Environ. Sci. Technol.
2000, 34, 1174-1181
Evidence for Diffuse Contamination
of River Sediments by Road Asphalt
Particles
PIERRE FAURE,* PATRICK LANDAIS,
LAURENCE SCHLEPP, AND
RAYMOND MICHELS
UMR 7566 G2R, “Géologie et Gestion des Ressources Minérales
et Energétiques”, and CREGU, Université Henry Poincaré, BP
239, 54506 Vandoeuvre Lès Nancy, Cedex, France
Saturated hydrocarbons analysis was carried out on
different river sediments from Alsace-Lorraine in order to
detect possible contaminations by petroleum byproducts.
The distributions of n-alkanes from all studied samples are
very similar and are characterized by an odd-over-even
carbon number predominance, underlining the higher plant
contributions. On the other hand, pentacyclic triterpanes
and steranes occur in all river sediments and display similar
signatures that are characteristic of a mature organic
matter contribution inherited from anthropogenic contamina-
tions. Among the different possible pollutants origins,
point industrial sources seem unlikely because of the highly
homogeneous biomarker signatures and the geographical
repartition of the studied rivers. Because of the intense
road traffic in Alsace-Lorraine, main vehicle fuels and exhausts
have been investigated. Unleaded and diesel fuels, used
engine oils, and engine exhausts cannot account for the
biomarker distributions observed in river sediments. On the
contrary, saturated hydrocarbons extracted from road
asphalts are chiefly composed of polycyclic biomarkers
with chromatographic signatures very close to those of river
sediments. Moreover, microscopic investigations of river
sediments allow us to identify asphalt particles and to confirm
that the different rivers studied are contaminated by
road asphalts. Such contaminations may distort biomarker
signatures and GC-MS data and overprint the possible
pollution by other petroleum byproducts.
Introduction
The efficient identification of sources of contamination in
natural environments is a major problem. It is then necessary
to study specific markers which allow the major anthropo-
genic sources that are responsible for pollutions to be
identified. Among organic pollutants, petroleum byproducts
are often detected in marine environments (1, 2) as well as
in continental systems (3-8). For example, approximately
750 000 ton of hydrocarbons is annually transported by rivers
to the Mediterranean Sea (9). The ubiquity of most of the
compounds involved in pollutions related to the petroleum
byproducts requires investigations using adapted method-
ologies in order to tentatively identify the contaminant
sources.
For 40 years, petroleum organic geochemistry has de-
veloped analytical techniques and routines to study the fossil
* Corresponding author telephone: 33 3 83 91 38 29; fax: 33 3 83
91 38 01; e-mail: Pierre.Faure@g2r.uhp-nancy.fr.
1174 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 34, NO. 7, 2000
organic matter from sedimentary basins (10-12). The mo-
lecular analysis of extractable organic matter by gas chro-
matography-mass spectroscopy (GC-MS) is one of the main
steps in fossil organic matter characterization. Numerous
molecules or molecule families, named biological markers
(or biomarkers), originating from living organisms have been
identified in the fossil organic matter. Among the most
frequently studied biomarkers, terpanes originate from
bacteria lipidic membranes (procaryotes) (13). They cor-
respond to bicyclic, tricyclic, tetracyclic, and pentacyclic
compounds. The latter named hopanes (Figure 1a) are mostly
formed from the C35 bacteriohopanepolyols that always
constitute the major series in all hopanoid-producing bacteria
(14, 15). Because of bacteria occurrence in all surface
sediments, terpanes are frequently found in crude oils and
kerogen extracts. Steranes (Figure 1b) that originate from
sterols (16, 17) constituting the membrane of eucaryotic cells
(18) are also frequently recorded in chromatographic analysis
of fossil organic matter. All developed organisms (plankton,
zooplankton, higher plants, or animals) contain relatively
high amounts of sterols. As hopanes, steranes are ubiquitous
because their precursors (sterols) are common in living
organisms.
Because of the relative chemical stability of their cyclic
structure and their resistance toward biodegradation (19,
20), triterpanes and steranes are widely distributed in all
sediments and often only slightly modified by diagenesis.
They are therefore used as biomarkers to assess the matura-
tion of a sediment (21, 22), for oil to source rock correlations
(23-26), and for the tentative reconstruction of paleoenvi-
ronments (27-29).
These two families of biomarkers (triterpanes and ster-
anes) can also be used in the environmental field for
characterizing petroleum byproduct contaminants encoun-
tered in polluted sites (30). These biomarkers are not affected
by distillation processes, and their respective distributions
remain unchanged (31). On the other hand, because poly-
cyclic biomarkers are generally stable toward chemical and
biological degradation processes, they still bear their source
and maturity signatures after dissemination. Thus, the
specific biomarker signatures should allow the petroleum
pollutants encountered in polluted sites to be correlated to
the source from which they are derived. The search for
identical signatures from potential sources may help to
reconstruct the pollution processes.
Industrial activities in the Alsace-Lorraine region have
been responsible for soils and rivers pollution. More specif-
ically, coal extraction and processing, petroleum refining,
and polymer manufacturing may constitute potential sources
for sediments and soils contamination by organic pollutants.
To evaluate the quality of river sediments, samples have been
collected in different zones of the region. The aim of the
present work is to characterize the saturated hydrocarbons
extracted from the collected river sediments and to use the
distribution of biomarkers in order to tentatively identify the
main sources of organic pollution.
Experimental Section
Samples. Different sediments coming from rivers of Alsace-
Lorraine (France) have been collected by the Water Agency
Rhin-Meuse. The samples localization is shown in Figure 2.
The watersheds drained by these different rivers and their
respective flows (Table 1) are representative of the different
river types generally encountered in Alsace-Lorraine: im-
portant rivers (Rhine, Moselle, Meurthe, Ill, and Meuse) and
smaller ones (Rosselle, Fensch, Sarre, and Thur).
10.1021/es9909733 CCC: $19.00  2000 American Chemical Society
Published on Web 03/03/2000

