Environ. Sci. Technol.
1994, 28, 1733- 1746
Study of 22-Year-Old Arrow Oil Samples Using Biomarker Compounds by
GC/MS
Zhendl Wang,' Merv Fingas, and Gary Sergy
Emergencies Science Division, ETC, Environment Canada, 3439 River Road, Ottawa, Ontario, Canada K 1A OH3
A GC/MS method for the characterization of 22-year-old
spilled Arrow oil is described. After 22 years of weathering
in the environment, most saturated hydrocarbons and
polycyclic aromatic hydrocarbons in most Arrow oil
samples have been lost. Their fingerprints give little
information of the source, characteristics, and fate of the
spilled oil. However, the method using biomarker com-
pounds by GC/MS offers the distinct advantages of being
better able to withstand interference from heavy weather-
ing effects and to identify and match the spilled oil source.
From 11 intertidal sediment samples collected from the
shorelines of Chedabucto Bay, 47 triterpanes and steranes
were positively identified. The relative abundance ratios
of several pairs of triterpane and sterane compounds,
especially the ratio of CdC30 hopanes that are displayed
as major peaks in the m/z 191 ion chromatograms, are
apparently independent of weathering effects and are
unambiguously used for identifying the source of the 22-
year-old Arrow oil samples.
Introduction
The Arrow spill began on February 4, 1970, following
the grounding at Cerberos Rock, 6.5 km from the north
shore of Chedabucto Bay, Nova Scotia, Canada. Ap-
proximately 2.5 million gal (10 000 t) of Bunker C oil was
released from the tanker Arrow during the subsequent
breakup and sinking of the tanker. As a result of the spill,
about 305 km of the 604 km of shoreline in Chedabucto
Bay was impacted to varying degrees, of which only 48 km
was treated and cleaned in the subsequent response
operation ( I ) .
Since the spill took place, a series of scientified surveys
and studies have been conducted to assess its effect. These
studies include a ground survey in 1973 (2-4), a recon-
naissance aerial survey with ground stops in 1982 (5),and
a systematic ground survey of the entire coast in September
1992 (1). The primary goals of the 1992 survey were to
provide an up-to-date, systematic, detailed analysis of
oiling conditions of the area. This included a regional
survey to map the distribution of surface oil and to locate
the presence of any subsurface oil in those areas where
residual oil has been located and, at selected sites, the
collection of residual oil samples for full compositional
analysis of residual oil in order to ascertain the nature of
the oil present.
This survey documents that, with a few localized
exceptions, the coast of the region is free of oil, indicating
that 22 years after the Arrow spill, most of the 260-km
shorelines oiled by the heavy Bunker C oil has self-cleaned
(Le., the natural weathering processes account for the
majority of the removal of oil). This survey also indicates
that where oil remains, it is usually either as a thin stain
on bedrock or coarse sediments (pebbles, cobbles, and
boulders) or as a resistant natural asphalt pavement (a
cohesive mixture of weathered oil and sediment). The
0013-936X/94/0928-1733$04.50/0 0 1994 American Chemical Society
presence or absence of oil residues on the coast 22 years
after the spill incident can be explained in terms of the
physical, biophysical, and biological degradation processes
that act upon stranded oil.
The major objectives of the chemical characterization
of the spilled Arrow oil in the samples collected from
Chedabucto Bay are as follows:
(a) All oil is thought to be from the 1970 Arrow spill;
however, it would be useful to verify that this is the case
through chemical characterization; (b) To determine the
residual composition of the oil and changes in its physical
and chemical characteristics as a result of physical,
chemical, and biological processes; (c) To quantitatively
determine the concentrations of key individual compo-
nents or compound classes used for evaluation of the spilled
oil behavior, fate, and its toxicity as it persists in the
environment.
The compositional analyses of sediment samples include
the following: (1) total petroleum hydrocarbons, (2)
distribution of n-alkanes and some selected isoprenoids,
(3) important petrogenic polynuclear aromatic hydrocar-
bons (PAH) and their alkylated homologues, and (4)
biomarker compounds (triterpanes and steranes). These
target analytes were valuable for many aspects of oil
assessment, because they include not only those environ-
mentally important comopunds but also those major
constituents that are useful as indicators and markers of
the fate and weathering degree of the spilled oil in the
environment (6).
We report in this paper our attempt to develop an
analytical method suitable for the identification of long-
term weathered oils (such as the Arrow oil samples)
primarily through the characterization of biomarker
compounds in addition to the analysis of saturates and
PAH compounds.
After the pioneering work of Albraiges and Albrecht
(7), molecular markers have been extensively used for oil
spill correlations (8-11). The method based on hopane
analysis to estimate the percent of oil depletion has been
recently proposed (12).
For weathering studies, chemical composition change
and biodegradation are both important factors to consider,
especially when there is a prolonged period of weathering.
A lightly degraded oil is usually indicated by partial
depletion of n-alkanes; amoderately degraded one is often
indicated by heavy loss of n-alkanes and partial loss of
lighter PAH compounds. But, for highly degraded oil such
as Arrow oil samples, the n-alkanes and branched alkanes
could be completely lost, and PAHs and their alkyl
homologues could be highly degraded. In such cases,
identification through the recognition of n-alkanes and/
or the PAH distribution pattern would suffer great
difficulties, and analysis of biomarker compounds would
be not only necessary but also particularly important and
valuable because only these highly degradation-resistant
compounds remain in samples after long-term weathering
and can give chemical fingerprinting information of the
Environ. Sci. Technoi., Voi. 28, No. 9, 1994 1733
source, degree of weathering, characteristics, and fate of
the spilled oil (8-12).
During the course of our work of developing methods
to identify oil source and studying the effect of weathering
on the chemical composition of oil, it has been demon-
strated that the advantages of using hiomarker compounds
to characterize the long-term and highly weathered oil are
apparent compared to other approaches: (1)these com-
pounds suffer little interference from weathering effect
due to their high resistance to degradation: (2) in general,
biomarker distribution patterns are different even for those
oils which have similar geographical origins and/or have
very similar chemical compositions especially after weath-
ering, their fingerprints can be used to diagnose different
sources of hydrocarbon input; (3) hiomarker compounds
are often more abundant in highly weathered oils, and
therefore quantitation can he easier and more accurate.
Experimental Section
Materials. The materials and standards used in this
study were identical to those described in ref 13.
Arrow Oil Samples. A total of 11intertidal sediment
samples were collected from the intertidal zone around
Black Duck Lagoon (samples A-7) and the eastern end of
Rahhit Island (samples 8-10) of Chedahucto Bay (Figure
1). Both sites were heavily oiled in 1970 as a result of the
Arrow spill and by 1992 were two of the few remaining
sites of "major" oil residue. The samples collected from
these two sites were of very different quality and forms,
including samples of oil in the upper and lower intertidal
zone: surface,subsurface, f i e and coarsegrained intertidal
sediments, oil which coated the cobble; encapsulated oil
1734 Envhon. Scl. Tedmol., Vd. 28. No. 9, 1994
pockets; free-flowing mobile oil; and oil contained within
severalvarieties of exposed asphalt pavement formations.
Field programs were designed to ensure that sampling
sites were properly documented and relatively representa-
tive and that rigorous sample collection procedures were
followed to minimize the possibility of hydrocarbon
contamination. A brief description of the samples is given
