Molecular studies of insoluble organic matter in river sediments from Alsace-Lorraine (France

Molecular studies of insoluble organic matter in riversediments from Alsace-Lorraine (France)

Pierre Faurea,*, Marcel Eliea, Laurence Mansuya, Raymond Michelsa,Patrick Landaisa, Marc Babutb

aUMR 7566 CNRS G2R, Universite Henri Poincare, Nancy I, BP 239, 54506 Vandoeuvre Les Nancy Cedex, FrancebUnite de Recherche Biologique des Ecosystemes Aquatiques–CEMAGREF, 3bis quai Chauveau, BP 220, 69336 Lyon Cedex 09, France

Received 3 March 2003; accepted 13 October 2003

(returned to author for revision 11 June 2003)

Abstract

Insoluble organic matter (IOM) from river sediments of Alsace-Lorraine (France) was examined by semi-quantitativepyrolysis-gas chromatography–mass spectrometry (Py-GC–MS). IOM in rivers can play a role in the production ofnoxious metabolites and mobilization of pollutants by complexation. The relative abundance of aliphatic hydro-

carbons, aromatic hydrocarbons and heteroatomic compounds was determined in IOM from natural and pollutantsources and small and large rivers. A ternary plot of these compound classes allowed the natural and pollutant endmembers to be distinguished. The IOM of the small rivers was similar to the pollutant end member whilst that of thelarge rivers was similar to the natural sources. This semi-quantitative Py-GC–MS approach constitutes a promising

tool for IOM characterization.# 2003 Elsevier Ltd. All rights reserved.

1. Introduction

The organic chemical composition of river water isimportant since river water is increasingly used as asupply for drinking water. River water quality is

becoming increasingly vital for drinking water resources.Among the possible contaminants in river water, organicmolecules such as hydrocarbons (Saliot et al., 1990;

Baekken, 1994; Faure et al., 1999a, 2000) and, morespecifically, polycyclic aromatic hydrocarbons (PAHs;Johnson and Larsen, 1985; Christensen and Zhang,

1993; Ollivon et al., 1995; Fernandes et al., 1997; Ngabeet al., 2000), polychlorinated biphenyls (PCBs; Colomboet al., 1990; Sanders et al., 1996) and pesticides (Squil-

lace and Thurman, 1992; Pereira and Hostettler, 1993;Pereira et al., 1996; Muller et al., 1997) are frequently

studied. Such compounds are soluble in organic solvents

and therefore belong to the extractable organic matterfraction. Investigations concerning contaminants relatedto the insoluble organic matter (IOM) fraction are lesswell developed (Kruge et al., 1998; Kruge, 1999). How-

ever, the properties of IOM are such that it may requireadditional attention. Indeed, the frequently high specificsurface area gives IOM significant adsorption capacity

and the ability to trap other pollutants. Also, physico-chemical modification of the IOM can allow the releaseof adsorbed pollutants into water and may induce

subsequent environmental problems. During physico-chemical and/or biological alteration (such as oxidationand biodegradation) of IOM, polar molecules can be

generated (Mahaffey et al., 1988; Faure et al., 1999b).Such molecules, which can themselves be pollutants,may allow the mobilization of other pollutants (such asheavy metals) by complex formation (Ogunsola and

Rao, 1993; Evangelou et al., 2002).After migration in the different environmental com-

partments (atmosphere, soil and river), an important

0146-6380/$ - see front matter # 2003 Elsevier Ltd. All rights reserved.

doi:10.1016/j.orggeochem.2003.10.008

Organic Geochemistry 35 (2004) 109–122

www.elsevier.com/locate/orggeochem

* Corresponding author. Tel.: +33-3-83-68-47-40; fax:

+33-3-83-68-47-01.

E-mail address: [email protected] (P. Faure).

http://www.sciencedirect.com



http://www.elsevier.com/locate/orggeochem/a4.3d

mailto:[email protected]

proportion of this IOM is accumulated in riversediments. Thus, the IOM from river sediments is anappropriate target for evaluating the impact of insolubleorganic pollution on water quality.