FIGURE 1. (a) Pentacyclic triterpane and (b) sterane structures and
(c) examples of different stereochemical isomarizations (r hydrogen
atoms are below, and β hydrogen atoms are above the plane of the
molecule, and R and S are the possible configurations of the
asymmetric carbon atom).
Extraction-Fractionation. The bitumen fraction was
recovered by sediment extraction in a chloroform/methanol
mixture (50/50) for 45 min at 60 °C. Asphaltene precipitation
in pentane and liquid chromatography of the extracts on
alumina and silica gel columns allowed the aliphatic hy-
drocarbons to be isolated (32). Blanks tests were carried out
in order to confirm the absence of laboratory contaminants.
Gas Chromatography-Mass Spectrometry (GC-MS).
Aliphatic hydrocarbons were analyzed by GC-MS (HP 5890
series II GC coupled to a HP 5971 mass spectrometer), using
an on-column injector, a 60 m DB-5 J&W, 0.25 mm i.d, 0.1
µm film fused silica column. The temperature program was
from 60 to 130 °C at 15 °C/min and from 130 to 300 °C at 3
°C/min, followed by an isothermal stage at 300 °C for 15 min
(constant helium flow of 1 mL/min). Electron impact mass
spectra were achieved in both full-scan and single-ion
monitoring (SIM). Mass fragmentograms of the fragments
m/z ) 191 (hopanes) and m/z ) 217+218 (steranes) were
recorded. Biomarkers were identified by examination of their
mass spectra and their respective distributions and by
comparison with published data (29, 31, 33-34).
Results and Discussion
River Sediments. The saturated hydrocarbons of the different
river sediments have been analyzed. Their distribution are
very similar. The saturated hydrocarbon distributions of two
river sediments (Ill and Meuse 1), which are representative
of all the studied sediments, are shown in Figure 3, panels
a1 and a2. They are characterized by the predominance of
n-alkanes and by the occurrence of lower intensity peaks of
polycyclic biomarkers.
n-Alkanes. The distribution of the n-alkanes of river
sediments show a marked odd-over-even predominance in
the C24-C32 range. By way of comparison, the saturated
hydrocarbon distributions of a typical forest soil mainly
composed of beach leafs and resinous needles is shown in
Figure 4. The n-alkanes odd predominance already observed
in higher plant cuticular waxes (35) characterizes this sample.
This suggests that all river sediments exhibit a major higher
plant input. This is confirmed by microscopic observation
of the sediments, which reveals that the organic fraction is
almost exclusively constituted by seeds, leafs, and woody
debris. Furthermore, information derived from flash pyrolysis
GC-MS of the sediments (8) confirms the above statements
as far as the pyrograms are dominated by methoxyphenols
that are typical of lignin and degraded lignin contribution
(36).
Polycyclic Biomarkers. The pentacyclic triterpane (m/z )
191) and the sterane (m/z ) 217+218) distributions have
been studied for all the samples. The pentacyclic triterpane
distributions (m/z ) 191) of all the river sediments are very
close and are characterized by the predominance of the 17R-
(H),21β(H)-30-norhopane and the 17R(H),21β(H)-hopane
associated with the progressive decrease of homohopanes
pairs with carbon number increase as shown in Figure 3,
panels b1 and b2 (Table 3). All the pentacyclic triterpane dis-
tributions show the occurrence of gammacerane, which is
generally observed in hypersaline sedimentary deposits (37).