in Table 1. Prior to analysis, the samples were tightly
sealed and stored in a cold room at 0 "C. The weathered
sourceArrow oil was suppliedfrom EricLevy'slab,Bedford
Institute of Oceanography (Dartmouth, Nova Scotia,
Canada).
Sample Extraction andcleanup. A 5-100gsediment
sample (the sample weights taken were dependent on how
much oil the samples contained) was placed in a 250-mL
solvent-rinsed Erlenmeyer flask, spiked with the ap-
propriate surrogates (0-terphenyl, dlo-acenaphthene, dlo-
phenanthrene, dlz-benzIalanthracene, and d12-perylene),
and mixed with equal amounts of sodium sulfate to dry
the sample. If the sample had excessive moisture, ad-
ditional amounts of sodium sulfate were added, and then
they were serially extracted three times with 60 mL of 1:l
hexane/dichloromethane (DCM), DCM, and DCM for 30
min using sonication. If there was visible color in the
third extraction, an additional extraction was performed.
The extracts were combined, dried with sodium sulfate,
and then filtered through a Gelman type A/E glass fiber
filter. The extracts were concentrated to appropriate
volumes hy using therotaryevaporationandnitrogen blow-
down techniques. An aliquot of the concentrated extract
(0.5-1.0 mL) was blown down with Nz to a residue and
weighed on a microbalance to obtain a total solvent-
~~ ~
Table 1. Description of the Arrow Oil Samplese
sample description
Amid-intertidal zone, south of sample 7
soft pavement over fine organic sediments,
marsh grasses growing through oil pavement
1 supratidal zone (above mean high tide level)
seaward side of spit, very exposed
oil cover on pebble-cobble beach material
collected from 20 X 20 cm plot excavated
20-30 cm deep in a cobble storm ridge
2 supratidal zone
seaward side of Black Duck Lagoon, very sheltered
asphalt pavement formation, 2-3 cm thick
over top of sand substrate
no fresh oil appearance but center of pavement
with some black shiny and sticky residues
3 upper intertidal zone, downslope of sample 2
asphalt pavement patch over dry course
sediment substrate
4 mid-intertidal zone, downslope of sample 3
asphalt pavement, internally tacky, 2-3 cm thick,
over dry coarse sand
5 lower intertidal zone, downslope of sample 4
on a low rise area
soft asphalt patch over wet, very fine sans-silt
sediments with eel grass
6 supratidal zone
below surface crust, “pure” oil, honey-like consistency,
flowed on disturbance of cobbles
contained in pockets between the large cobbles and
topped by a hard crust oil layer
7 upper intertidal zone
landward side of lagoon in heavily vegetated marsh
soft pavement over fine organic sediments,
marsh grasses growing through oil pavement
8 mid to upper intertidal zone
moderately exposed site in terms of wave-energy levels
free flowing subsurface oil sample collected from
a pit trenched in sandy-cobble substrate
9 upper intertidal zone, upslope from sample 8
asphalt pavement, over sandy-cobble
very weathered in appearance, surface turned to
light brown color
10 mid-intertidal zone, very sheltered lagoon of fine silts/
mud (anaerobic conditions?)
sample taken 3 cm subsurface
sulfur-containing compounds smell
a Samples A-7 are from Black Duck Lagoon. Samples 8-10 are
from the eastern end of Rabbit Island.
extractable material weight (TSEM, expressed as mg/g of
sample).
The weathered source Arrow oil was directly dissolved
in hexane at a concentration of 100 mg/mL and spiked
with the appropriate surrogates.
The microcolumn fractionation technique developed in
our laboratory was employed for sample cleanup and
fractionation of the oil (13). Half of the hexane fraction
(Fl) was used for analysis of saturates and biomarker
compounds; half of the 50% benzene fraction (F2) was
used for analysis of target PAHs and alkylated PAH
homologues. The remaining half of F1 and F2 were
combined (F3) and used for the determination of total
GC-detectable petroleum hydrocarbons (TPH). These
three fractions were concentrated under a steam of nitrogen
to appropriate volumes, spiked with internal standards
(Cao-P,@-hopane, dderphenyl, and 5-a-androstane for F1,
F2, and F3 respectively), and then adjusted to the accurate
preinjection volume for GC/FID and GC/MS analysis.
For gravimetric determination of the percentage of
saturates and aromatics, the entire hexane and 50 %
benzene fractions were evaporated to residues under
nitrogen, and the residues were quantitated gravimetrically
using a microbalance. The percentage of the saturates
and aromatics in the extract can be readily estimated by
their weight divided by the TSEM. The sum of the
saturates and aromatics was defined as the gravimetrically
determined total petroleum hydrocarbons (GTPH). The
asphaltenes plus polars account for the difference between
TSEM and GTPH.
Capillary Gas Chromatography (GC) and Gas
Chromatography/Mass Spectrometry (GUMS). For
the instrumentation and quantitation, please refer to ref
13.
Results and Discussion
Determination of Oil Residues. Table 2 presents the
gravimetric results of the sediment hydrocarbon analyses.
In addition to the TSEM and GTPH, some other
definitions used in Table 2 are interpreted as follows: (a)
TPH, total GC-detectable petroleum hydrocarbons, are
the sum of all resolved and unresolved distillable hydro-
carbons detected by GC. The unresolved complex mixture
of hydrocarbons (UCM) appear as the “envelope”or hump
area between the solvent baseline and the curve defining
the base of resolvable peaks; (b) GC-undetectable high
molecular weight (MW) hydrocarbons, the difference
between GTPH and TPH, represents the high MW
hydrocarbons retained on the GC column and undetected
by the GC.
Note that all results of the sample chemical composition
discussed below are expressed on the TSEM basis. TSEM
supplies an equal basis for the determination of the relative
composition of saturates, aromatics, and asphaltenes plus
polars in samples. It is only by this way that the
quantitation results are comparable.
Key points from Table 2 can be summarized as follows:
(1)the major chemical composition changes observed for
the Arrow oil samples are that the more the sample was
weathered, the smaller the ratios of GTPH to TSEM and
TPH to TSEM are, the greater the percentage of asphalt-
enes plus polars in TSEM is; (2) among all samples, the
weathered source Arrow oil, which was used as a com-
parison reference, has the highest concentration of GTPH,
composed of 40% saturates and 30% aromatics; (3)
samples 1and 10 show some distinct compositional traits
relative to other samples, such as the lowest GTPH/TSEM
and TPE/TSEM values, very low concentrations of
saturates and aromatics, and very high concentration of
aspheltenes plus polars in the TSEM (70%); (4) the values
of TPH, saturates, and aromatics determined by GC are
exclusively smaller than the corresponding values by
gravimetric method for all samples. The GC-undefined
high MW hydrocarbons account for the difference between
them. For example, the GC-detectable TPH represents
about 33% of TSEM of the sample A by weight, and
asphaltenes plus polars represent about 45 % . About 22 %
of TSEM was not detected by GC, but was still accounted
for by the gravimetric mass balance. This observation
was in accordance with the previous works on the oil
weathering and degradation (9, 14, 15).
Qualitative and Quantitative Comparison of GC
Traces. The oil weathering rate depends on the extent
of initial oiling, the degree of cleanup, and the weathering
conditions (16). The question “How heavily weathered
was the oil?” can be illustrated in a qualitative manner by
Environ. Sci. Technol., Vol. 28, No. 9, 1994 1735
Table 2. Analysis Results of Arrow Oil Samples by Gravimetric and GC/FID Method
asphaltenes
TSEM GTPH + polars saturates aromatics TPH by GC UCM
(mgk of (mdg of (mg/g of GTPH/ in TSEM of TSEM (mg/g of (mgk of TPH/
sample no. sample) sample) sample) TSEM (%) (%) sample) sample) TSEM
weathered source oil 825 575 250 0.70 40 30 450 410 0.55
S-A 100 54.7 45.3 0.55 37 17 33.3 32.8 0.33
s-2 194 97.0 97.0 0.50 37 13 51.0 50.0 0.26
s-3 124 72.0 52.0 0.58 39 19 47.5 46.8 0.38
s-4 76.0 51.4 24.6 0.68 41 27 33.1 32.6 0.44
s-5 5.3 3.7 1.6 0.70 36 34 2.2 2.1 0.42
S-6 500 330 170 0.66 40 26 229 215 0.46
s-7 76.0 49.7 26.3 0.65 40 25 31.6 31.3 0.42
S-8 29.5 20.0 9.5 0.68 39 29 12.8 12.6 0.43
s-9 34.6 17.1 17.5 0.49 21 27 9.0 8.9 0.26
s-1 3.0 0.8 2.2 0.25 18 7 0.5 0.5 0.15
s-10 1.0 0.3 0.7 0.30 15 15 0.2 0.2 0.18