Flash pyrolysis-gas chromatography–mass spectro-metry (Py-GC–MS) appears to be an appropriateanalytical tool for the molecular characterization of the

IOM of soil (Hatcher and Clifford, 1994) and aquaticsediments (Peulve et al., 1996). Indeed, moleculardistributions obtained after flash-pyrolysis of macro-

molecules might be useful in elucidating the overallmolecular structures of IOM and for determining finger-prints (i.e. reproducible, distinctive chromatographic

profiles) which are related to specific organic sources.The present study applied Py-GC–MS to character-

ization of IOM of river sediments from the Alsace-Lorraine region (France), where an inheritance from

past industrial activity and current important economicactivity is to be expected. Coal extraction and proces-sing, petroleum refining and polymer manufacturing

all constitute potential sources for contamination ofsediments by organic pollutants in this area. Moreover,road traffic and the occurrence of important urban

centres may contribute. Thus, river sediments from thisregion represent a useful substrate for the evaluation ofmolecular-scale IOM characterization.

2. Materials and methods

2.1. Samples

Sediments (sampled by dredging the river bed) from

rivers in Alsace-Lorraine (France) were collected by theWater Agency Rhin-Meuse during spring 1998 (Fig. 1).The watersheds drained by these different rivers and

their respective flows (Table 1) are representative of thedifferent river types encountered in Alsace-Lorraine:large rivers (Rhine, Meuse Moselle, Meurthe and Sarre)

and smaller ones (Rosselle, Fensch, Rau les Moulinsand Merle).Different types of possible anthropogenic sources

were also sampled (Table 2): coke and coal particles,

petrochemical industry effluent and road asphalt. High-way and rain retention basins were also investigated.The natural samples selected (‘beech leaves, pine

needles’; Table 2) are typical of some of the major naturalsources encountered in the watersheds. They were chosenbecause they contain biopolymers such as lignin and

cellulose, which are generally encountered in land plants.Because of the widespread livestock production in sev-eral Lorraine areas, cow manure was also investigated.

2.2. Extraction

The river sediments and natural and anthropogenic

samples containing water in high proportions werecentrifuged. Then, all were ground to a size smaller than500 mm and quartered in order to ensure sample homo-

geneity. An aliquot (�10 g) of each sample was extrac-ted with 250 ml chloroform/methanol (50/50 v/v).Extraction was carried out under magnetic agitation in

a glass bottle for 45 min at 60 �C, which enabled theinsoluble residue to be isolated from the extractablefraction. The IOM yields and total organic carbon con-

tents of the different river sediments are given in Table 1.

2.3. Flash pyrolysis-gas chromatography–massspectrometry (Py-GC–MS)

Flash pyrolysis of extracted solid residues wasperformed with a CDS 2000 pyroprobe. After homo-

genization of the pre-extracted samples, aliquots (�10mg) were loaded into quartz tubes and heated at 620 �Cfor 15 s. The products were analyzed by gas chromato-

graphy–mass spectrometry (HP 5890 Series II GCcoupled to a HP 5972 mass spectrometer), using a split–splitless injector and a 60 m DB-5 J&W, 0.25 mm i.d,

Table 1

General sample information, river watershed surface (SB), flow (DBT 1/5: flow of low water level find 1 year over 5), total organic

carbon (TOC) content (wt.% dry sediment) and amount of insoluble organic matter (IOM) isolated (% of TOC)