The presence of gammacerane underlines a common origin
for the chloroform-soluble fraction of the organic matter.
The hop(22)29-ene (a pentacyclic hopene) is also observed
in most of the samples. This compound is typical of a biogenic
input (38) and has already been observed in subaquatic recent
sediments (ferns and procaryotes) (33, 39). The m/z ) 191
distribution of a reference sediment sampled in the upper
waters of the Thur River (Figure 5, Table 3) is characterized
by the single occurrence of this hop(22)29-ene.
The biologically produced hopanes precursors carry a 22R
configuration that is gradually converted to a mixture of 22R
and 22S diastereoisomers (Figure 1c). The proportions of
22R and 22S can be calculated for all of the C31-C35 com-
pounds (40, 41). The 22S/(22R+22S)- C31:C35 hopane ratios
of the river sediments are shown in Table 2. Such values,
which are similar for all samples, are characteristic of an
organic material that has reached the oil window (29, 42).
The sterane distributions (m/z ) 217+218) of the different
samples exhibit the predominance of C27-C29 groups (Figure
3, panels c1 and c2, Table 4). A triangular diagram showing
the relative proportions of the C27-C29 steranes is currently
used to determine the environment of deposition of the
organic matter (43, 44). In the triangular diagram shown in
Figure 6, the river sediments group in the same zone of the
diagram, thus suggesting a common origin for all the studied
steranes.
The isomerization of 5R(H),14R(H),17R(H),20R configu-
ration (RRRR) inherited from living organisms is gradually
converted during thermal maturation in other possible ster-
eoisomers RRRS, RββS, and RββR until an equilibrium ratio
is reached. The C29 sterane isomerization ratios 20S/(20S
+20R) and ββ/(ββ+RR) (22, 44) increase progressively with
maturity level until equilibrium values (0.52-0.55 and 0.67-
0.71, respectively) (46). The diagram 20S/(20S+20R) versus
ββ/(ββ+RR) C29 steranes of the river sediments is shown in
Figure 7. The different samples show similar maturation levels
as compared to the large scattering obtained when plotting
in this diagram with different crude oils of variable maturity.
The analysis of both pentacyclic triterpanes and steranes
extracted from river sediments reveals:
(i) very similar distributions of all the samples collected.
The occurrence of a specific triterpane (gammacerane) as
well as the relative proportions of C27-C29 steranes suggest
a common organic source for these two families of bio-
markers.
(ii) the isomerization indices calculated on both steranes
and pentacyclic triterpanes correspond to a thermal maturity
level that is compatible with the oil genesis window, thus
suggesting that they are derived from fossil organic matter.
These two observations strongly suggest that all the studied
river sediments have been contaminated by hydrocarbons
derived from a similar type of organic matter.
Petroleum Byproducts. To put forward a proposal that
could explain the recorded contaminations, different hy-
pothesis have been reviewed. The contribution of point
source pollutions from petrochemical industries or refineries
seems unlikely because of the homogeneous polycyclic
biomarker signatures of all the river sediments. They can
generate such biomarker distributions (8) but do not explain
VOL. 34, NO. 7, 2000 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 1175
FIGURE 2. Localization of the different river sediment samples.

