identiﬁcation of speciﬁc organic contaminants for …directory.umm.ac.id/data...

Identi®cation of speci®c organic contaminants forestimating the contribution of the Elbe river to

the pollution of the German Bight

J. Schwarzbauer a,*, R. Littke a, V. Weigelt b

aInstitute of Geology and Geochemistry of Petroleum and Coal, Aachen University of Technology, Lochnerstr. 4-20,

D-52056 Aachen, GermanybFederal Maritime and Hydrographic Agency, Bernhard Nocht Str. 78, D-20359 Hamburg, Germany

Abstract

GC/MS analyses have been applied to sediment samples of the German Bight in order to document the state oforganic contamination as well as to identify speci®c molecular markers that are appropriate to estimate the dischargeof anthropogenic compounds derived from the Elbe river. Detailed screening analyses revealed a wide variety oforganic lipophilic compounds of biogenic, petrogenic as well as anthropogenic origin. Potential marker compounds

indicating the contribution of the Elbe river could be attributed mainly to the chlorinated aromatic contaminants.Speci®cally, these include tetra- to hexachlorobenzenes, mono- to dichloronaphthalenes, hexachlorobutadiene, tetra-butyl tin, alkylsulfonic acid phenylesters, 1,2,3,6,7,8-hexahydro-1,1,6,6-tetramethyl-4-isopropyl-as-indacene and 4,40-dichlorodiphenylsul®de. These compounds are suitable to indicate the spatial distribution of Elbe river derived organicmatter. # 2000 Elsevier Science Ltd. All rights reserved.

1. Introduction

The marine environment of the North Sea is highly

in¯uenced by anthropogenic input as a result of intensenavigation, petroleum and gas production, atmosphericdeposition as well as riverine contribution of terrestrialpollutants. The qualitative and quantitative composi-

tion of the organic material in the sediment and thewater column re¯ects the discharge of anthropogeniccontaminants. Hence, natural biogenic substances are

accompanied by a wide variety of anthropogenic com-pounds.In the German Bight a signi®cant proportion of the

anthropogenic organic matter is contributed by con-taminated riverine systems discharging into the NorthSea. Next to the Ems and Weser rivers, the Elbe river is

the most polluted riverine system due to well known

industrial emissions and partly de®cient sewage treat-ment in the catchment area. In order to estimate the¯uvial input to the organic contamination of marine

sediments, analyses of carbon ¯uxes by bulk parametersuch as dissolved organic carbon (DOC), particulateorganic matter (POM), terrestrial organic matter(TOM) are useful (Ittekkot, 1988; Gupta et al., 1997;

Keil et al., 1997; Alberts and TakaÂ cs, 1999). Moredetailed information about the terrestrial contributionto the marine organic matter could be obtained by

identi®cation and quanti®cation of several speci®cmolecular markers (Hedges et al., 1997). For example,analyses of carbohydrates, amino carbohydrates and

amino acids in the suspended particulate matter of theriver Indus indicated a signi®cant terrigenous input tothe marine environment (Ittekkot and Arain, 1986).

Hedges and Parker (1976) characterized the terrestrialorganic matter in surface sediments from the Gulf ofMexico using lignin oxidation products as markers. Thecontribution of the Mackenzie river to the Beaufort sea

coastal sediments was assessed by examination of spe-ci®c aliphatic and aromatic hydrocarbons (Yunker etal., 1991, 1993). With a similar aim, Zegouagh et al.

0146-6380/00/$ - see front matter # 2000 Elsevier Science Ltd. All rights reserved.

PI I : S0146-6380(00 )00076-0

Organic Geochemistry 31 (2000) 1713±1731

www.elsevier.nl/locate/orggeochem

* Corresponding author. Tel.: +49-241-805750; fax: +49-

241-8888152.

E-mail address: [email protected] (J.

Schwarzbauer).

(1996, 1998) studied the molecular and isotopic proper-ties both of hydrocarbons and acids in sediments of theLena River delta and the Laptev Sea.Information about the ¯uvial discharge into the mar-

ine environment can also be achieved with anthro-pogenic substances (Eganhouse, 1997; Takada et al.,1997). Well known anthropogenic markers include e.g.

tetrapropylene-based alkylbenzenes (TAB), linear alkyl-benzenes (LAB) and the sulfonated analogues (linearalkylbenzenesulfonates, LAS). The LAS are widely used

surfactants and the LAB are synthetic raw material.Their occurrence in the aquatic environment re¯ects theemission of municipal waste water e�uents (Takada

and Eganhouse, 1998, and references cited therein).Fecal steroids derived from sewage contaminated rivershave also been used to document the discharge of ¯uvialanthropogenic matter to coastal sediments (Takada and

Eganhouse, 1998, and references cited therein).Natural and anthropogenic marker compounds are

useful to distinguish between marine and terrigenous

organic matter in coastal sediments and water. But inorder to point out the contributions made by di�erentestuaries situated close together, such as in the area of

the German Bight, more speci®c molecular markerinformation is needed. The emission of speci®c anthro-pogenic compounds from point sources or the common

usage of characteristic technical formulations results inquite di�erent patterns of organic substances. These canbe used as river-speci®c molecular markers.Detailed analyses of the organic matter are necessary

to identify such speci®c marker compounds, but only afew investigations have been carried out on organiccontaminants in coastal water and sediments of the

North Sea. Previous detailed analyses of lipophilic andlow molecular compounds in Elbe river water haveindicated a high abundance of river-speci®c organic

substances (Franke et al., 1995; Theobald et al., 1995).For preselected compounds (e.g. thiophosphates, ben-zothiazoles, nitrobenzenes and polycyclic musk fra-grances) the contribution of the Elbe river to the

contamination of coastal waters has been demonstratedquantitatively (Gatermann et al., 1995, 1996; Bester etal., 1997, 1998).

In order to document the state of organic pollution inthe sediments, GC/MS screening analysis has beenapplied to samples from the German Bight. Based on

full scan electron impact mass spectra, gas chromato-graphic retention times and synthetic reference com-pounds, several classes of biogenic and anthropogenic

compounds were identi®ed. The main focus of our studywas to isolate Elbe-speci®c molecular markers that areappropriate to estimate the discharge of riverineanthropogenic compounds to the sediments of the Ger-

man Bight. These compounds can only be potentialmarkers because little information is available about theorganic matter of the Ems and Weser rivers, which are

situated close to the Elbe and also in¯uence the sedi-ments of the German Bight.