No.
River Sample locality SB (km2) DBT 1/5 (m3/s) TOC Isolated IOM (% TOC)
SW1
Merle L’Hopital 29 0.3 3.9 90.2
SW2
Rau les Moulins Rocroi 60 <0.1 5.9 89.7
SW3
Fensch Florange 83 3.5 3.5 69.5
SW4
Rosselle Petite Rosselle 190 1.3 8.5 91.8
LW1
Sarre Herbitzheim 878 1.8 2.3 84.0
LW2
Meurthe Bouxiere-aux-Dames 3085 8.5 1.5 78.6
LW3
Moselle (n�1) Ars-sur-Moselle 7867 18.8 2.4 87.9
LW4
Moselle (n�2) Moulins les Metz 7883 18.8 1.1 90.5
LW5
Meuse Revin 9376 23.8 4.9 82.3
LW6
Rhin Barrage d’Iffezheim 45,515 510 1.5 86.8
110 P. Faure et al. / Organic Geochemistry 35 (2004) 109–122

0.1 mm film, fused silica column. After cryofocusing(�30 �C), the GC oven was temperature programmedfrom �30 to 40 �C at 10 �C/min and 40–300 �C at 5 �C/min, followed by an isothermal stage at 300 �C for 10

min (constant helium flow of 1 ml/min).

2.4. Identification and quantification of compoundsproduced by pyrolysis

Compounds generated during flash pyrolysis were

identified from their GC retention times and from mass

Fig. 1. Location of river sediment samples.

Table 2

Type, nature and location of organic sources

No.
Sample type Nature Source/location
NS1
Beech leaves Fresh leaves Lorraine, France
NS2
Pine needle Fresh needles Lorraine, France
NS3
Cow manure Fresh mud Lorraine, France
AS1
Highway retention basin Sediment Moulins-les-Metz, Lorraine, France
AS2
Rain retention basin Sediment Maxeville, Lorraine, France
AS3
Coke Particles Seremange, Lorraine, France
AS4
Petrochemical waste Effluent Sarralbe, Lorraine, France
AS5
Coal particles Particles Petite Rosselle, Lorraine, France
AS6
Road asphalt Particles Lorraine, France
P. Faure et al. / Organic Geochemistry 35 (2004) 109–122 111

spectra with reference to the Wiley and US NationalBureau of Standards computerized mass spectrallibraries. Identification was also based on comparisonwith published mass spectra of pyrolysis products of

proteins, polysaccharides, lipids, lignins and fossilorganic matter (Van de Meent et al., 1980; Hatcheret al., 1988; Saiz-Jimenez and De Leeuw, 1986a,b;

Stout et al., 1988; Van der Hage et al., 1993; Kruge,1999).Integration of mass chromatograms with relevant

m/z values was performed and the peak areas obtainedwere multiplied by a correction factor, which takes intoaccount differences in mass spectrometric responses for

various compounds. The correction factor was calcu-lated from the mass spectrum of each authenticcompound by taking the inverse of the percentage ofthe total ion current of the relevant m/z value and

multiplying it by 100 (Hartgers et al., 1992). As aresult of this mathematical procedure, distributionpatterns were obtained showing the relative concentra-

tions of the different compounds. The different com-pounds were then grouped into three different familiesdepending on their chemistry: aliphatic, aromatic and

heteroatomic (containing nitrogen, sulfur and oxygen)molecules and their respective concentrations weresummed.

3. Results and discussion

In order to correlate the molecular signatures of riversediments with potential sources, samples from specificnatural and anthropogenic sources were analyzed by Py-

GC–MS (Table 2). They were selected in order to pro-vide a typical image of the environment of the Lorrainewatersheds: (i) Anthropogenic: different types of anthro-

pogenic sources were investigated: petrochemical waste,coke, coals and road asphalts (Fig. 2a–d respectively) aswell as highway and urban rain basin sediments (Fig. 2eand f respectively); (ii) Natural: Lorraine rivers are

characterized by a predominance of terrigenous organicmatter input, which derive from land plants such asleaves and needles (Fig. 3a and b). Manure from cows is

also common (Fig. 3c).After removal of the extractable fraction in each case,

the insoluble organic fraction was analyzed by Py-GC–

MS.

