Anthropogenic Organic Contaminants in Sediments of the Lippe River, Germany Alexander Kronimus*, Jan Schwarzbauer, Larissa Dsikowitzky, Sabine Heim, Ralf Littke

ARTICLE IN PRESS

Water Research 38 (2004) 3473–3484

Anthropogenic organic contaminants in sediments of the Lippe river, Germany Alexander Kronimus*, Jan Schwarzbauer, Larissa Dsikowitzky, Sabine Heim, Ralf Littke

Institute of Geology and Geochemistry of Petroleum and Coal, RWTH Aachen University, Lochnerstrasse 4-20, D-52056 Aachen, Germany

Received 13 August 2003; received in revised form 27 January2004; accepted 8 April 2004

Abstract

Sediment samples of the Lippe river (Germany) taken between August 1999 and March 2001 were investigated by GC–MS-analyses. These analyses were performed as non-target-screening approaches in order to identify a wide range of anthropogenic organic contaminants. Unknown contaminants like 3,6-dichlorocarbazole and bis(4-octylphenyl) amine as well as anthropogenic molecular marker compounds were selected for quantification. The obtained qualitative and quantitative analytical results were interpreted in order to visualize the anthropogenic contamination of the Lippe river including spatial distribution, input effects and time dependent occurrence. Anthropogenic molecular markers derived from municipal sources like polycyclic musks, 4-oxoisophorone and methyltriclosan as well as from agricultural sources (hexachlorobenzene) were gathered. In addition molecular markers derived from effluents of three different industrial branches, e.g. halogenated organics, tetrachlorobenzyltoluenes and tetrabutyltin, were identified. While municipal and agricultural contaminations were ubiquitous and diffusive, industrial emission sources were spatially isolated. Specific seasonal trends of distribution patterns were not observed. r 2004 Elsevier Ltd. All rights reserved.

Keywords: Riverine sediments; Organic contaminants; Xenobiotics; GC–MS; Non target screening; Anthropogenic molecular markers

1. Introduction determine and to distinguish between several anthropogenic sources. Useful municipal anthropogenic mar- Anthropogenic molecular markers are either xenobio- kers are environmentallystable ingredients in detergents tics or natural compounds which are discharged into and bodycare products, for example syntheticfra- environmental compartments byhuman activities. Ad- grances. Industrial markers are usuallytechnically ditionallytheyhave to complywith three conditions: (1) applied compounds or production residues. Further source-specifity, (2) massive and widespread use and (3) details are described elsewhere (Takada and Eganhouse, environmental persistence. Such compounds can be used 1998; Ricking et al., 2003). to trace pathways of source specific effluents as well as to Onlya few publications have considered the anthropogenic organic contamination of the Lippe river. Friege *Corresponding author. Tel.: +49-241-8095749; fax: +49- et al. (1991) investigated the herbicide pollution of Lippe 241-8092152. water and Scho¨ berl and Spilker (1996) determined linear E-mail address: [email protected] alkylbenzenesulphonates (LAS) in a dated sediment (A. Kronimus). core. The historical pollution with polycyclic aromatic

0043-1354/$ - see front matter r 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.watres.2004.04.054 ARTICLE IN PRESS 3474 A. Kronimus et al. / Water Research 38 (2004) 3473–3484 hydrocarbons and several chlorinated compounds were medium-grained quartz sand. The solids contents ranged also investigated on sediment cores derived from a from 45% to 75%. corresponding riparian wetland (Klo¨ s and Schoch, 1993). Polychlorinated biphenyls (PCB) and tetrachlor- 2.3. Extraction and fractionation obenzyltoluenes (TCBT) in sediments were investigated by Poppe et al. (1991). Dsikowitzkyet al. (2002) The samples were treated bysequential dispersion investigated the occurrence and distribution of poly- extraction with acetone and hexane. Each extraction was cyclic musks in water and sediments of the Lippe river. followed bycentrifugation and decantation of the All investigations described focused mainlyon a solvent. The raw extracts were dried with anhydrous preselected set of contaminants, especiallypriority granulated sodium sulphate and elemental sulphur was pollutants. In contrast, the goal of the present study removed with activated copper powder. The extracts was to reveal a varietyof organic compounds in order to were separated into six fractions byliquid chromato- obtain a comprehensive overview on emission sources graphyon silica gel using mixtures of pentane, affecting the river, within one single investigation. dichloromethane and methanol as eluates. After fractio- Consequently, a non target screening approach was nation 50 mL of internal standard mixture containing 1 1 applied. Main focus was to identifyand to distinguish d34-hexadecane (5.0 ng mL ), d10-anthracene (5.0 ng mL ) 1 qualitative different anthropogenic sources (e.g. muni- and d12-chrysene (5.0 ng mL ) in hexane were added. cipal, agricultural or industrial sources) bythe concept Acidic compounds in the methanol fraction were of anthropogenic molecular markers. Further aims were methylated with a methanolic diazomethane solution. to supplement former investigations concerning anthro- Recoveries were determined byspiking four aliquotes of pogenic contamination of Lippe river sediments, to pre-extracted sediments with a mixture of reference identifyunnoticed or unknown anthropogenic com- compounds and subsequent execution of the analytical pounds and to investigate seasonal influences on procedure. Details of these methods are described distribution patterns of contaminants. elsewhere (Franke et al., 1998; Schwarzbauer et al., 2000). 1-Formylpiperidine was synthesized by reaction of formylchloride and piperidine, 3,6-dichlorocarbazole by 2. Materials and methods reaction of carbazole with pentachlorophosphorus (Moskalev et al., 1985) and methyltriclosan was 2.1. Site studied synthesized by reaction of triclosan and dimethylsul- phate. Bis(4-octylphenyl)amine was obtained from a The Lippe river, a tributaryto the Rhine river, is manufacturer. Reference material for pentachlorobuta- situated in North Rhine Westfalia, Germany( Fig. 1). diene isomers were not available. All further reference Due to several municipal communities and industrial compounds and those needed for syntheses were settlings along this small river, it is verysuitable for purchased from Promochem, Aldrich and Merck. targeting numerous anthropogenic contaminants within The recoveryrates determined range from 21% to a restricted area of investigation. Generally, the popula- 88% (see Table 1). These high variations are caused by tion densityand industrial activities along the river different compound-specific affinities to particulate increases from the upper reaches towards the down- matter but also bydifferent volatilities of the com- stream areas. Therefore, less contamination was ex- pounds inducing evaporation losses during extract pected within the upper reaches. preparation.