2. Experimental

2.1. Samples

Sediment samples (Table 1) were taken in 1998 by theGerman Federal Maritime and Hydrographic Agency

(Hamburg) using a van Veen grab. This yielded materialfrom the sediment surface to a depth of approximately15 cm. All sampling locations are shown in Fig. 1. The

wet sediments were stored in glass ¯asks with Te¯onlined screw caps at 4�C in the dark.

Because of the intense analytical approach (Fig. 2)only the samples of these seven locations were investi-

gated. Three of the samples seemed to be directly in¯u-enced by the Elbe river (A,B) and the Weser and Emsrivers (G), whereas the contributions of the riverine sys-

tems to the organic matter of the sediments situated farerfrom the coastal area (C,D,E,F) are still ambiguous.

2.2. Extraction

Amounts of 200±400 g fresh wet sediments were

extracted sequentially with 50 ml of acetone, twice with50 ml n-hexane/acetone 50/50 (vol/vol) and twice with50 ml n-hexane. Extraction was carried out by disper-sing the samples in portions of 20 g for 5 min in the

solvent using a high-speed dispersion tool (Ultra-TurraxT25, IKA, Stau�en, FRG). Each extraction step wasfollowed by centrifugation at 4000 rpm and separation

of the solvent. After combining the extracts and separ-ating the aqueous phase, the organic layer was driedwith anhydrous granulated sodium sulphate and con-

centrated to a volume of 1 ml. Sulfur was removed byaddition of 50 mg of activated copper powder andultrasonic agitation. After 16 h, the extract was pre-pared for chromatographic fractionation by ®ltration

over 1 g of anhydrous granulated sodium sulphate andconcentration to 0.5 ml.

Table 1

Sediment samples collected from the German Bight (see Fig. 1

for locations)

Sample Altitude Latitude Fraction of

grain size < 63 mm

Dry weight

(%)

A 54�020 8�12.50 > 50% 73.4

B 54�040 8�07.50 > 50% 58.3

C 54�22.50 7�38.750 < 5% 79.9

D 54�300 6�300 5±10% 78.8

E 54�500 6�350 11±20% 72.1

F 55�000 6�300 21±50% 69.5

G 53�490 6�230 < 5% 82.6

1714 J. Schwarzbauer et al. / Organic Geochemistry 31 (2000) 1713±1731

2.3. Fractionation

Sediment extracts were separated into six fractions bycolumn chromatography (Baker, silica gel 40 mm) using

mixtures of n-pentane and dichloromethane as the elu-ent according to Franke et al. (1995). Fraction 1: n-pentane (5 ml), fraction 2: n-pentane/dichloromethane

95/5 v/v (8.5 ml), fraction 3: n-pentane/dichloromethane90/10 v/v (5 ml), fraction 4: n-pentane/dichloromethane40/60 v/v (5 ml), fraction 5: dichloromethane (5 ml),

fraction 6: methanol (5 ml). The acidic compounds offraction 6 were methylated by addition of 0.5 ml of amethanolic diazomethane solution. Prior to analysis, 50ml of an internal standard solution containing 6.0 ng/mld36-hexadecane, 5.1 ng/ml d10-anthracene and 4.7 ng/mld12-chrysene in n-hexane were added to each fraction,and the volume was reduced to approximately 50 ml byrotary evaporation at room temperature. All fractionswere analysed on a gas chromatograph equipped with¯ame ionization and electron capture detector (GC-

FID/ECD) and on a gas chromatograph linked to amass spectrometer (GC±MS).Dry weights of sediments were determined by drying

separate aliquots of samples at 110� C to constant weight.

2.4. Gas chromatographic analysis

Gas chromatographic analysis was carried out on aGC8000 gas chromatograph (Fisons instruments, Wies-baden, FRG) equipped with a 25 m � 0.25 mm i.d. �

0.25 mm ®lm SE54 fused silica capillary column (CSChromatographie Service, Langerwehe, FRG). The endof the capillary column was split to lead the eluateseparately to a ¯ame ionization detector (FID) and an

electron capture detector (ECD) for a simultaneousdetection of the analytes. Chromatographic conditionswere: 1 ml split/splitless injection at 60�C, splitless time

60 s, 3 min hold, then programmed at 3�/min to 300�C,hydrogen carrier gas velocity was 25 cm/s.

2.5. GC/MS-analysis

GC/MS analyses were performed on a FinniganMAT 8222 mass spectrometer (Finnigan, Bremen,

FRG) linked to a Varian Series 3700 gas chromato-graph (Varian, Walnut Creek, USA) which was equip-ped with a 30 m � 0.25 mm i.d. � 0.25 mm ®lm BPX5

fused silica capillary column (SGE, Weiterstadt, FRG).Chromatographic conditions were: 1 ml split/splitlessinjection at 60�C, splitless time 60 s, 3 min hold, then

programmed at 3�C/min to 300�C, helium carrier gasvelocity was 40 cm/s.For low resolution mass spectra the mass spectro-

meter was operated at a resolution of 1000 in electronimpact ionization mode (EI+, 70 eV) with a sourcetemperature of 200�C with scanning from 35 to 700 amuat a rate of 1 s/decade with an inter-scan time of 0.1 s.

Identi®cation of individual compounds was based oncomparison of EI+-mass spectra with those of referencecompounds, mass spectral data bases (NIST/EPA/NIH

Fig. 1. Sampling locations of sediments in the German Bight.

J. Schwarzbauer et al. / Organic Geochemistry 31 (2000) 1713±1731 1715

Mass Spectral Library NIST98, Wiley/NBS Registry ofMass Spectral Data, 4th Ed., electronic versions) and

gas chromatographic retention times, elution patterns orretention indices (e.g. Vassilaros et al., 1982; Rostad andPereira, 1986; Ballschmitter et al.; 1987, Bundt et al.,1991; Paschke et al., 1992; Peters and Moldowan, 1993;

Wang et al., 1994). For correction of injection timeinaccuracies the retention times of the internal standardcompounds were used.