3.1. Anthropogenic sources

Except for sediments AS1 and AS2, pyrograms ofeach anthropogenic source showed specific fingerprints:The road asphalt pyrogram (Fig. 2d) was character-

ized by n-alkene/n-alkane doublets [�,*] predominantlyin the carbon number range of 8–31. Aromatic hydro-carbons [3,7,14,21,27,38] and phenolic compounds

[16,22,26] occurred in lower proportions (numerals insquare brackets indicate peak numbers in the differentchromatograms; Table 3 lists the compounds).The coal particles pyrogram (Fig. 2c) was dominated

by phenolic compounds [16,22,26,34] and aromatichydrocarbons, especially alkylbenzenes [3,7,14] andalkylnaphthalenes [27,38,46].

A predominance of n-alkene/n-alkane doublets [�,*]was observed in the petrochemical waste pyrogram(Fig. 2a), whereas the abundance of aromatic hydro-

carbons [3,7,8,21] and phenolic compounds [16,22] waslimited. Moreover, pristane, phytane, indole and methylindoles [Pr,Ph,37,43 respectively] and an UCM occurred

in high proportions.The coke pyrogram (Fig. 2b) showed a signature

intermediate between those of the coal and road asphalt.Aliphatic hydrocarbons [�,*], aromatic hydrocarbons

[3,7,8,14,27,38,40,46,54] as well as phenolic compounds[16,22,26,34] occurred.The two sediments from highway (AS1) and rain

(AS2) retention basins (Fig. 2e and f) showed similarpyrograms dominated by toluene [3] and styrene [8] and,in lower abundance, phenolic compounds [16,22,26] and

n-alkene/n-alkane doublets [�,*]. However, these twomolecular distributions are more complex than theabove specific sources (petrochemical waste, coke, coal

and road asphalt) and could correspond to a morecomplex mixture of organic source contributions.Eugenol [42] and trans-isoeugenol [52] were detectedonly in these two anthropogenic sediments, revealing a

contribution form ligin (Saiz-Jimenez and De Leeuw,1986a).

3.2. Natural sources

The pyrogram from the beech leaves (Fig. 3a)

was characterized by the high abundance ofphenols [16,22,26,31] and methoxyphenols[23,28,36,39,41,42,45,51,52,57,58,59]. Such a distribu-tion is typical of lignin (Saiz-Jimenez and De Leeuw,

1986a; Van de Hage et al., 1993; Saiz-Jimenez, 1994;Fabbri et al., 1996) which is one of the principalconstituents of leaves. The other pyrograms of products

from natural sources were also dominated by phenolsand methoxyphenols (Fig. 3b and c).

3.3. Small watershed river sediment

Pyrograms from sediments from small watershed

rivers are shown in Fig. 4. The major identified peaks(Table 3) are similar, but their relative abundances var-ied from one sample to another. Alkylbenzenes [3,7,14],styrene, alkylstyrenes [8,17], phenol [16] and alkylphe-

nols [22,26,34] were systematically present in allsamples. However, these different compound classes arenot characteristic of specific sources.


Fig. 2. Examples of anthropogenic sources pyrograms: (a) highway retention basin, (b) rain retention basin, (c) petrochemical w ) coke, (e) coal particles and (f) road asphalt

(cf. Table 3 for component identification).

P.Faure

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113

aste, (d

Fig. 3. Pyrograms of (a) beech leaves, (b) pine needles and (c) cow manure (cf. Table 3 for component identification).