inspection of its GC trace. For example, Figure 2 compares
the GC/FID traces (F3) for the samples S-6, S-2, and S-1.
Figure 3 presents the GC/MS chromatograms of the m/z
85 fragment (one of the characteristic fragments for
n-alkanes) of the saturated hydrocarbon fraction (Fl) of
the weathered source oil, S-6 and S-4. The remaining
samples show almost identical GUMS chromatographic
profiles as sample S-4. These GUMS chromatograms are
not particularly useful for determining the source of the
spill, but they give information on the degree of weathering
or freshness of the sample, which is indicated by the
distribution of n-alkanes and by the profile of the hump.
Figures 2 and 3 clearly demonstrated the effects of
weathering and degradation on the chemical compositions
of the oils. The GC/MS chromatogram of the saturated
hydrocarbons in the weathered source oil (Figure 3A) shows
a mixture dominated by a homologous series of n-alkanes
ranging in carbon number from n-Cg to n-C4o with the
maxima around n-Czo-n-Cz~. Isoprenoid hydrocarbons
which are commonly considered in weathering studies are
also present, and pristane and phythane are the most
abundant. It is suprising to note that the existence of
what is apparently original Arrow oil after 22 years in S-6
sampled from pools on a beach has characteristics almost
identical to the same oil stored in a sealed container (i.e.,
the weathered source oil). In sharp contrast, the n-alkanes
including the five less degradable isoprenoids (2,6,10-
trimethyldodecane, 2,6,10-trimethyltridecane, norpris-
tane, pristane, and phytane) in the sample S-4 and other
samples were nearly completely lost, indicating that these
samples have undergone extreme alternation. Another
pronounced feature for the S-4 and other samples is the
big humps representing the GC unresolved complex
mixture of hydrocarbons in the chromatograms, which is
characteristic of heavily weathered and biodegraded oil
(17).
Table 3 presents the quantitation results for n-alkanes
in the weathered source oil and S-6. Figure 4 compares
the n-alkane distribution patterns from these two samples,
based on the amount of the n-alkane c26 (cZ6is selected
as it is at the point in the series where the relatiev changes
go from loss to gain). The concentration reduction of the
low boiling components and the buildup of the high boiling
components relative to the smaller n-alkanes indicate that
the source oil and S-6 have been significantly weathered,
even though the n-alkanes in these two samples were not
completely lost. The lower value of the weathering index
(WI),defined as the ratio of (n-Cs+ n-Clo + n-Clz + n-C14)/
(n-czz + n-C24 + n-C26 + n-Cz8) (18),indicates the greater
extent and degree of weathering of S-6 in comparison to
the weathered source oil. It is interesting to note from
Figure 4 that due to the additional weathering, the relative
concentrations of n-alkanes before n-Cz6 in S-6 are lower
than the corresponding n-alkanes in the weathered source
oil, and the n-alkanes after n-C26 show the reverse trend.
The only exception before n-C26 is pristane and phytane
with the relative concentrations in S-6 being significantly
higher than in the weathered source oil, which is an
indication that the isoprenoids pristane and phytane were
degraded at a slower rate in comparison to n-alkanes. A
preferential loss of n-alkanes often indicates the occurrence
of biodegradation (19).
For S-4 and the remaining samples, only unresolved
envelopes or humps were observed in their GC traces. By
visual comparison, these broad humps are very similar in
the distribution patterns, indicating that they were highly
weathered and possibly came from the same source.
Obviously, such GC traces cannot provide much informa-
tion about compositional changes nor be very useful for
the purpose of matching the samples to the known source
oils.
Quantitation of Target PAHs and Their Alkylated
Homologues. PAH compounds are relatively stable and
diagnostic constituents of petroleum. Some studies have
been done using the distribution of the alkylated PAH
homologues as environmental fate indicators and source
specific markers of oil in sediments (17,20,21)and tissue
samples (22, 23).
Table 4 summarizes the quantitation results of alkylated
PAH homologues in the Arrow oil samples. Figure 5
depicts graphically the PAH distributions of the weathered
source oil, S-6, S-A, and S-9. In order to more clearly see
the changes in the distribution patterns within the different
PAH families, the different scales for Y-axis were applied
to Figure 5A (0-3200), 5B (0-800), and 5C and 5D (0-400
yg/g TSEM). The aromatic fraction of the weathered
source oil contains primarily alkylated naphthalene and
phenanthrene homologues with CZ-and Cs-naphthalenes
being dominated (3073 and 3013 pg/g, respectively).
Alkylated dibenzothiophenes are also present, but in lower
concentrations than the phenanthrene series. The loss of
PAH compounds and their alkyl homologues in the Arrow
oil samples is very apparent. The factors affecting the
weathering process of the spilled oil in the environment
during the past 22 years are very complex (24). The
combined effects of weathering (such as evaporation,