3. Results and discussion

The non-target screening analyses revealed a largenumber of individual organic compounds occurring insediments of the German Bight. All identi®ed con-taminants are listed in Table 2. These are subdivided

and arranged either by their structural properties ortechnical applications in case of some anthropogenicsubstances.

Fig. 2. Analytical procedure for non-target screening analyses of sediment samples.


Table 2

Organic compounds identi®ed in sediments of the German Bight

Compounds A B C D E F G

Alkanes, cycloalkanes and alkenes

Homologous series of n-alkanes (C9 to C30)a + + + + + + +

2,2,4,4,6,8,8-Heptamethylnonanea + + + + + + +

Homologous series of n-alkylcyclohexanes + (+)g (+) + + + (+)

(C4- to C20 side chain)c

Homologous series of n-alkenes (C12 to C20)a +

Terpenoids and degradation products

Limonenea + + + + + + +

Dihydroactinidiolidec + + + + + +

a-Iononec + + + + + +

b-Iononec + + + + + +

b-Cyclocitrala + + +

Cadalenec +

Calamenenec + + + + + + +

a-Cedrenec +

Longicyclenec + +

Junipenec + +

7-Isopropyl-1-methylphenanthrenee + + + + + + +

1,2,3,4-Tetrahydro-7-isopropyl-1-methylphenanthrenee + + + + + + +

Dehydroabietine +

Dehydroabietanee +

2,6-Dimethylundecanee + + + + + + +

Pristanea + + + + + + +

Phytanea + + + + + + +

Phytene (1 isomer)d + + + + + +

Phytadienes (3 isomers)d + + + + + +

6,10-Dimethylundecan-2-onee + + + + + + +

6,10-Dimethyl-5,9-undecadien-2-onee + + + + + + +

6,10,14-Trimethylpentadecan-2-onee + + + + + + +

Phytola

Phytolic acide + + + + +

4,8,12-Trimethyltridecanoic acide + + + + + +

4,8,12-Trimethyltetradecanoic acidc + + + + +

Squalenea + + + + + + +

Hopanoids

18a(H)-Trisnorneohopane, Tsc + + + + + + +

17a(H)-Trisnorhopane, Tmc + + + + + + +

18a-Norneohopanec + + + + + +

17a(H),21b(H)-Norhopanec + + + + + + +

17b(H),21a(H)-Norhopanec + + + + + + +

17b(H),21b(H)-Norhopanec + + + + + + +

17a(H),21b(H)-Hopanec + + + + + + +

17b(H),21b(H)-Hopanec + + + + + + +

(22S)-17a(H),21b(H)-Homohopanec + + + + + + +

(22R)-17a(H),21b(H)-Homohopanec + + + + + + +

(22S)-17a(H),21b(H)-Bishomohopanec + + + + + + +

(22R)-17a(H),21b(H)-Bishomohopanec + + + + + + +

(22S)-17a(H),21b(H)-Trishomohopanec + + + + + + +

(22R)-17a(H),21b(H)-Trishomohopaned + + + + + + +

Steranes and steroids

C20-5 a(H),14a(H),14a(H)-Steranec + + + + + + +

C21-5a(H),14b(H),17b(H)-Steranec + + + + + + +

C22-5a(H),14b(H),17b(H)-Steranec + + + + + + +

(continued on next page)


Table 2 (continued)


C27-20S-13b(H),17a(H)-Diasteranec + + + + + + +

C27-20R-13b(H),17a(H)-Diasteranec + + + + + + +

C27-20S-13a (H),17b(H)-Diasteranec + + + + + + +

C27-20R-13a(H),17b(H)-Diasteranec + + + + + + +



20S-5a(H),14a(H),17a(H)-Cholestanec + + + + + + +

20R-5a(H),14b(H),17b(H)-Cholestanec + + + + + + +

20S-5a(H),14b(H),17b(H)-Cholestanec + + + + + + +

20R-5a(H),14a(H),17a(H)-Cholestanec + + + + + + +

Cholestenes (1 isomer)d + + + + + + +

Cholestadienes (3 isomers)d (+) (+) + (+) + + +

Cholestatrienes (3 isomers)d + + + + + + +

5a(H)-Cholestan-3-onea + + + + + +

5b(H)-Cholestan-3-onea + + + + + +

20S-5a(H),14a(H),17a(H)-Ergostanec + + + + + + +

20R-5a(H),14b(H),17b(H)-Ergostanec + + + + + + +

20S-5a(H),14b(H),17b(H)-Ergostanec + + + + + + +

20R-5a(H),14a(H),17a(H)-Ergostanec + + + + + + +

Ergostanones (2 isomers)d + + +

20S-5a(H), 14a(H),17a(H)-Stigmastanec + + + + + + +

20R-5a (H),14b(H),17b(H)-Stigmastanec + + + + + + +

20S-5a(H),14b(H),17b(H)-Stigmastanec + + + + + + +

20R-5a(H),14a(H),17a(H)-Stigmastanec + + + + + + +

Stigmastened + + + + + + +

Stigmastadienes (1 isomer)d + + + + + + +

Stigmastatrienes (2 isomers)d + + + + + + +

Stigmastanones (2 isomers)d + + + +

Alkylbenzenes

Ethylbenzenea + + + + + + +

m-/p-Xylenea + + + + + + +

o-Xylenea + + + + + + +

C3-Benzenes (8 isomers)d (+) + + (+) + (+) +

C4-Benzenes (15 isomers)d (+) (+) + + + + +

C5-Benzenes (10 isomers)d (+) + + + + + +

C6-Benzenes (6 isomers)d (+) + (+) (+) + + +

C7-Benzenes (7 isomers)d (+) + (+) + (+) + +

C8-Benzenes (9 isomers)d (+) + (+) (+) (+) + (+)

C9-Benzenes (11 isomers)d (+) + (+) (+) + + (+)



C12-Benzenes (5 isomers)d (+) + (+) + + + (+)

C13-Benzenes (5 isomers)d (+) + (+) + + + (+)

C14-Benzenes (11 isomers)d (+) + (+) + + (+)