Table 3

Components indicated in pyrograms in Figs. 2–5

No.
Compounds M/z of characteristic fragments
1
Pyridine 52, 79
2
Pyrrole 67
3
Toluene (C1-Benzene) 91.92
4
C1-Thiophene 97.98
5
Furancarboxaldehyde (2-furaldehyde) 95.96
6
C1-Pyrrole 80.81
7
C2-Benzene 91.106
8
Styrene 78.104
9
2-Cyclopenten-1-one, 2-methyl- 53,67,96
10
Cyclopentanone, 2-methyl- 55,69,98
11
C2-Pyrrole 80,94,95
12
Benzaldehyde 51,77,105,106
13
C1-Furancarboxaldehyde (5-methyl-2-furaldehyde) 53,109,110
14
C3-Benzene 105.12
15
Benzonitrile 76.103
16
Phenol 66.94
17
C1-Styrene 91,117,118
18
C3-Thiophene 111,125,126
19
2-Cyclopenten-1-one, 2-hydroxy-3-methyl- 55,69,83,112
20
Limonene 67,68,93,107,121,136
21
Indene 115.116
22
C1-Phenol (m- + p-Cresol) 77,79,90,107,108
23
2-Methoxyphenol (Guaiacol) 81,109,124
24
Benzeneacetonitrile 90.117
25
C1-Indene 115,129,130
26
C2-Phenol 77,107,121,122
27
Naphthalene 128
28
4-Methylguaiacol 95,123,138
29
Benzothiazole 69,82,91,108,135
30
Benzothiophene 134
31
4-Vinylphenol (Phenol, 4-ethenyl-) 65,91,120
32
Benzenepropanitrile 91.131
33
Indanone (1H-Inden-1-one, 2,3-dihydro-) 51,78,104,132
34
C3-Phenol 77,91,121,136
35
1,2-Benzenediol, 3-methoxy- 51,79,97,125,140
36
4-Ethylguaiacol 137.152
37
Indole 89,90,117
38
C1-Naphthalene 115,141,142
39
4-Vinylguaiacol 77,107,135,150
40
Biphenyl 154
41
Syringol (Phenol, 2,6-dimethoxy-) 139.154
42
Eugenol (Phenol, 2-methoxy-4-(2-propenyl)) 55,77,91,103,131,149,164
43
C1-Indole 130.131
44
Vanillin (Benzaldehyde, 4-hydroxy-3-methoxy-) 81,109,123,151,152
45
cis-Isoeugenol (Phenol, 2-methoxy-4-(1-propenyl)) 55,77,91,103,131,149,164
46
C2-Naphthalene 115,141,156
47
Acenaphthalene 152
48
C1-Biphenyl 152,153,165,167,168
49
C2-Indole 130,144,145
50
Dibenzofuran 139.168
51
4-methylsyringol 125,153,168
52
trans-Isoeugenol (Phenol, 2-methoxy-4-(1-propenyl)) 55,77,91,103,131,149,164
53
Acetoguaiacone 123,130,151,166
54
C3-Naphthalene 115,128,155,170
(continued on next page)


Monoaromatic hydrocarbons, corresponding to lowmolecular mass compounds, result from extensive

thermal degradation during flash pyrolysis of both (i)primary sources such as specific individual amino acids(tyrosine, phenylalanine); Tsuge and Matusbara, 1985),

lignin (Saiz-Jimenez, 1994), and (ii) naturally-evolvedorganic matter. Indeed, primary compounds undergocyclization, aromatization and polycondensation duringhumification, diagenesis and thermal maturation (Tissot

and Welte, 1984). In fact, aromatic units which aregenerally encountered in humic acids (Schulten et al.,1991), kerogens and coals (Van de Meent et al., 1980;

Hartgers et al., 1994; Faure et al., 1999a) cannot beeasily related to specific sources.Phenol and alkylphenols are also ubiquitous in pyr-

olysates. They can derive from primary sources such aslignin-derived products from higher plants (pine needles,leaves; Saiz-Jimenez and De Leeuw, 1986a,b), phlor-

otannins and phlorotannin-like materials from algae(Ragan 1976, Van Heemst et al., 1996), as well asnaturally- (fossil organic matter such as coals and kero-gens; Van de Meent et al., 1980; Faure et al., 1999a) or

artificially-evolved organic matter (e.g. industrial by-products such as cokes; Faure et al., 1999a). In addition,compounds observed in lower abundance are derived