1738 Envlron. Scl. Technol., Vol. 28, No. 9, 1994

 2.2e4-
A
2.0e.i

1 .sed

1.4e4-

12e43

10-4.-

EOOO-,

4
6000-

4000-

2ooo+-
0 20 40 60

1 , ’
0 1 0 20 30 40 50 60 7 0

2.2’q C
2.0’43

1.2-4 IS

8000-1

60004

4000j

0 20 40 60

Flgure 2. GC/FID traces for the Arrow oil samples S-6 (A), S-2 (B), and S-1 (C). IS means internal standard.

Envlron. Sci. Technol., Vol. 28, No. 9, 1994 1737

 I
25000 i
1

ic000 -

1
15000.

, lG000!

~ 5000; !I
pbundance Ion 85.00
30000 ! B

25000 -I

20000 -! I

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:: I
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10000

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Tire--> 5.00 10.00 15.00 20.00 25.00 30.00 35'00 40.00 45.00 50.00 55.00

Aburdance Ion 85.00

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i

1 250COj

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10000 -

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Flgure 3. GC/MS chromatograms of saturated hydrocarbons (mlz 85) for the weathered source oil (A), S-6 (B), and S-4 (C). Numbers represent
carbon numbers of +alkanes. i-C15, 1416, 1418, Pr, and Ph represent the five most abundant isoprenoids (2,6,10-trimethyidodecane, 2,6,10-
trimethyitridecane, norpristane, pristane, and phytane, respectively).

dissolution, photooxidation, and biodegradation) of the PAHs. Major compositional changes of PAHs observed
spilled oil may be responsible for the progressive loss of are as follows: (1)pronounced decrease in naphthalene