5-Phenyldecanea + + + + + + +

4-Phenyldecanea + + + + + + +

3-Phenyldecanea + +

6-Phenylundecanea + + + + + + +





6-Phenyldodecanea + + + + + + +






Table 2 (continued)



7-/6-Phenyltridecanea + + + + + + +

5-Phenyltridecanea + + + + + + +

4-Penyltridecanea + + + + + + +

3-Phenyltridecanea + + + + + +

2-Phenyltridecanea + + + + +

Polycyclic aromatic compounds, PACs

Naphthalenea + + + + + + +

Ethylnaphthalene (1 isomer)d + + + + + + +

1-Methylnaphthalenea + + + + + + +

2-Methylnaphthalenea + + + + + + +

C2-Naphthalenes (6 isomers)d + + + + + + +

C3-Naphthalene (10 isomers)d + + + + + + +

C4-Naphthalene (8 isomers)d + + (+) (+) + + (+)

Biphenyla + + + + + + +

3-Methylbiphenylb + + + + + + +

4-Methylbiphenylb + + + + + + +

C2-Biphenyls (3 isomers)d + + + + + + +

C3-Biphenyls (3 isomers)d (+) + + + (+) (+) +

1,1-Diphenylethaneb +

Acenaphtylenea + + + + + + +

Acenaphtenea + + + + + + +

Fluorenea + + + + + + +

9-Methyl¯uorenea + + + + + + +



Methyl¯uorenes (1 isomer)d + + + + + + +

C2-Fluorenes (6 isomers)d (+) + (+) (+) (+) (+) (+)

1-Phenylnaphthalenea + + + + + + +

2-Phenylnaphthalenea + + + + + + +

Phenanthrenea + + + + + + +

Anthracenea + + + + + + +

3-Methylphenanthreneb + + + + + + +


2-Methylanthraceneb + + + + + +

4-/9-Methylphenanthreneb + + + + + + +


Dimethylphenanthrene (1 isomer)d + + + + + + +

3,5-Dimethylphenanthreneb + + + + + + +


1,3-3,10-Dimethylphenanthreneb + + + + + + +

1,6-/2,9-Dimethylphenanthreneb + + + + + + +


1,9-/4,9-Dimethylphenanthreneb + + + + + + +



C3-Phenanthrenes/-anthracenes (7 isomers)d + + + + + + +

4H-Cyclopenta(def)phenanthreneb + + + + + + +

Fluoranthenea + + + + + + +

Acephenanthryleneb + + + + + +

Pyrenea + + + + + + +

Methyl¯uoranthenes/-pyrenes (6 isomers)d + + + + + + +

Dimethyl¯uoranthenes/-pyrenes (9 isomers)d + + + + + + +

Ethyl¯uoranthenes/-pyrenes (2 isomers)d +

o-Terphenylb + + + + + + +



Table 2 (continued)


m-Terphenylb + + + + +

p-Terphenylb + + + + + + +

Benz(ghi)¯uoranthenea + + + + + + +

Benz(c)phenanthrenea + + + + + + +

Benz(a)anthracenea + + + + + + +

Cyclopenta(cd)pyrenea + +

Chrysene/Triphenylenea + + + + + + +

Naphthaceneb + + + + + + +

Methyl-228 (5 isomers)d,f + + + + + + +

C2-228 (7 isomers)d,f + + + + + + +

1,20-Binaphthylb + + + + + + +

2,20-Binaphthylb + + + + + + +

9-Phenylphenanthreneb + + + + + + +

Phenylphenanthrene/-anthracenes (3 isomers)d + + + + + + +

Benz(x)¯uoranthene (x=j,b,k)a + + + + + + +

Benz(e)pyrenea + + + + + + +

Benz(a)pyrenea + + + + + + +

Perylenea + + + + + + +

Methyl-252 (5 isomers)d,f + + + + + + +

Indeno(1,2,3-cd)pyrenea + + + + + + +

Benzo(ghi)perylenea + + + + + + +

Dibenzo(a,h)anthraceneb + + + + + + +

Dibenzo(a,c)anthraceneb + + + + + + +

Benzo(b)chrysenea + + + + + + +

Piceneb + + + + + + +

Anthanthreneb +

Hydrogenated aromatic compounds

Decalina + + + + + +

Tetralina + + + +

1,1,6-Trimethyletraline + + + + +

3,3,7-Trimethyl-1,2,3,4-tetrahydrochrysenee + + +

Cyclohexylbenzenee + + + + + +

Cyclohexylcyclohexanee + + + +

Sulphur containing PACs

Benzo(b)thiophenea + + + + +

Dibenzothiophenea + + + + +

Benzo(b)naphtho(2,1-d)thiopheneb + + + + + + +


Phenanthro(9,10-b)thiopheneb + + + + + + +


Methylbenzonaphthothiophenes (4 isomers)d + + + + + + +

Oxygen containing PACs

Benzofurana + + + + + + +

Methylbenzofuran (2 Isomers)d + + + + + + +

Dibenzofurana + + + + +

Methyldibenzofuran (2 isomers)d + + + + + +

C2-Dibenzofuran (4 isomers)d + + + + + + +

Benzonaphthofuran (6 isomers)d + + + (+) + + +

Methylbenzonaphthofuran (4 isomers)d + + + + +

Nitrogen containing PACs

Carbazola + + + + + + +

Methylcarbazoles (2 isomers)d + + + + + + +

Benzcarbazoles (2 isomers)d + + + + (+) +



Table 2 (continued)


Oxygenated aromatic compounds

Cyclpenta(def)phenanthren-4-oneb + + +

9,10-Anthraquinonea + +

Benzanthronea + + + + +

Sul®des

Di-iso-propyldisul®dea + + + + + + +

Di-iso-propyltrisul®dee + + + + + +

Alcohols and phenols

2,9-Dihydroxy-6-methyl-4,7-dioxadecanee + + + + + + +

Phenola + + + + +

4-Cresola + + +

2-/3-Cresola + + +

Aldehydes and ketones

Homologous series of n-aldehydes (C9 to C32)a + + + +

Homologous series of 2-alkanones (C23 to C29)b + + (+) (+)