from carbohydrates (chitin [1,2,3,10,32] and cellulose[5,13,19]), proteins [1,2,6,37,43] and chlorophyll

pigments [2, 60] included in the macromolecularstructure (Tsuge and Matusbara, 1985; Ishiwatari et al,1996, Sihombing et al., 1996; Marbot, 1997; Stankiewicz

et al., 1998).Each sediment also showed specific molecular

characteristics: the Merle river and the Rosselle riversediments (Fig. 4a and d respectively) yielded significant

amounts of naphthalene [27] and alkylnaphthalenes[38,46]. Moreover, heavy molecular mass n-alkene/n-alkane doublets [�,*] (C15–C27) also occurred in these

two river sediments as well as in Rau les Moulins riversediment. However, low molecular mass n-alkene/n-alkane doublets [�,*] (C8–C13) were only observed in

the Merle river sediment. The Fensch river pyrogram(Fig. 4c) was devoid of n-alkene/n-alkane doubletswhereas polycyclic aromatic hydrocarbons

[63,64,70,72,73] occurred. The Rosselle river sediment(Fig. 4d) showed an unresolved complex mixture(UCM).Even if river sediments from small watersheds showed

specific signatures, it still remains difficult to associatethese different molecular characteristics with specificorganic sources.

Table 3 (continued)

No.
Compounds M/z of characteristic fragments
55
Fluorene 165.166
56
4-vinylsyringol 77,165,180
57
Methoxyeugenol (Phenol, 2,6-dimethoxy-4-(2-propenyl)) 91,119,194
58
cis - Phenol, 2,6-dimethoxy-4-(1-propenyl) 91,119,194
59
trans - Phenol, 2,6-dimethoxy-4-(1-propenyl) 91,119,194
60
Neophytadiene 68,123,278
61
C1-Dibenzofuran 152,181,182
62
C1-Fluorene 165.18
63
Phenanthrene 178
64
Anthracene 178
65
Hexadecanitrile 57,97,110,124,236
66
C1-Phenanthrene 165.192
67
Phenylnaphtalene 101.204
68
Molecular sulfur (S8) 64,96,128,160
69
C2-Phenanthrene 191.206
70
Fluoranthene 101.202
71
Octadecanitrile 57,97,110,124,264
72
Pyrene 101.202
73
Terphenyl 115.23
74
Hexadecanamide 59,72,255
75
Octadecanamide 59,72,283
*
n-Alkenes (with Ci carbon number) 55,69,83
�
n-Alkanes (with Ci carbon number) 57,71,85
Pr
Pristane 57,71,85,183
Ph
Phytane 57,71,85,183,197
UCM
Unresolved complex mixture

Fig. 4. Sediment pyrograms from small watershed river sediments: (a) Merle, (b) Rau les Moulins, (c) Fensch and (d) Ros f. Table 3 for component identification).

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selle (c

3.4. Large watershed river sediments

Pyrograms from the six large watershed riversediments are shown in Fig. 5.

The distribution of the major products (i.e. alkylben-zenes [3,7], styrene [8], phenol [16] and alkylphenols[22,26] and indole [37]) was similar in the sediments

from the Meurthe, Moselle and Rhine rivers. The simi-larity between the two Moselle river sediments, showingalmost identical molecular signatures (Fig. 5c and d), is

not surprising because these two sediments were sam-pled only five kilometers apart (Fig. 1). Indeed, theyresult from the same watershed drainage, so common

organic sources are to be expected. The similarity to thetwo other rivers (Rhine and Meurthe) is noticeable,although the watersheds are different. This suggestscommon sources for the organic insoluble material of

the four samples from the Meurthe, Moselle and Rhinerivers.The Sarre and Meuse sediment pyrograms (Fig. 5a

and e) are rather different. In particular, the Sarre riversediment was characterized by the noticeable occurrenceof alkyl-2-methoxyphenols [23,28,39], which occurred

only in trace abundances in the other river sediments.These compounds are typical of lignin flash pyrolysisproducts and underline (i) a higher land plant contribu-

tion or (ii) a less intense dilution by other organiccontributors. The Meuse River sediment pyrogramshows a noticeable UCM.Considering the complexity of the pyrograms from

both the small and large watershed river sediments, theidentification of specific natural or anthropogenicsources cannot be easily accomplished. Only general

natural contributions of chlorophyll pigments, proteins,carbohydrates and lignin could be confirmed.