collected upstream (Figure 5, Table 3), their chromatographic

TABLE 1. Identification, Localization of the Different Sediments fingerprints bear the same characteristics as the other sedi-
Studied and River Watersheds Surface, Flow,a and Total ments and display the same terpane and sterane distributions.
Organic Carbon Contentb Then, it can be considered as a reference sample that can
sample SBc DBT 1/5 total org only be contaminated by road traffic-derived pollutants. The
code river sample locality (km2) (m3/s) C (%) other studied sites are located in industrial developed zones
Thur Thur Barrage 26.6 0.425 ndd and associated with an important road network.
Kruth-Wildenstein Vehicle traffic generates petroleum byproducts that may
Rosselle Rosselle Petite Rosselle 190 1.3 8.5
be taken into account in explaining the widespread con-
Sarre Sarre Herbitzheim 878 1.8 2.3
Moselle1 Moselle Bainville 1 750 6.9 1.9 tamination observed in the sampled sediments:
Meurthe Meurthe Bouxière-aux-Dames 3 085 8.5 1.5 Gasoline. The analysis of two different types of gasoline
Ill Ill La Wantzenau 4 754 28 5.2 (unleaded and diesel fuel) by gas chromatography does not
Meuse 1 Meuse Nouzonville 7 820 20.4 4.4
allow the identification of any biomarkers. These petroleum
Moselle2 Moselle Ars-sur-Moselle 7 867 18.8 2.4
Moselle3 Moselle Moulins les Metz 7 883 18.8 2.2 products correspond to light distillation fractions and do
Meuse 2 Meuse Revin 9 376 23.8 4.9 not contain heavy molecules as polycyclic biomarkers (47,
Rhin Rhin Barrage d'Iffezheim 45 515 510 1.5 49).
a DBT 1/5: flow of low-water level find 1 year over 5. b Weight % of Used Engine Oil. Used engine oils of two vehicle types
sediment. c SB, river watershed surface. d nd, not determined. have been analyzed by GC-MS (unleaded and diesel engine)
and show similar characteristics. The saturated hydrocarbon
their occurrence in all the collected samples. Similarly, the distributions of the unleaded fuel engine is shown in Figure
absence of any pollution marker in the upper waters of the 8, panel a1. It is characterized by an intense unresolved
Thur River sediment (Figure 5, Table 3) collected far away complex mixture (UCM) probably formed by iso- and cyclo-
from any road rules out any significant contribution of wind- alkanes that are not separated in the chromatographic
blown dust or atmospheric organic contaminants. conditions used in this study (49) and by the occurrence of
Then, it seems necessary to relate these contaminations n-alkanes in the C22-C32 range without any predominance
to more diffuse sources. Among the different sites studied, (Figure 8, panel a1, Tables 3 and 4). Some polycyclic bio-
the sediments sampled from the Thur River are interesting. markers are observed in low abundance as shown in Figure
As a matter of fact, the Thur River is located in a deep valley 8, panels b1 and c1, but the yield of these compounds is very
of the Vosges Mountains (glacial carved valley) mainly low as compared to the UCM. Their contribution to the
surrounded by coniferous and beech forests and devoid of polycyclic biomarkers observed in river sediments is unlikely
any industrial activities (Figure 2). Contrary to the sample because an intense UCM should also be observed in the

1176 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 34, NO. 7, 2000

FIGURE 3. (a1 and a2) Saturated hydrocarbons, (b1 and b2) pentacyclic triterpanes (m/z ) 191), and (c1 and c2) steranes (m/z ) 217+218)
distributions of the Ill and Meuse 1 River sediments (see identification in Tables 3 and 4).