2.2. Sediment sampling 2.4. Gas chromatographic (GC)/mass spectrometric (MS) analyses All sampling locations are presented in Fig. 1. Four sampling campaigns were performed in August 1999, Qualitative and quantitative GC/MS analyses were February2000, August 2000 and March 2001 including performed on a Trace MS quadrupole mass spectro- nine surface sediment samples, respectively. All samples meter (ThermoQuest, Egelsbach, Germany) linked to a were taken from stagnant water zones directlyat the HRGC 5160 (Carlo Erba, Milano, Italy), which was riverside with a high-grade steel scoop and filled in glass equipped with a 45 m 0.25 mm id 0.25 mm film SE-54 vessels with PTFE seals. The samples were stored at fused silica capillarycolumn (CS, Langerwehe, Ger- +4C until extraction. Further details of the applied many). Chromatographic conditions were 1 mL splitless sampling techniques have been described previously injection at 60C, 3 min hold, then programmed at (Schwarzbauer et al., 2001). Most sediment samples 3 K min1 to 300C; Helium carrier gas flow was were composited of clayand silt. Samples taken near the 1.5 mL s1. The mass spectrometer operated in the spring (sampling location 1) were dominated by electron impact ionization mode (El+, 70 eV) with a ARTICLE IN PRESS A. Kronimus et al. / Water Research 38 (2004) 3473–3484 3475

Fig. 1. Map of sampling sites (arrows) with the locations and molecular structures corresponding to the three identiﬁed industrial point sources as well as the structures of the diffused occurring agricultural and municipal anthropogenic markers.

source temperature of 200C, an interface temperature calibratrion per target compound (see Table 1). Reten- of 270C and scanned from 35 to 700 amu in full scan tion times of all quantified analytes deviated less than mode with a scan time of 1 s and an inter-scan time of 15 s from those of the reference standards. Quantifica- 0.1 s. Quantification was performed byintegration of tion limits were calculated at 0.5 ng g1 drymatter two representative ion chromatograms and a 4-point (signal to noise ratio of approximately10:1 in real ARTICLE IN PRESS 3476 A. Kronimus et al. / Water Research 38 (2004) 3473–3484

Table 1 Recovery7standard deviation of the quantiﬁed compounds

Ions (m=z) Recovery(%) 7Std. dev. (%)

Chlorinated compounds Tetrachlorobenzyltoulenes 283.0, 285.0 2171 Dichlorobenzenes 145.9, 147.9 1973 Trichlorobenzenes 179.9, 181.9 3275 Tetrachorobenzenes 213.9, 215.9 42712 Pentachlorobenzene 250.0, 252.0 59714 Hexachlorobenzene 283.9, 285.9 81710 Methyltriclosan 302.1, 304.1 3577 Bis(1-chloro-2-propyl)ether (1-Chloro-2-propyl-2-chloro-1-propyl)ether 45.1, 121.1 4377 Petachlorobutadiene 225.9, 227.9 3278 Hexachloro-1,3-butadiene 259.9, 261.9 3278 Octachlorostyrene 307.9, 309.9 88714

Nitrogen containing compounds Bis(4-octylphenyl)amine 322.4 2473 N- Formylpiperidine 112.2, 113.2 2574 3,6-Dichlorocarbazole 235.0, 237.0 3377