3.5. Semi-quantification

The molecular distribution in the pyrograms of thesmall watershed river sediments depends on the sam-

pling location, whereas the large watershed river sedi-ments exhibit quite similar distributions despite thedifferences in sampling locations. The comparison of

the Py-GC–MS fingerprints of (i) potential natural andanthropogenic organic sources and (ii) river sedimentsdid not enable determination of discriminant

parameters that could help in the reconstruction of theprocesses accumulating IOM in the sediments.In addition, to focus on specific molecular markers, it

was thought useful to study the proportion of thedifferent molecular families as carried out by differentauthors (Kruge et al., 1998; Kruge, 1999; Cotrim daCunha et al., 2000). Indeed, the proportion of aliphatic

hydrocarbons, aromatic hydrocarbons and heteroa-tomic molecules in each pyrogram was calculated(Table 4) and plotted in a triangular diagram (Fig. 6).

Because of the difficulty in identification of the mole-cular nature of the components associated with UCMs,UCM intensities were not taken into account. The riversediments could be split into two different groups. The

large watershed river sediments were characterized by amajor heteroatomic contribution (between 66 and 50%)whereas the small watershed river sediments showed a

molecular signature enriched in aliphatic and aromatichydrocarbons (between 12–21, and 32–47% respectively).The samples from natural sources (leaves, pine

needles and cow manure) were characterized by amolecular composition dominated by heteroatomiccompounds (more than 83%), which is in good agree-

ment with the high intensity of the chromatographicpeaks attributed to phenols and methoxyphenols.The anthropogenic sources revealed two well defined

domains:

1. Road asphalt (AS6) and petrochemical waste(AS4) were characterized by a high proportion

of aliphatic structures (88 and 60% respectively).2. Coke (AS3) and coal (AS5) produced an

approximately equal mixture of hydrocarbons

and polar compounds (about 45% heteroatomiccompounds and 55% hydrocarbons, Table 4).

The retention basin sediments (AS1 and AS2) showedmolecular signatures intermediate between those ofthe natural and the two anthropogenic end membersdescribed above. These sediments do not correspond to

Table 4

Proportion of aliphatic, aromatic and heteroatomic compounds

deduced from integration of pyrograms

No.
Aliphatic
compounds (%)

Aromatic

compounds (%)

Heteroatomic

compounds (%)

NS1
8.3 6.1 85.6
NS2
10.5 3.2 86.3
NS3
8.9 7.3 83.8
AS1
25.0 41.5 33.5
AS2
11.7 32.5 55.7
AS3
23.6 34.3 42.1
AS4
59.4 13.6 27.0
AS5
12.6 39.9 47.5
AS6
88.7 6.2 5.1
SW1
20.7 37.1 42.1
SW2
17.6 32.3 50.0
SW3
11.8 47.2 41.0
SW4
14.6 37.0 48.3
LW1
14.4 24.4 61.2
LW2
13.1 36.0 50.9
LW3
6.7 28.4 64.9
LW4
14.9 27.1 57.9
LW5
14.9 26.2 58.9
LW6
7.0 27.3 65.7

Fig. 5. Sediment pyrograms from large watershed river sediments: (a) Sarre, (b) Meurthe, (c) Moselle (Ars-sur-Moselle), (d) M Moulins-les-Metz), (e) Meuse and (f) Rhine

(cf. Table 3 for component identification).