1738 Envlron. Sci. Technol., Vol. 28, No. 9, 1994

Table 3. n-AIkane Distribution of Weathered Source and ita alkylated homologues relative to other PAHs
Arrow Oil and Sample 6 (compared to the weathered source oil, greater than 95%
of naphthalenes were lost in most samples); (2) develop-
weathered murce
Arrow oil sample 6 ment of a profile in each PAH group showing the
@g/g of TSEM) ( d g of TSEM) distribution of CO< C1< CZ< Ca; (3)gradual buildups in
the relative abundancesof the substituted phenanthrenes
0 0
59 9 (C2, C3, and C,), dibenzothiophenes (C2 and C3), and
148 27 chrysenes (CI, Cz, and C,) as the lighter and more soluble
249 57 components in the same families were lost. The chrysenes
341 103 exhibit the most pronounced relative increase due to their
426 169 very low solubilities in water and high resistance to
544 240 degradation. For example, the relative ratios of the s u m
694 299
854 440 of the alkylated chrysene to the alkylated phenanthrenes
1020 560 and dibenzothiophenes increased from 0.13 and 0.19 for
615 409 the weathered source oil to 6.7 and 55 for the S-1,
1044 541 respectively.
708 546
1101 561 It is noted from Table 4 that compared to the weathered
1202 603 source oil, S-6 shows three important PAH weathering
1295 643 features: (1) S-6 and the weathered source oil display
1364 682 approximatelythe same raticm of chrysenes/phenanthrenea
1320 669 (0.13and 0.13, respectively) and chrysenes/dibenzothio-
1301 672
1127 611 phenes (0.19 and 0.20, respectively); (2) they have very
1036 598 close concentration values (pglg of TSEM) of total
991 581 phenanthrenes, dibenzothiophenes,and chrysenes;(3)the
917 552 determined relative ratios of Co-:C1-:Cz-:C3-chrysene are
846 495 almost identical (0.781.161.481.M)and0.731.11:1.401.00,
755 428 respectively). Combiningthis fact with the fact of n-alkane
602 374
506 320 distribution, it can be concluded that (1)S-6 had very
358 265 similar chemical composition to the weathered source oil,
296 222 even though it was more weathered and (2) S-6 was the
155 152 least weathered one among all samples.
113 106
99 92 Very recently, a method using the double ratio plots of
87 66 alkyl PAH homologue for petroleum source identification
76 48 has beenpropoaed(21). Thismethodhasbeensueesafully
55 42 used to correlate the 1989 Exxon Valdez spilled oil
22 316 12 200 sedimentsamples to the source oil. The relative constancy
of the ratios of Cz-D/C2-P and Cs-D/Cs-P for over 140
1.66 1.37 samples was observed. Figure 5 and Table 4demonstrate
1.41 1.00
0.87 0.75 that, compared to the weathered source oil, more than
0.99 0.99 80% of the total PAH compounds were lost for most
0.22 0.15 samples. It is also noted from Table 4 that except for the
sample S-6 (which shows almost identical ratios of Cr
DICz-P and CsD/Cs-P to the weathered source oil), the
CPI, Carbon Preference Index = (sum of odd n-alkanes)/(sum remaining samples did not show such obvious correlation.
of even n-alkanes). This fact impliesthat, for the long-termheavily weathered

Wealhered Souroe A m Oil

".Ab".,
Flgure 4. Comparison of t b relstlve Raikane concentrations and the ~ h n distribution
a patterns for Uta weamered m c e oil and the sample
S-6. The arrows indicate that before the reletbe concentrations of pristane and phylane in the sample S-6 are h i g k than in the weathered
source oil.

En*. x(. Tedno(.. Vd. 28. No. 9, 1994 1750

 S I oil samples such as the 22-year-old Arrow oil samples in
which the aromatic compounds have been degraded and
altered extensively, it would be difficult if not impossible
to match them to the source oil based only on the PAH
analysis results.
9
Figure 6 shows the plot of the relative ratios of the total
4
alkylated chrysenes to phenanthrenes and dibenzothio-
phenes versus the oil samples (the samples S-9, S-1, and
S-10 were not shown due to their excessive relative ratio
values, see Table 4). The plot may imply the extent and
the degree of weathering of the Arrow oil samples. The
S more weathered the oil, the greater the buildup of
I chrysenes in the relative abundances, resulting in higher
ratios of chryseneslphenanthrenes and chryseneldiben-
0 zothiophenes. The highest ratios of chrysenes/phenan-
threnes and chrysenes/dibenzothiophenes for the samples
9 S-1, S-10, and S-9 were determined to be 6.7, 1.5, and 1.6
3
2 and 55,3.4, and 4.3, respectively, indicating that they were
0 the most highly weathered ones among all samples.
Identification and Quantitation of Biomarker
Compounds. As described above, the hexane fraction
-h :
2
from the silica gel column cleanup was used for analysis
of biomarker compounds. The group separation prior to
w
GC analysis is necessary because it minimizes interference
from other oil components.
The structural identification of biomarker compounds
3q is based on mass data in both scan and SIM modes, pattern
3 recognition of mass spectra, comparison of GC retention
data with reference standards, and literature data. The
common features of the mass spectra of triterpanes and
9
2 steranes are that they have a relatively large parent ion,
an important parent minus a methyl ion, and a base peak
a t mlz 191 and 217 (or 218), respectively. Figure 7 shows
the distribution profiles of triterpanes at m/z 191 of the
weathered source oil and S-4. Table 5 lists the names,
molecular weight, and empirical formulas for 47 positively
identified triterpanes and steranes.
The hopane distribution reflects the petroleum inputs.
Figure 7 is characterized by the triterpane distribution in
a wide range from C 2 0 to C 3 5 with c 2 3 and c 2 4 tricyclic
9
3 hopanes and C29 a,@-and C 3 0 a,@-pentacyclichopanes being
c?
3 quite prominent. Table 6 presents the quantitation results
for the four most abundant and prominent hopanes: C 2 3
and c 2 4 tricyclic hopane, C 2 9 a,& and c 3 0 a,@-pentacyclic
9 hopane. The relative ratios of 18a(H),21@(H)-22,29,30-
d
W trisnorhopane (Ts) to 17a(H), 21@(H)-22,29, 30-trisnor-
9
F!
3
hopane (Tm), and 20S/(20S+20R) of C 3 2 and C 3 3 hopane
isomer pairs are also listed in Table 6. Please note that
in order to compare the quantitation results on an
evenfooted basis, the concentrations of all hopanes were
3 expressed in micrograms per gram of TSEM. It can be
seen from Table 6 that (1)the concentrations (pglg) of
3
3
c 2 9 , c 3 0 , c 2 3 , and C 2 4 hopanes are comparable; (2) except
for S-1 and 53-10, the weathered source oil has the lowest
concentrations of C 2 9 and C 3 0 hopane; (3) S-6 shows very
similar concentrations of hopanes to the weathered source
oil; and (4) the buildup of hopanes relative to the weathered
source oil are apparent for the remaining samples.
At most locations sampled, any Arrow oil present had
3 undergone extensive weathering, which was characterized
by the total loss of n-alkanes and isoprenoids and the nearly
total loss of the lighter naphthalenes and fluorenes. If
identification of the spill source and oil matching was just
based on comparison of saturate and PAH distribution
patterns, it would be extremely difficult if not impossible