Benzaldehydea + + + + +

Methylacetophenoned + + + + + + +

1-(2,3-Dihydro-1,1-dimethyl-1H-inden-4-yl)-ethanonee + + + +

Alkanoic acids

Homologous series of n-alkanoic acids (C9±C26)a (+) (+) (+) +

Homologous series of iso-alkanoic acids (C12±C20) + (+) (+) +

Homologous series of anteiso-alkanoic acids (C12±C20) + (+) (+) +

9-Hexadecenoic acid, palmitoleic acida + +

9,12,15-Octatrienoic acid, linolenic acida + +

9,12-Octadienoic acid, linoleic acida

9-Octadecenoic acid, oleic acida + + + +

Eicosatetraenoic acid, arachidonic acida +

Eicosapentaenoic acidd +

Phenylacetic acida + + + + +

Esters

Complex mixture of wax esters (C27 to C32)d (+) + + + +

Methyldodecanoatea + + +

Methyltetradecanoatea + + +

Methyl-iso-pentadecanoatee + + +

Methyl-anteiso-pentadecanoatee + + +

Methylpentadecanoatea + + +

Methyl-iso-hexadecanoatee + + +

Methylpalmitoleatea + +

Methylhexadecanoatea + + +

Methyl-iso-heptadecanoatee + +

Methyl-anteiso-heptadecanoatee + +

Methylheptadecanoatea + + +

Methyloleatea + +

Methyloctadecanoatea + + +

Methyleicosanoatea + +

Isopropyldodecanoatee + +

Isopropyltetradecanoatee + + + + + +

Isopropylhexadecanoatee + + +

Dibutyl-2-butenoatee + + +

Amides

Pentadecanamidee + + + +

Hexadecanamidea + + + + + + +

Heptadecanamidee + + + + + + +

Octadecanamidea + + + +



Table 2 (continued)


Ethylmethylmaleimidee + + + + +

Tocopherols and degradation products

a-Tocopherola + + + + + + +

3,4-Dimethyl-2,5-furandionea + + +

4,8,12,16-Tetramethylheptadecan-4-olidea + + + + + + +

Plasticizers

Dimethylphthalatea + + + + + + +

Dimethylterephthalatea + + + + + + +

Diethylphthalatea + + + + + + +

Di-iso-butylphthalatea + + + + + + +

Di-n-butylphthalatea + + + + + + +

Bis(2-ethylhexyl)phthalatea + + + + + + +

2,4,4-Trimethylpentan-1,3-diol-diisobutyratea + + + + +

Tributylphosphatea + + + + + +

Complex mixture of alkylsulfonic acid phenylesters (C12 to C18 side chains)a (+) +

Fragrances and UV-protectors

Galaxolidea + + + + + + +

Tonalidea + + + + + + +

2,6,6-Trimethyl-2-cyclohexen-1,4-dionea + + + + + +

1,2,3,6,7,8-Hexahydro-1,1,6,6-tetramethyl-4-isopropyl-as-indacene +

4-Methoxycinnamic acid 2-ethylhexyl estera + + + + + +

Halogenated compounds

Complex mixture of tetra- to heptachlorinated biphenylsa,d + + (+) (+) + + +

Hexachlorobutadienea + +

1,3-Dichlorobenzenea + + + + + + +



1,3,5-Trichlorobenzenea + + + + + + +

1,2,4-Trichlorobenzenea + + + + + + +

1,2,3,5-/1,2,4,5-Tetrachlorobenzenea + + + +

1,2,3,4-Tetrachlorobenzenea + + + +

Pentachlorobenzenea + + + + +

Hexachlorobenzenea + + + + +

4,40-Dichlorodiphenylsul®dea + + + + +

1-Chloronaphthalenea + + +

1,4-Dichloronaphthalenea + + +

1,5-/1,6-Dichloronaphthalenea + +

1,7-/2,6-/2,7-Dichloronaphthalenea + +

Bromophenold +

Pesticides and degradation products

4,40-DDMUa +

4,40-DDEa + + +

4,40-DDDa + + + + + +

Organometallic compounds

Tetrabutyltina + + + + +

a Identi®ed by comparison of gas chromatographic and mass spectral data with those of reference compounds.b Identi®ed by comparison of gas chromatographic and mass spectral data with those of mass spectral data bases and published

retention indices.c Identi®ed by comparison of gas chromatographic and mass spectral data with those of mass spectral data bases and published gas

chromatographic elution patterns.d Molecular structure is not more speci®ed.e Identi®ed by comparison of mass spectral data with those of mass spectral data bases.f Only molecular masses of the parent PAH are given.g Not all isomers were detected.


3.1. Commonly observed organic compounds in coastalsediments of the German Bight

Biological activity in theGerman Bight produces several

groups of low molecular lipophilic compounds depositedin the surface sediments together with land-derivedorganic matter. Carotenoid degradation products (e.g.

ionenes, dihydroactinidiolide ) and compounds structu-rally related to phytol (e.g. pristane, phytane, phytene,phytadiene, 6,10,14-trimethylpentadecan-2-one, 4,8,12-

trimethyltetradecanoic acid) were observed. Also fattyacids from C9 to C26 were identi®ed as main componentsin the ®fth liquid chromatographic fraction. Next to the

n-alkanoic acids, several methyl branched acids withanteiso and iso substitution (chain length from C12 toC17) as well as the unsaturated components, palmitoleicacid, linolenic acid, linoleic acid, oleic acid, arachidonic

acid and an eicosapentaenoic acid, were detectable atmost of the sampling locations. It is well known thatthese classes of biogenic compounds detected in lacus-

trine sediments are derived from both autochthonousand allochthonous emission and are, therefore, of mar-ine and terrigenous origin (Cranwell, 1981a; Cranwell et

al., 1987; Riley et al., 1991). In addition, complex mixt-ures of wax esters with chain lengths from C27 to C32

could be detected in sediment samples of sites B, F,G,and

E. The mass spectral data and gas chromatographic

properties (Fig. 3) suggest an isomer distribution similarto that described by Cranwell (1981b), who assumed thatthe wax esters were produced by microbial activity.Terpenoids are not always diagnostic of biogenic

contributions to the organic matter in sediments. Wide-spread use of monoterpenoic compounds in productssuch as perfumes and odour agents (e.g. mixtures of a-and b-ionenes, limonene), in organic solvents (oil of tur-pentine) and as plasticizers (e.g. campher, fenchone) andthe resulting discharge into riverine systems prevents an

absolute association of such compounds with naturalsources. Also a-tocopherol, detected in all sedimentextracts, could not be associated only with biogenic

sources because of its widespread use as an antioxidantand vitamin in food as well as food supplements (Egan-house and Kaplan, 1985). The occurrence of 3,4-dime-thyl-2,5-furandione and 4,8,12,16-tetramethylheptadecan-