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119
oselle (

a pure organic pool but result from the accumulation ofdrained particles from different types of surface (pave-ments, soils and roofs). As a matter of fact, their

molecular signatures reflect the mixture of natural andanthropogenic sources. Highway basin sediment (AS1)exhibited a significant aliphatic hydrocarbons percen-

tage (25%), underlining the predominance of contribu-tions from vehicle exhaust, used engine oil and roadasphalt particles relative to natural inputs. This road

traffic predominance can explain the relatively highproportion of aliphatic hydrocarbons encountered inAS1. In contrast, the higher proportion of heteroatomiccompounds (55%) in the rain retention basin sediments

(AS2) is compatible with predominantly natural sour-ces. Rain retention basins collect water, which drainsless specific areas, as opposed to highway basins.

Therefore, the signature of the insoluble organic matterin the rain retention basin sediment reflects variouscontributions (natural and anthropogenic) and explains

the location of the AS2 sample in the large watershedriver sediment domain (Fig. 6).Small watershed river sediments seem more affected

by anthropogenic contributions. The restricted waterflow and the small watershed areas probably (i) limitthe anthropogenic contamination dilution and (ii)favour a limited natural contribution. In contrast, large

watershed rivers are under the major influence of a nat-ural pool (higher plants), suggesting a higher contribu-tion due to the drainage of important watershed areas

and probably a significant dilution of anthropogenicpollution. Moreover, in contrast to small watershedrivers, the influence of rapid source fluctuations is more

limited, resulting in more stable molecular signatures.This stability, as well as the similar vegetation type foreach watershed studied, explains the consistency of the

pyrograms resulting from the large watershed riversediments.

4. Conclusion

Molecular investigations of the insoluble organic

matter from different Alsace-Lorraine river sediments(France) have shown that:

1. The insoluble organic matter pyrograms fromboth small and large watershed river sedimentsreveal a complex molecular composition. Such

distributions do not allow specific sources to bedistinguished; only natural contributions fromproteins, polysaccharides and lignin can be

detected.2. Upon flash pyrolysis, anthropogenic sources yield

similar typesofproducts, underlining thedifficultyin distinguishing discriminant markers. Indeed,

highway and rain retention basins receive acomplexmixture of contributionswhich precludesthe determination of specific contaminants.

Fig. 6. Triangular diagram of composition of solid organic matter from small watershed river (SW), large watershed river (LW),

anthropogenic sources (AS) and continental natural sources (NS).


The lack of distinct signatures from anthropogenicsources and the ubiquitous or undiagnosed major com-pounds produced during flash pyrolysis indicates thatthe specific marker approach does not allow correlation

between contaminated sediments and anthropogenicsources in the region investigated.In contrast, semi-quantitation of the different

pyrograms from river sediments and sources enabledtwo end members to be distinguished in a triangulardiagram: (i) a natural pool rich in heteroatomic com-

pounds and (ii) a more dispersed anthropogenic endmember rich in hydrocarbons. The river and retentionbasin sediments are intermediate. The small watershed

rivers are significantly influenced by anthropogenicsources, probably as a result of limited water flow andlimited natural organic dilution. Specific drained areas(pavements) in the case of highway basins may help to

explain the greater anthropogenic signature. The largewatershed rivers as well as the rain basin show a naturalsignature predominance, suggesting phenomena invol-

ving intense organic dilution by natural sources.

Acknowledgements

This research benefitted from the financial support

and the sampling capacities of the Agence de l’Eau Rhin-Meuse. P.F. was supported by a Region de Lorrainepostdoctoral fellowship. We particularly acknowledgeC. Breuzin of the Agence de l’Eau Rhin-Meuse for

information concerning the different rivers studied andfor thoughtful discussions. The authors would like tothank P. Van Bergen, C. Largeau, M. Sephton, S.J.

Rowland and J.R. Maxwell for scientific and editorialimprovements to the manuscript

Associate Editor—S. Rowland

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Molecular studies of insoluble organic matter in river sediments from Alsace-Lorraine (France

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