FIGURE 5. Pentacyclic triterpanes (m/z ) 191) distributions of a

FIGURE 4. Saturated hydrocarbons distribution of beach leafs and
resinous needles (full scan).
river sediments chromatograms as well as even carbon-
numbered n-alkanes. Furthermore, the dissemination of used
engine oils may not account for such a widespread con-
tamination.
reference sediment sampled in the upper waters of the Thur River.
Engine Exhausts. Numerous authors have studied engine
exhausts (47, 50-52). Because they do not originate from
gasoline or diesel fuels, pentacyclic triterpanes and steranes
are introduced into the exhausts via the engine oil. However,
the unresolved organic mixture (UCM) represents between
84.6% (catalyst-equipped autos) and 90.3% (heavy-duty diesel
trucks) of the elutable organic mass (46). As for used engine

VOL. 34, NO. 7, 2000 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 1177

TABLE 2. 22S/(22S+22R)-C31-C35 Hopanes Isomerization Ratios of River Sediments and Road Asphalts
sample 22S/(22S+22R)-C31 22S/(22S+22R)-C32 22S/(22S+22R)-C33 22S/(22S+22R)-C34 22S/(22S+22R)-C35
code hopanes hopanes hopanes hopanes hopanes
Thur 0.57 0.63 0.64 0.61 0.64
Rosselle 0.57 0.59 0.61 0.62 0.60
Sarre 0.56 0.60 0.62 0.60 0.66
Moselle 1 0.55 0.59 0.63 0.66 0.67
Meurthe 0.55 0.58 0.64 0.58 0.63
Ill 0.56 0.61 0.61 0.60 0.66
Meuse 1 0.57 0.60 0.62 0.62 0.70
Moselle 2 0.55 0.59 0.61 0.63 0.65
Moselle 3 0.55 0.60 0.61 0.62 0.62
Meuse 2 0.56 0.60 0.60 0.65 0.56
Rhine 0.55 0.59 0.60 0.62 0.65
av 0.56 0.60 0.62 0.62 0.64
SD 0.009 0.013 0.014 0.021 0.039
road asphalt 1 0.57 0.59 0.62 0.60 0.60
road asphalt 2 0.56 0.57 0.59 0.59 0.62
road asphalt 3 0.56 0.59 0.60 0.60 0.61
av 0.57 0.58 0.60 0.60 0.61
SD 0.005 0.009 0.017 0.005 0.007

TABLE 3. Pentacyclic Triterpanes Identification in

Chromatograms of Figure 3, Panels b1 and b2, and of Figure
7, Panels b1 and b2
symbol name carbon no.
1 18R(H)-22,29,30-trisnorhopane C27
2 17R(H)-22,29,30-trisnorneohopane C27
3 17R(H),21β(H)-30-norhopane C29
4 18R(H)-30-norneohopane C29
5 17R(H),21β(H)-hopane C30
6 22S-17R(H),21β(H)-30-homohopane C31
7 22R-17R(H),21β(H)-30-homohopane C31
G gammacerane C30
8 22S-17R(H),21β(H)-30-bishomohopane C32
9 22R-17R(H),21β(H)-30-bishomohopane C32
10 22S-17R(H),21β(H)-30-trishomohopane C33
11 22R-17R(H),21β(H)-30-trishomohopane C33
12 22S-17R(H),21β(H)-tetrakishomohopane C34
13 22R-17R(H),21β(H)-tetrakishomohopane C34 FIGURE 6. Triangular diagram of the relative proportion of C27-C29
14 22S-17R(H),21β(H)-pentakishomohopane C35 steranes of the different river sediments, road asphalts, and used
15 22R-17R(H),21β(H)-pentakishomohopane C35 engine oils.
H hop(22)29-ene