4-olide, previously described as oxidation products forthe structure elucidation of tocopherols (Fernholz,1938), suggests a possible oxidative degradation of a-tocopherol in the aquatic environment.Long chain n-aldehydes (C9±C32) found at sampling

locations A,B and G, situated near to the estuaries of

the Elbe and Ems rivers, could be indicative of the con-tribution of terrestrial organic matter. Such long-chainn-aldehydes (C20±C32) with even-to-odd carbon chain

length predominance have been attributed to the input

Fig. 3. Gas chromatographic elution of wax esters in the range from C27 to C32 illustrated by their molecular ion chromatograms. The

chain lengths of the acidic and alcoholic components (R and R0) range between C7 and C21.


of terrestrial plant waxes, whereas the origin of n-alde-

hydes with shorter side chains is not known (Prahl andPinto, 1987; Stephanou, 1989). In the studied sedimentsthe homologous series of the n-aldehydes show a dis-tribution in the range from C20 to C32 according to

previously published results (Fig. 4). N-aldehydes oflower molecular weight (C9±C19) maximizing at C10 andC15 occurred in the same concentration range as the

higher homologous, but a carbon chain length pre-

dominance is not observable. In sample A, mainly in¯u-enced by the Elbe river, the composition of n-aldehydeswas di�erent to that of sample G, which is situated nearthe estuary of the Ems Rivers. In both samples dis-

tributions maximized at C26, but the even-over-oddpredominance is higher at sample location G. Also theamount of short-chain n-aldehydes (C9±C18) relative to

Fig. 4. Comparison of gas chromatographic elution pattern of n-aldehydes at sample sites B, E and G. Chain lengths are marked by

numbers.


the long-chain components (C19±C32) in sample G isgreater than in sediments from sample site A. The pre-sence of n-aldehydes in sediments from sampling loca-tion E indicates a terrigenous contribution at this site

too. The homologous pattern in this sample could beconstructed by mixing of the n-aldehydes at samplinglocation A and G. Accordingly, the land-derived

organic matter at site E seemed to originate from theElbe river as well as from the Ems and Weser rivers.

In addition, the occurrence of n-alkan-2-ones (C23±C29) at sampling locations A,B,E and G suggested ter-rigenous contributions to the coastal sediments due tothe proposed formation by microbial b-oxidation of

corresponding higher plant derived n-alkanes (Allen etal., 1971; Cranwell, 1981a; Riley et al., 1991).A second group of lipophilic compounds in sediments

of the German Bight were petrogenic substances. Thedistributions of hopanoids and steranes identi®ed in the

Fig. 5. Gas chromatographic elution pro®les of hopanes (m/z 191) and steranes (m/z 217) re¯ecting petrogenic input into coastal

sediments.


sediment samples (Fig. 5) were indicative of petrogenicinput due to their unique structures, persistence and wellknown diagenetic and catagenetic transformations(Volkman et al., 1997). For instance the occurrence of

C31- to C33-hopanes with similar concentrations of 22R-and 22S-isomers as well as the ratio of trisnorhopanes(Ts/Ts-Tm) is characteristic of thermally mature organic

material that could only be introduced to recent sedi-ments by contamination from fossil fuels. Unresolvedcomplex mixtures (UCM's) are generally observed in the

aliphatic fractions. These UCMs and high amounts ofalkylated cyclohexanes and benzenes also re¯ect thecontribution of petrogenic emissions, whereas the pet-

rogenic n-alkanes were superposed by biogenic con-tributions indicated by an odd-over-even carbon chainlength predominance. A successful di�erentiation ofaliphatic hydrocarbons from both biogenic and petro-

genic sources in coastal sediments is rather di�cult(Fernandes et al., 1997; Tran et al., 1997).Polycyclic aromatic compounds (PACs) are ubiqui-

tous contaminants in several environmental compart-ments. In coastal sediments, direct input of PAC byatmospheric deposition or discharge of petroleum

products is supplemented by riverine contribution ofurban and industrial e�uents as well as urban runo�containing PACs from asphalt and car exhaust parti-

cles (Mattiasson et al., 1977; Wakeham et al., 1980;Wang et al., 1995; Bence et al., 1996; Aboul-Kassimand Simoneit, 1996; Burns et al., 1997; Dachs et al.,1997). In sediments of the German Bight we identi-

®ed di- to hexacyclic aromatic compounds accom-panied by C1- to C3-substituted isomers in the sameconcentration range. Pyrogenic PACs originating from

incomplete combustion processes are represented by apredominance of ¯uoranthene and pyrene as well as®ve- and six-membered ring compounds in the fourth

chromatographic fraction of each sediment extract.PACs of fossil origin are indicated by high amountsof naphthalene, phenanthrene and alkylated isomers ofseveral parent polycyclic aromatic hydrocarbons that

were main components in the third chromatographicfraction.Hydrogenated PACs were identi®ed in minor con-

centrations such as tetralin, decalin, 1,1,6-trimethylte-tralin and hydrogenated biphenyls. Nitrogen-, sulphur-and oxygen-containing PAC with alkylated isomers

occurring in higher amounts were indicative for organicmatter of fossil origin. Sulphur containing PACs arewell documented constituents of crude oils and petro-

genic products (e.g. Grimmer et al., 1981a,b; Later etal., 1981; Glinzer et al., 1983; Arpino et al., 1987; Wangand Fingas, 1995; Chakhmakhchev et al., 1997). Theidenti®ed oxygenated PACs, cyclopenta(def)phenanthren-

4-one, 9,10-anthraquinone and benzanthrone, probablyoriginate from oxidation of polycyclic aromatic hydro-carbons during incomplete combustion or atmospheric

transport (Schuetzle et al., 1981; KoÈ nig et al., 1983;Tong and Karasek, 1984).In addition to biogenic and petrogenic compounds, a

wide variety of anthropogenic substances were identi-

®ed. Several low molecular weight organic compoundsrepresenting domestic source contamination were intro-duced to the coastal sediments by riverine discharge.

