18
4.19
4.24
4.88
4.29
4.33
4.39
4.39
4.43
4.52
fraction 1
fraction 1
fraction 1
fraction 1
fraction 2
fraction 2
fraction 1
fraction 2
fraction 1
fraction 2
fraction 2
fraction 2
fraction 2
fraction 2
fraction 3
fraction 4
fraction 4
fraction 3
fraction 3
fraction 4
fraction 4
fraction 4
fraction 5
fraction 4
fraction 4
fraction 4
fraction 5
fraction 6
fraction 6
fraction 4
fraction 5
fraction 6
fraction 6
fraction 6
fraction 7
fraction 6
fraction 6
fraction 6
fraction 7
fraction 6
fraction 7
4 MBA
I
e
r e f e r e n c e compound
?
z.
c
ZI
.rn
h
7
c
&.
c
a?
.-
E
+
.-
Q
v)
c
0
c
a?
c
t
.-c
a?
0
ln
a?
0
Philadelphia a i r
L
a?
0
3
c
0
a?
particulate matter
i
i
u)
a?
L
fraction
Washington urban dust
fraction 5
0
a
LL
11;1,
362
365
2
360
W a v e l e n g t h (nm)
3a5
390
fnm)
Wavelength (nm)
Figure 7. Fluorescence spectra of 4-MBA in n-octane at T = 15 K
(excitation at 294 nm): (a) reference compound (c = lo-' M); (b)
Washington urban dust subfraction.
isomers contribute to the HPLC fingerprint (see Figures 4 and
5 where peak 7 is due only to 2-MC).
The 11MBA and four MC presented in Table I11 could be
identified by comparison of their HRS emission spectra with
that of the respective standard spectra. Both a coincidence
in the position of the quasi-lines and also a good agreement
in the relative intensities of the quasi-lines provide a definitive
identification of each compound (Figures 7 and 8). 12-MBA
is absent from the three natural extracts. Steric hindrance
could be responsible for the lack of 12-MBA as well for the
lack of 4-and 5-MC, which has been previously mentioned
Fluorescence spectra of 6-MC in n-octane at T = 1
(excitai I at 274 nm): (a) reference compound (c = lo-' M);
subfraction from Philadelphia air particulate matter. Note the lac1
the highly carcinogenic 5-MC which would be eluted with 6-MC,
present.
Figure
K
3)
f,
if
(21). 1-and 7-MBA have been specifically identified in the
rock extract but where not found in the air particulate extracts.
These two compounds are presumably less stable than the
other isomers. Methyl shift reactions could occur at higher
temperatures in aerosol formation than in the sedimentary
matter and would favor the formation of more stable methyl
isomers. The absence of 7- and 12-MBA in the atmospheric
particulate samples is in good agreement with the only previously reported determination of these compounds in air
particulate matter ( 3 ) .
These studies on the methylbenz[a]anthracene and methylchrysene series demonstrate the capability of HRS coupled
with HPLC separations for the differentiation of very closely
1700
ANALYTICAL CHEMISTRY, VOL. 59, NO. 13, JULY 1, 1987
related compounds such as MBA and MC. Positive identification of the 12 MBA isomers has not been reported previously due to the chromatographic interferences of MBA from
each other or from other methyltetraaromatic isomers.
This work is only the first step toward a better understanding of MC and MBA behavior in environmental samples.
Further developments will lead to the relative quantification
of these methyl-PAH in various natural samples to give a real
evaluation of biological activity of PAH fractions.
ACKNOWLEDGMENT
We thank J. Joussot-Dubien for his continuous interest and
support. Thanks are due to J. L. Oudin (CFP-TOTAL) for
providing sedimentary rock samples and to J. Lewtas (U.S.
EPA) for providing the Philadelphia air particulate sample.
The authors also wish to thank R. De Sury and N. Chedozeau
for technical assistance with the analytical work.
Registry No. 1-MBA, 2498-77-3; 2-MBA, 2498-76-2;3-MBA,
2498-75-1;4-MBA, 316-49-4; SMBA, 2319-96-2; 6-MBA, 316-14-3;
7-MBA, 2541-69-7; 8-MBA, 2381-31-9; 9-MBA, 2381-16-0; 10MBA, 2381-15-9 11-MBA, 6111-78-0; 12-MBA,2422-79-9; 1-MC,
3351-28-8; 2-MC, 3351-32-4; 3-MC, 3351-31-3; 4-MC, 3351-30-2;
5-MC. 3697-24-3: 6-MC. 1705-85-7.
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Grimmer, G.;Jacob, J.; Naujack, K. W.: Dettbarn, G. Fresenius' 2.
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RECEIVED
for review November 20, 1986. Accepted March
2, 1987. Certain commercial equipment, instruments, or
materials are identified in this report to specify adequately
the experimental procedure. Such identification does not
imply recommendation or endorsement by the National Bureau of Standards, nor does it imply that the materials or
equipment identified are necessarily the best available for the
purpose.