TABLE 4. Sterane Identification in Chromatograms of Figure 3,

Panels c1 and c2
symbol name carbon no.
1 5R(H),14β(H),17R(H)- + 5R(H),14R(H),17R(H)- C21
pregnane
2 5R(H),14β(H),17R(H)- + 5R(H),14R(H),17R(H)- C22
homopregnane
3 20S-5R(H),14R(H),17R(H)-cholestane C27
4 20R-5R(H),14β(H),17β(H)-cholestane C27
5 20S-5R(H),14β(H),17β(H)-cholestane C27
6 20R-5R(H),14R(H),17R(H)-cholestane C27
7 20S-5R(H),14R(H),17R(H)-24-methylcholestane C28
8 20R-5R(H),14β(H),17β(H)-24-methylcholestane C28
9 20S-5R(H),14β(H),17β(H)-24-methylcholestane C28
FIGURE 7. 20rrrS/(20rrrS+20rrrR)-C29 sterane versus (ββ/
10 20R-5R(H),14R(H),17R(H)-24-methylcholestane C28 (ββ+rr)-C29 sterane diagram comparing a series of immature and
11 20S-5R(H),14R(H),17R(H)-24-ethylcholestane C29 mature crude oils with river sediments, road asphalts, and used
12 20R-5R(H),14β(H),17β(H)-24-ethylcholestane C29 engine oil.
13 20S-5R(H),14β(H),17β(H)-24-ethylcholestane C29
14 20R-5R(H),14R(H),17R(H)-24-ethylcholestane C29 polycyclic biomarkers in the river sediments. On the other
hand, Pieri et al. (31) have already studied the distribution
oil, the intense UCM of the exhausts may appear in the of aliphatic compounds extracted from road asphalts and
n-alkane distributions observed in river sediments, which is have shown that asphalt contains significant concentrations
not the case. of polycyclic biomarkers.
Thus, whatever their source, the different engine exhausts Road Asphalts. Three different road asphalts have been
cannot explain the occurrence and the distribution of studied. They have been sampled in the vicinity of the Thur

1178 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 34, NO. 7, 2000

FIGURE 8. (a1 and a2) Aliphatic (m/z ) 57), (b1 and b2) pentacyclic triterpanes (m/z ) 191), and (c1 and c2) steranes (m/z ) 217+218)
distributions of a used engine oil and a road asphalt (see identification in Tables 3 and 4).
River on two different roads. All these asphalts are totally
extractable by chloroform and display similar characteristics
that have been already recorded in other studies on road
asphalts (31). A characteristic saturated hydrocarbon dis-
tribution of road asphalts is shown in Figure 8, panel a2.
High amounts of pentacyclic triterpanes and steranes are
observed while the UCM intensity remains limited (Figure
8, panels b2 and c2, Tables 3 and 4). On the other hand,
n-alkanes are generally not observed (Figure 8, panel a2).
The pentacyclic triterpane distributions of these asphalts
are similar to the sediment ones. Especially, the specific
pentacyclic triterpane (gammacerane) is observed in the three
road asphalts. The 22S/(22R+22S)-C31:C35 hopane ratios
calculated for the three road asphalts show values similar to
those obtained for the river sediments (Table 2).
The sterane distributions of road asphalts are very similar
to those recorded from river sediments extracts. In the C27-
C29 steranes triangular diagram, the road asphalts plot in a
part of the diagram which overlaps that of the river sediments
(Figure 6). The diagram showing the plot of the C29 sterane
isomerization ratios, 20S/(20S+20R) vs ββ/(ββ+RR) (Figure
7), indicates that the maturity level reached by the asphalts
is very close to that deduced from the analysis of the steranes
from the river sediments. It should also be pointed out that,
as expected, used engine oil samples fall in the same region
as road asphalts on Figures 6 and 7.
Thus, the hopane and sterane distributions of road
asphalts as well as used engine oil show similar characteristics
to those of river sediments. First, the deposition conditions
parameters (occurrence of gammacerane, distribution of
steranes in the C27-C29 triangular diagram) are similar.
Second, the maturity indices based on isomerization ratios
of hopanes and steranes show that road asphalts and used
engine oil studied and river sediment contaminants have
reached the same maturity level.
On this basis, used engine oil as well as road asphalts can
be considered as potential contaminants for the sediments
analyzed in this work. However as already discussed, gas
chromatograms of n-alkanes from the sediments do not
exhibit any distribution that can be related to that of used
engine oil (Figure 8). An intense biodegradation of the used
oil engine could have removed these n-alkanes. However,
this biodegradation must occur before the incorporation of
the used engine oil in the sediment. Otherwise, the n-alkanes
from the natural input should also be biodegraded. Fur-
thermore, the intense biodegradation of the used engine oil
should also induce some changes in the distribution of the
steranes and hopanes (33) that is not observed in the present
work. The alteration of the used engine oil on the road prior
to incorporation into the sediment should be associated with
an air oxidation. It has already been shown that such an
alteration provokes the preferential alteration of the bio-
markers (53), which is not observed in the different samples
studied. Even if additional quantitative data should be
available to confirm this hypothesis, it is strongly suggested
that the specific biomarker distributions observed in all the
VOL. 34, NO. 7, 2000 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 1179