Methyl and isopropyl esters of fatty acids originatingfrom soaps and washing agents are main componentsof household e�uents (Paxeus, 1996). Their occurrence

is associated with anthropogenic emissions and further-more riverine contribution to coastal sediments. Also thehigher concentrations of coprostanone in comparison to

cholestanone suggest contributions from sewage e�u-ents and are, therefore, indicative for organic matter ofriverine origin (Chalaux et al., 1995; Takada et al., 1997;Chan et al., 1998). Major components in the ®fth liquid

chromatographic fraction of each analysed sedimentextract were a group of plasticizers, including phtha-lates, 2,4,4-trimethylpentan-1,3-diol-diisobutyrate and

tributylphosphate. These compounds are well knownubiquitous pollutants and were also detected in Elberiver water (Franke et al., 1995). Fragrances and odor-

ants also indicate municipal and, therefore, land derivedcontamination in coastal sediments. In the sedimentsamples from the German Bight we identi®ed in most

samples the musk fragrances galaxolide and tonalideused as odorants in detergents as well as 2,6,6-trimethyl-2-cyclohexen-1,4-dione (4-oxoisophorone). This com-pound is industrially produced via oxidation of iso-

phorone and mainly used in perfumes (Papa andSherman, 1981). In addition a 2-ethylhexyl ester of 4-methoxycinnamic acid was frequently identi®ed which is

commonly used as a UV-protector in cosmetics. Further-more a group of organic contaminants could be detectedat all sample locations re¯ecting the widespread use of

synthetic detergents. Linear alkylbenzenes (LABs), withside chain length from C10 to C13, are common detergentresidues due to their use as a raw material for the synth-esis of the alkylbenzenesulfonate surfactants and are

therefore useful anthropogenic markers for domesticwaste emissions (Takada and Eganhouse, 1998, andreferences cited therein). The isomeric composition of

LABs (Fig. 6) di�ers from the pattern of technical for-mulations because of the more rapid degradation ofexternal isomers (phenyl group attached near the end of

the alkyl chain, e.g. 2- and 3-substitution) in comparisonto internally substituted isomers (phenyl group attachednear the middle of the alkyl chain, e.g. 5- and 6-substitu-

tion). The relatively decreasing abundance of externalisomers described as increasing I/E-ratio has been usedas indicator for the state of LAB degradation in theaquatic environment (Takada and Ishiwatari, 1990).

Also alkylated benzenes (C10-14-benzenes) with mole-cular masses corresponding to those of LABS weredetected. But shifted gas chromatographic retention


times and di�erent mass spectral data of these com-

pounds in comparison to those of LABs and TABs indi-cated a multiple substitution at the benzene ring.Well known halogenated organic pollutants of

anthropogenic origin include the polychlorinated biphe-

nyls (PCBs) frequently used in a wide range of technicalapplications. Low aqueous solubility, low vapor pressureand a high resistance to chemical and biological degra-

dation result in the ubiquity of PCBs in aquatic sedi-

ments (Lang, 1992). In each sample investigated in thisstudy a complex mixture of tetra- to heptachlorinatedcongeners could be identi®ed by gas chromatographicanalyses with simultaneous electron capture and ¯ame

ionisation detection (ECD/FID). The individual con-generic composition corresponding to technical mixtureswith a similar content of chlorine is illustrated in Fig. 6.

Fig. 6. Ion chromatogram of LABs (m/z 91) and ECD chromatogram of PCBs indicating anthropogenic inputs from non-point

sources. The superscript on each peak of the LABs indicates the substitution position. Congeners of PCBs are numbered according to

Ballschmitter et al. (1987).


All anthropogenic land-derived contaminants descri-bed above are mainly introduced to the coastal sedi-ments by atmospheric deposition and in higher quantityby riverine contributions. But these compounds can

only be linked to multiple sources or widespread tech-nical use and are, therefore, inappropriate to assess thedischarge of the Elbe river to the German Bight.

3.2. Potential organic molecular marker compounds forestimating the contribution of the Elbe river

Beside the components described above several com-pounds could be identi®ed that seemed to be indicative

of the contribution of the Elbe river to the pollution ofthe sediments in the German Bight (Table 3). The use ofthese compounds as potential Elbe-speci®c markers is,however, limited because of the limited information

about the organic matter derived from other rivers alsodischarging into the German Bight.Two classes of substances are appropriate as Elbe-

speci®c marker compounds: 1. common compoundsonly detected in high amounts at the locations close tothe Elbe river (A,B), and 2. compounds with speci®c

molecular structures that are not ubiquitous con-taminants or have been described formerly as con-taminants of the Elbe river.

A well known Elbe-speci®c compound is tetrabutyltin, the parent substance for the synthesis of mono- totributyl tin compounds widely used as antifoulants, sta-bilizers in poly(vinyl chloride)s (PVC) and industrial as

well as agricultural biocides. The origin of tetrabutyl tinin sediments and suspended particulate matter of theElbe river can be linked to an industrial point source

situated near the con¯uence of the Mulde and the Elberivers (Wilken et al., 1994, Schwarzbauer, 1997). Theoccurrence of tetrabutyl tin not only at sample sites

mainly in¯uenced by the Elbe river (sample sites A,Band C), but also in sediments situated farer from theElbe estuary (sample sites E,F) indicates a wide spatial

distribution of Elbe-derived organic matter in the Ger-man Bight.Also 1,2,3,6,7,8-hexahydro-1,1,6,6-tetramethyl-4-iso-

propyl-as-indacene, attributed to a group of synthetic

fragrances, can be used as Elbe-speci®c tracer molecule.It was detectable only at sampling location B, whereas4-oxoisophorone, 2,4,4-trimethylpentan-1,3-diol-diiso-

butyrate and the musk fragrances, galaxolide and tona-lide, are ubiquitous contaminants of both the Elbe river(Franke et al., 1995) and the sediments investigated in

this study. The indacene compund is part of the largeemission of an industrial plant situated near the Mulderiver (Schwarzbauer, 1997).