1740 Envlron. Scl. Technol., Vol. 28, No. 9, 1994

 A
PAH Homologues
Flgure 5. PAH flngerprints of the weathered source oil (A), S-6 (B), S-A (C), and S-9 (D) illustratingthe effects of weathering on PAH compositions.
N, P, D,F, and C represent naphthalene, phenanthrene, dibenzothiophene, fluorene, and chrysene, respectively; 0-4 represent carbon numbers
of alkyl groups In alkylated PAH homologues.
09-
08-
-
-i-
ChryrIPhens
ChryslDibenr
07-
06-
0% ~ _ _ -
D vi
4
: found in this work that the ratios of two pairs of the most
Figure 6. Plot of the relative ratios of the total alkylated chrysenes
to phenanthrenesand dibenzothiophenesversus the Arrowoil samples.
to draw any positive conclusion on whether these 22-year-
old samples came from the same source. Fortunately, the
fingerprinting of triterpanes provides us with a powerful
tool for tracking the source of the long-term weathered
oil. In this work, two criteria were used for matching the
long-term weathered oil with the source oil: (1)whether
the distribution profile and pattern of m/z 191 and 217
fragments are the same and (2) whether the computed
ratios of some target pairs of hopane and sterane com-
pounds are near identical.
The GUMS measurements demonstrate that the pro-
files and patterns of the m/z 191 and 217 ion chromato-
grams of the Arrow oil samples are nearly identical, except
that the samples S-1 and S-10 showed the similar
distribution patterns but with some peaks being less
abundant and even undetectable. More importantly, the
ratios of five pairs of target hopane compounds [Ts/Tm,
c 2 3 / c 2 4 , c 2 9 / c 3 0 , c 3 2 20S/(20S+20R), and C 3 3 2 0 8
(2OS+2OR)] are almost the same (Table 6) for most
samples. These facts strongly suggested that they may
come from the same source.
The ratio of Ts to Tm has been used as a geochemical
parameter to characterize both source input and maturity
of a crude (25) and as a indicator for oil matching (26).
However,in many cases, these two peaks are not abundant
enough to give a precise and accurate ratio of Ts/Tm. We
abundant hopanes (C23/C24 and c 2 9 / c 3 0 ) , especially the
ratio of the hopanes c 2 9 / c 3 0 , can be used as very good
indicators for oil matching and oil source tracking. Table
6 shows that the values of Ts/Tm range from 0.26 to 0.29,
the values of c 2 3 / c 2 4 and c 2 9 / c 3 0 range from 1.98 to 2.10
and from 0.84 to 0.87 for samples from S-A to S-9,
respectively. But for samples S-1and S-10,the values of
Te/Tm, c 2 3 / c 2 4 and c 2 9 / c 3 0 are 0.31 and 0.36, 0.62 and
1.00, and 0.87 and 0.89, respectively. Among them, only
the c 2 9 / c 3 0 ratios appear to be consistent and to be the
best indicator to track the oil source for these two most
highly weathered samples. Beside that, the relatively lower
abundant but well-resolved C 3 2 (peaks 25 and 26) and C 3 3
(peaks 27 and 28) 20S/20R hopanes also show very good
consistency in thevalues of 2OS/(2OS+2OR) ratios, ranging
from 0.57 to 0.61 for c 3 2 bishomohopanes and from 0.60
to 0.64 for C 3 3 trishomohopanes, respectively.
Environ. Sci. Technol., Vol. 28, No. 9, 1994 1741
 fbundance
1 A Ion 191.00
Ion 1 7 7 . 0 0

J
I

I
~ 3500

!I
6
19

2000 4
1 5

4
Isi
22
1500

2
-1
~

1000

01 I I ' ' ' . ' I ' ' ' ' I '

/rime-->25 100 ' ' 30.00 35.00 40.00 45.00 50.00

bundance Ion 191.00 I

1 0

IS

3000 1 20 I
1 19
2500 1

0 i " " I " " l " " / " " l " " I "
ime-->25.00 30.00 35.00 40.00 45.00 50.00
~

Flgure 7. Distribution of triterpanes (mlz 191) for the weathered source oil (A) and S-4 (B). The right inset in panel A is the chromatogram of
m/z 177 in 38-42 min. See Table 6 for component identification. The peaks 14 and 17 are identified as C27 254risnorhopane and CZ825-
blsnorhopane, which show significantly higher abundance of the mlz 177 fragments. The general structure for hopanes is shown in the lefi inset
of panel A.

Under most natural weathering conditions, which usu-
ally has evaporation as the main process, the Ts/Tm ratio
should suffer little change, if any, and remain characteristic
of the source crude. The same is true for C23/C24. But,
under very long and extreme weathering conditions, the
ratios of Ts/Tm and c 2 3 / c 2 4 may suffer change. I t has
also been found that Tm has a relatively faster rate of
depletion than Ts in the process of crude maturation (26).
In contrast, the ratios of C29/C30, c 3 2 2OS/(2OS+2OR),and
C 3 3 20S/(20S+20R) appear to be unaltered, which may
reflect differential weathering of pentacyclic vs tricyclic
terpanes and of higher carbon number vs lower carbon
number pentacyclic terpanes. This feature is very valuable
in studies on the behavior and fate of spilled oil in the
environment and can be used to unambiguously distin-
guish one highly weathered oil from another. For S-1and
S-10,the fact that they have the much lower C23/C24 values,
the lower Ts/Tm values, and almost the same c 2 9 / c 3 0
values, as well as the same C 3 2 2OS/(2OS+2OR) and C 3 3
20S/ (20S+20R) values, strongly suggests that they may
come from the same source, but were very highly weath-
ered.