FIGURE 9. Road asphalt particles in the coarse fraction (>620 µm)
of the Thur River sediment (magnification ×8).
river sediments studied may be inherited from road asphalt
contamination.
To understand the dispersion mode of road asphalt, the
river sediments have been observed under microscope. In
the coarse granulometric fraction (>620 µm) of the Thur
sediments, asphalt particles have been identified (Figure 9).
To confirm the origin of the particles, they have been
impregnated with a drop of chloroform. The particles are
quickly dissolved and replaced by a brown halo. In the others
rivers, sediment particles are generally too small to be
identified under an optical microscope. However, chloroform
impregnation of these sediments allows a brown halo to be
detected, thus suggesting the presence of small asphalt
particles. On the contrary, the microscopic observation of
the sediments does not allow us to detect impregnation
figures related to oil pollution. Clearly, the contamination
results in a particulate transport that can only be of concern,
in this case road asphalt particles or particles resulting from
the insolubilization of engine oil after severe surface alter-
ation. In this last case, the observed particles should no longer
be chloroform-soluble. Thus, the microscopic observations
confirm the occurrence of a contamination by road asphalts
with a predominant dispersion mode occurring as a solid
phase.
Such a type of diffuse contamination introduces an organic
background in river sediments marked by the occurrence of
polycyclic biomarkers. The characterization of specific
petroleum byproducts in river sediments by using these
biomarkers and the subsequent identification of the possible
pollution sources are required to take into account this
anthropic background that may occur in all industrialized
zones. As a matter of fact, it may distort the interpretation
of GC-MS data and overprint the message of other petroleum
derivatives. Thus, detailed inspection of both the analytical
data and the microscopic information should be carried out
before establishing any pollutant source correlations for
petroleum byproducts. Further studies are still needed in
order to more precisely quantify the input of such contami-
nants and to evaluate their contribution to sediment an-
thropization.
Acknowledgments
This research benefited from the financial support and the
sampling capacities of the Agence de l’Eau Rhin-Meuse. P.F.
was been supported by an MENRT doctoral grant and by a
Region de Lorraine postdoctoral fellowship. We particularly
acknowledge C. Breuzin and M. Babut of the Agence de l’Eau
Rhin-Meuse for information concerning the different rivers
studied and thoughtful discussions.
1180 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 34, NO. 7, 2000
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Received for review August 18, 1999. Revised manuscript
received December 13, 1999. Accepted December 29, 1999.
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