As described above, plasticizers were main compo-nents in all gas chromatograms of the semi-polar andpolar fractions obtained from the sediment samples.Examples include phthalates, tributyl phosphate and in

addition a technical mixture of alkylsulfonic acid phe-nylesters. These arylesters were detected recently in highamounts in sediments as well as in the particulate matter

of the Elbe system (Franke et al., 1998). We detectedthese plasticizers only at sampling locations A and Bwith a pattern similar to the isomeric distribution found

in the Elbe river (Franke et al., 1998). The sample sitesA and B are most in¯uenced by the Elbe river and,therefore, we suggest that alkylsulfonic acid pheny-

lesters are Elbe-speci®c.With respect to halogenated compounds, several sub-

stances were identi®ed that are also frequently found insediments of the Elbe river (Schwarzbauer, 1997).

Chlorinated benzenes with 2±6 chlorine substituentswere identi®ed in sediments of the Elbe river as well asin the samples of the German Bight. Dichloro- and tri-

chlorobenzenes are used as synthetic raw material formany technical products such as antiseptic agents, sol-vents and additives (Bryant, 1993). These compounds

were detected in all samples and are, therefore, not Elbe-speci®c. On the contrary higher substituted congeneresappeared at sample sites A,B,C,E and F, but not atsample sites D and G, which are mainly in¯uenced by

input of the Ems river. The occurrence of tetra- andpentachlorbenzenes in the environment is not attributedto speci®c sources due to industrial processes or techni-

cal applications. Only hexachlorobenzene is well knownas a formerly used herbicide and synthetic by-product ina number of organic syntheses (Bryant, 1993; SchloÈ r,

1970). Therefore, the appearance of tetrachloro- tohexachlorobenzenes in the sample sites described abovecould be suggestive for Elbe-speci®c contribution of

organic matter.Mono- and disubstituted chloronaphthalenes with

patterns related to those of technical agents (e.g. Halo-wax 1000) may be appropriate as Elbe-speci®c mole-

cular markers due to their presence only at locationsA,B and C. Although the occurrence of only lowchlorinated naphthalenes is rarely reported (Falandysz,

Table 3

Potential organic marker compounds of the Elbe river

Halogenated

compounds

Nonhalogenated

compounds

� 4,40-Dichlorodiphenylsul®de � Complex mixture of

alkylsulfonic phenylesters

� Tetrachlorobenzenes � 1,2,3,6,7,8-Hexahydro-

1,1,6,6-tetramethyl-4-

isopropyl-as-

indacene

� Pentachlorobenzene � Tetrabutyl tin� Hexachlorobenzene

� 1-Chloronaphthalene� Dichloronaphthalenes

� Hexachlorobutadiene


1998), these substances were identi®ed in sediments ofthe Elbe river (Schwarzbauer, 1997) as well as in thesediment samples described above. In contrast higherchlorinated naphthalenes with up to 8 chlorine atoms

were detected frequently in several environmental com-partments (Falandysz, 1998).Beside the congeneric groups of chlorinated aromatic

substances, individual halogenated compounds such as4,40-dichlorodiphenylsul®de and hexachlorobutadiene, aknown organic agent used as solvent and in hydraulic

¯uids (Koch, 1995), could only be detected at samplesites A,B and C. The origin of 4,40-dichlorodiphenylsul®de in sediments of the Elbe river and in the

investigated samples of the German Bight is stillunknown.To a minor degree degradation products of the pesti-

cide DDT might be useful Elbe-speci®c marker com-

pounds, because of the longer period of DDTapplication in the catchment area of the Elbe river incontrast to the Weser and Ems rivers and the high con-

centration of DDD and DDE found in water as well assuspended particulate matter of the Elbe river (Goetz etal., 1994). The para-substituted isomer of DDE could be

detected only in sediment samples mainly in¯uenced bythe Elbe river (sites A,B,C), whereas 4,40-DDD occurredadditionally at sites D, E and F, but not at site G that is

in¯uenced by the Weser river.

4. Summary and conclusion

Detailed screening analyses revealed a wide variety oforganic lipophilic compounds of biogenic, petrogenic

and anthropogenic origin in sediments of the GermanBight. The biological activity in the marine environmentis be re¯ected by the occurrence of several compounds,

e.g. carotenoids, fatty acids and wax esters. Con-tamination of petrogenic origin are indicated by an iso-meric distribution of saturated steranes and hopanes,characteristic fossil markers occurring in high amounts

in the examined sediments. Substances indicating theterrestrial input of low molecular organic matter to thecoastal sediments might be both biogenic long chain n-

aldehydes and isomers with shorter side chains ofunknown origin. Also several anthropogenic com-pounds characterized the land-derived contribution to

the organic matter in the coastal sediments. Sewage-speci®c marker compounds include coprostanone, linearalkylbenzenes, plasticizers and fragrances.

Speci®c organic marker compounds indicating thecontribution of the Elbe river to the pollution in sedi-ments of the German Bight were attributed mainly tochlorinated aromatic contaminants. Speci®cally, tetra- to

hexachlorbenzenes, mono- and dichloronaphthalenes,hexachlorobutadiene and 4,40-dichlorodiphenylsul®deoccurring only in sediments in¯uenced by the Elbe river

were useful in describing the spatial distribution of Elbe-derived organic matter.Also, an isomeric mixture of alkylsulfonic acid phe-

nylesters, the individual contaminants tetrabutyl tin and

1,2,3,6,7,8-hexahydro-1,1,6,6-tetramethyl-4-isopropyl-as-indacene as well as degraded compounds of DDTcould be attributed to the group of Elbe-speci®c marker

compounds.All identi®ed Elbe-speci®c substances are only poten-

tial molecular markers at present, because marker com-

pounds re¯ecting the input of the Weser and the Emsriver to the sediments of the German Bight are notknown.

Acknowledgements

The authors would like to acknowledge a very helpfuland thorough review of this manuscript by R.P. Egan-house.

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