1742 Envlron. Scl. Technol., Vol. 28, No. 9, 1994

Table 5. Biomarker Compounds Identified in Arrow Oil Samples
peak no. compound empirical formula MW
Tricyclic Terpanes
1 Cm tricyclic terpane 276
2 Cz1 tricyclic terpane 290
3 Czztricyclic terpane 304
4 Cz3 tricyclic terpane 318
5 C24 tricyclic terpane 332
6 CZStricyclic terpane 346
7 cz6 tricyclic terpane 360
8 Cze tricyclic terpane 360
TetracyclicTerpanes
9 C27tetracyclic terpane 372
10 C27 tetracyclic terpane 372
11 c28 tetracyclic terpane 386
12 Czs tetracyclic terpane 386
PentacyclicTerpanes
13 Ts:18a(H),21@(H)-22,29,30-trisnorphane 370
14 17a(H),18a(H),21@(H)-25,28,30-trisnorphane 370
15 Tm:17a(H),21@(H)-22,29,3O-trisnorphane 370
16 17cx(H),18a(H),21@(H)-28,30-bisnorphane 384
17 17a(H),21@(H)-25,30-bisnorhopane 384
18 unidentified (3%hopane 398
19 17a(H),21@(H)-30-norhopane 398
20 17a(H),21@(H)-hopane 412
21 17@(H),2la(H)-hopane 412
22 22S-17a(H),21@(H)-3O-homohopane 426
23 2W1-17~t(H),21@(H)-3O-homohopane 426
24 17@(H),2la(H)-hopane
25 22S-l7a(H),21@(H)-30,31-bishomohopane 440
26 22R-17~(H),21@(H)-30,3l-bishomohopane 440
27 22S-17~(H),21@(H)-30,31,32-trishomohopane 454
28 22R-17a(H),21@(H)-30,31,32-trishomohopane 454
29 22S-l7a(H),21@(H)-30,31,32,33-tetrakishomohopane 468
30 22R-17a(H),21@(H)-30,31,32,33-tetrakishomohopane 468
31 22S-17~(H),21@(H)-30,31,32,33,34-pentakishomohopane 482
32 22R-17a(H),21@(H)-30,31,32,33,34-pentakishomohopane 482
Steranes
33 CZO5@(H)-sterane 274
34 Czl5a(H)-sterane 288
35 C22 5a(H)-sterane 302
36 C27 20S-5a(H),14a(H),17a(H)-cholestane 372
37 CZI20R-5a(H),14@(H),17@(H)-cholestane 372
38 C ~20S-5a(H),14@(H),17@(H)-cholestane
I 372
39 C27 20R-Sa(H),l4a(H),17a(H)-cholestane 372
40 (2%20S-5a(H),14a(H),17a(H)-ergostane 386
41 Cas 20R-5a(H),14@(H),17@(H)-ergostane 386
42 C28 20S-5a(H),14@(H),l'l@(H)-ergostane 386
43 (2% 20R-5a(H),14a(H),17a(H)-ergostane 386
44 Cm 20S-5a(H),14a(H),17a(H)-stigmastane 400
45 Cm 20R-5a(H),14@(H),17@(H)-stigmastane 400
46 Ca 20S-5a(H),14@(H),17@(H)-stigmastane 400
47 C Z20R-5a(H),14a(H),17a(H)-stigmastane
~ 400

Table 6. Analysis Results of Selected Hopanes and Steranes in Arrow Oil Samples
hopanes steranes
CW@- CWB-
c23 triterpanes Ca triterpanes ( p g / g of (pglg of C23/ Ts/ Cm/ c32 s/ C33 SI czsa@@/ czs a@@/
sample ( p g l g of TSEM) ( p g / g of TSEM) TSEM) TSEM) C24 TmO Cm (S+R) (S+R) (a@@+ a 4 (a@@ +
weathered 104 50 91 106 2.07 0.26 0.86 0.60 0.62 0.55 0.52
sourceoil
S-A 146 71 125 145 2.05 0.27 0.86 0.58 0.63 0.58 0.52
s-2 122 59 112 134 2.05 0.28 0.84 0.60 0.63 0.56 0.53
5-3 203 99 157 183 2.06 0.26 0.86 0.58 0.62 0.57 0.51
s-4 147 67 117 136 2.07 0.27 0.86 0.58 0.61 0.56 0.52
5-5 121 57 115 132 2.10 0.27 0.87 0.57 0.62 0.56 0.52
S-6 115 57 92 107 2.06 0.26 0.86 0.59 0.62 0.55 0.51
s-7 166 79 125 143 2.09 0.27 0.87 0.57 0.63 0.56 0.53
S-8 153 74 118 137 2.07 0.28 0.86 0.57 0.62 0.58 0.51
s-9 77 39 104 120 1.98 0.29 0.86 0.61 0.64 0.56 0.53
s-1 5 8 32 37 0.62 0.31 0.87 0.60 0.61 0.60 0.54
s-10 40 40 53 60 1.00 0.36 0.89 0.57 0.60 0.59 0.52
Ts: 18a(H),21fl(H)-22,29,30-trisnorhopane;
Tm: 17a(H),21@(H)-22,29,30-trisnorhopane.

Envlron. Sci. Technol., Vol. 28, No. 9, 1994 1743

 /Abundance < A Ion 217.00

I 0 1 , I , I , , , , , , , , , , , , , , , ,
bime--> 32;OO 34100 36100 38:OO 40.'00 ' 42;OO 44100 ' ' 46,'OO ' 48.00 '

bundance Ion 217.00

B I

- 0 I " ~' I ' " I " ' I " " I " " I " ' I "
ime--> 32.00 34.00 36.00 38.00 40.00 42.00 44.00 46.00 48.00
Flgure 8. Distribution of steranes (mlr 217 and 218) for the weathered source 011 (A) and S-4 (B). See Table 6 for component identification.
The dashed lines show a:,b,b-steranes which glve higher abundances of the mlr 218 fragment than the mlz 217 fragment. The general structure
for steranes Is shown in the right Inset of panel A.
It is evident that the most important advantage using relative intensities of m/z 149-151 fragments were used
c29/c30 as the source indicator is that C 2 9 and c 3 0 are the to distinguish between 5-a: and 5-p stereo isomers. It has
most degradation-resistant compounds compared to C23/ been recognized that the only significant difference
C24 and Ts/Tm. Secondly, they are often the most between 5-a: and 5-0 isomers is that the m/z 149 fragment
abundant among hopanes from C 1 9 to C36; therefore, the is more abundant than the m/z 151 moiety of the 5-a isomer
c 2 9 / c 3 0 ratio can be most accurately computed. So far, (23,27). Furthermore, the retention time of the 5-@isomer
hundreds of oil samples have been analyzed in our is shorter than that of the 5-a: isomer. In addition, it was
laboratory. The combination of these ratios, especially found from studying the paired standard compounds of
C z g / C 3 0 a s well C 3 2 2OS/(2OS+2OR) and C 3 3 20S/(20S+20R), C27, (328, and C 2 9 a:,a:,a:- and a,P,P-steranes that the P,a,a:-
has been satisfactorily applied to match and identify oils. and a,a,a-steranes have a base peak at m/z 217, while
For sterane identification, in addition to the base peak a,P,P-steranes have a base peak at 218. This feature,
chromatograms of steranes at 217 and 218 (Figure 8), the combined with the measurement of the ratio of the m/z

1744 Envlron. Scl. Technol., VoI. 28, No. 9, 1994

149 and the mlz 151 fragment has been used to unam-
biguously assign c27,c28,and C29 a,a,a-, P,a,a-,and a,P,P-
steranes in the Arrow oil samples.
The sterane hydrocarbons in the Arrow oil samples are
much less abundant than hopanes and essentially con-
stituted by C27 5a(H),14a(H),17a(H)-and c27 5a(H),14P-
(H),17P(H)-cholestane;C28 24-methyl-5a(H),14a(H),l7a-
(H)-and c 2 8 24-methyl-5a(H),14~(H),l7~(H)-cholestane
(ergostane); and C29 24-ethyl-5a(H),14a(H),17cu(H)-and
Czg 24-ethyl-5a(H),14P(H),l7/3(H)-cholestane(stigmas-
tane) (including the 20s and 20R isomers) with the lower
molecular weight C ~ OC, ~ I and , CZZsteranes being also
present. The C27, c28, and C29 group steranes exhibit
roughly the same abundances in most samples (top, F’g -1 ure
8). Another notable feature is that the epimers of a,P,P-
C27, c28, and C29 sterane give relatively higher intensities
of the mlz 218 ion than the mlz 217 ion (bottom, Figure
8). Unlike the ASMB oil (13),no significant contribution
from diasteranes was noted.
The similarity of values of a,a,Pl(a,p,fl+a,a,a) ratios
within C28 and C Zsterane
~ families (Table 6) from mlz 217
fragmentograms further suggeststhat all Arrow oilsamples
are related. One significant difference of the mlz 217 and
218 fragmentograms of the S-1and S-10from other samples
is that the four a,a,a-and a,P,P-isomers Of C27 series were
greatly decreased in their abundances relative to c28 and
C29 series, indicating that C27 steranes may be preferentially
degraded among C27-Czg sterane series under extreme
weathering conditions.
As discussed above, two criteria must be me in order to
provide a useful and definitive source indicator of weath-
ered oil: (1)stability and (2) uniqueness. The stability
of hopane compounds after environmental exposure (even
after extensive weathering) has been addressed by this
study and others. The weathering processes such as
evaporation, dissolution, biodegradation, and photodeg-
radation have little effect on the fingerprint of biomarker
hydrocarbons. A second and equally important require-
ment is the uniqueness of the source indicator. Some
properties of weathered oils vary over relatively small
ranges and, thus, are of limited use in differentiating
hydrocarbon sources. However, the distribution finger-
prints of hopane and sterane compounds vary significantly
from oil to oil. The ratios of some selected paired hopanes
and steranes are sensitive to and characteristic of the
originaloil source. Also, these paired hopanes and steranes
in different samples from the same source show great
consistency in ratios. The present work demonstrates that
the efficient oil source identification can be accomplished
by the selective use of biomarker parameters capable of
providing high specificity within a well-defined system.
Conclusions
The method using biomarker compounds by GCIMS
described in this paper complements all existing methods
useful for oil characterization and oil spill identification
but has the distinct advantages of being better able to
withstand interference from weathering effects and to
distinguish oils of different origins from their fingerprints.
These features are particularly important and useful for
characterization, identification, and matching of verylong-
term andlor very highly weathered oils, which are often
encountered in fate and behavior studies of spilled oil in
the environment.
The combined ratios of the selected pairs of triterpanes
and steranes, especially the ratio of c29/c30hopane, are
apparently independent of weathering effects in most cases
and can be extremely useful in the identification of oil
source and in oil matching. It should be understood,
however, that there is no single method which can identify
the source of an unknown spilled oil by itself without
matching it to known oils. Other analytical approaches
(such as tracing the distribution patterns of n-alkanes and
alkylated PAH homologues) remain necessary and useful
for oil source identification and characterization work.
All evidence obtained in this work indicate that, after
22-years of weathering, most n-alkanes including iso-
prenoids in the Arrow oil samples were lost arid that the
target PAHs and their alkylated homologues were heavily
degraded, but high ring alkyl PAH homologues such as
chrysenes and, in particular, the biomarker (triterpanes
and steranes) compounds remain and accumulate. For
the series of hopane and sterane compounds, the degrada-
tion-resistant order is (c23and (224) < (Ts and Tm) < (C2g
and C ~ O )and
, c27 steranes < c 2 8 and C29 steranes,
respectively. The facts that ratios of the hopanes c29/c30,
C32 20S/(20S+20R), and C33 2OS/(2OS+2OR) remain
unaltered while the ratios of CZ3/C24and TsITm have been
altered and that the c27 sterane series was greatly reduced
in its abundance while the ratios of a,@,Pl(a,P,P + a,a,a)
within the c28 and Czg series were unaltered may strongly
suggest that the S-1 and S-10 samples were more heavily
weathered than other samples but still shared the same
source.
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*Abstract published in Advance ACS Abstracts, July 1, 1994.