Fragrances 4-Oxoisophorone 68.2, 152.2 5275 HHCB 243.3, 258.3 43716 AHTN 243.3, 258.3 46717

Metalorganic compounds Tetrabutyltin 289.2, 291.2 3979

(m/z) means mass/charge ratio of the selected ions for quantiﬁcation.

samples), whereas detection limits were specified at spatial distribution within the riverine system. All 0.1 ng g1 drymatter. All concentrations are recovery quantitative data are given in Table 2. The emission corrected and normalized on dryweight bases. In case of situation resulting from the analytical data discussed in the detected pentachlorobutadiene isomer the recovery the following is summarized in Fig. 1. rate and response factor of hexachlorobutadiene was used, which might cause an imprecision of the corre- 3.1. Municipal markers sponding quantitative data. Identification of individual compounds was based on In this studythe quantitativelymost important comparison of mass spectra and retention times with polycyclic musk fragrances, 7-acetyl-1,1,3,4,4,6-hexam- those of reference material or with assistance of mass ethyl-1,2,3,4-tetrahydronaphthalene (AHTN, Tona- spectral databases (NIST/EPA/NIH Mass spectral lides) [Appendix, Structure 1] and 1,2,3,4,6,7,8- libraryNIST98, Wiley/NBSRegistryof Mass spectral hexahydro-4,6,6,7,8,8-hexacyclopenta[g]-2-benzopyrane Data 4th Ed., electronic versions) and published (HHCB, Galaxolides) [Appendix, Structure 2] were retention times or indices. In order to ensure authenti- considered. Samples from the first campaign were cityof the analyticaldata two blank experiments were not considered, because theywere formerlyinvesti- performed which revealed no relevant laboratorycon- gated from Dsikowitzkyet al. (2002) for synthetic taminations. musks. Generallylow concentrations between the limit of detection (LOD) and approximately90 ng g 1 were detected without a distinct trend along the long- 3. Results and discussion itudinal transect of the river. These results are in accordance with the observations by Dsikowitzky The GC/MS non-target screening analyses revealed et al. (2002). numerous compounds of which selected ones are Synthetic fragrances are appropriate municipal mar- subsequentlypresented and discussed in the following ker compounds, especially the polycyclic musks, which mainlywith respect to their source specifityand their are ingredients in detergents, bodylotions, shampoos, ARTICLE IN PRESS A. Kronimus et al. / Water Research 38 (2004) 3473–3484 3477

Table 2 Concentration of the quantiﬁed compounds in samples taken in August 1999, February2000, August 2000 and March 2001 (ng g 1)

Sampling location 1 2 3 4 5 6 7 8 9

(a) August 1999 Chlorinated compounds Tetrachlorobenzyltoluenes 260 40 40 40 100 60 20 n.d n.d Dichlorobenzenes (3 isomers) 27 39 8 n.d. n.d. 58 5 n.d. n.d. Trichlorobenzenes (3 isomers) 11 10 0.5 n.d. n.d. o0.5 2 n.d. n.d. Tetrachorobenzenes (3 isomers) 11 6 n.d. n.d. n.d. n.d. 3 n.d. n.d. Pentachlorobenzene 6 2 o0.5 n.d. n.d. n.d. 1 n.d. n.d. Hexachlorobenzene 27 17 1 o0.5 1 o0.5 2 n.d. 1 Methyltriclosan 220 49 32 34 n.d. 28 18 29 o0.5 Bis(1-chloro-2-propyl)ether (1-Chloro-2-propyl-2-chloro-1-propyl)ether 18 31 n.d. n.d. n.d. n.d. n.d. n.d. n.d. Hexachloro-1,3-butadiene 18 58 o0.5 n.d. o0.5 n.d. n.d. n.d. n.d. Petachlorobutadiene (1 Isomer) 13 8 n.d. n.d. n.d. n.d. n.d. n.d. n.d. Octachlorostyrene 4 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

Nitrogen containing compounds Bis(4-octylphenyl)amine 31 8 5 1 o0.5 18 o0.5 o0.5 o0.5 N- Formylpiperidine 250 12 40 450 n.d. n.d. n.d. n.d. n.d. 3,6-Dichlorocarbazole n.d. n.d. n.d. n.d. n.d. n.d. n.d. 50 n.d.

Fragrances 4-Oxoisophorone 18 35 32 39 57 12 1 28 17

Metalorganic compounds Tetrabutyltin 15 50 10 12 37 26 n.d. n.d. n.d.

(b) February2000 Chlorinated compounds Tetrachlorobenzyltoluenes 210 n.d. 100 70 570 2400 210 n.d. n.d. Dichlorobenzenes (3 isomers) 4 o0.5 7 33 120 17 3 n.d. n.d. Trichlorobenzenes (3 isomers) o1 n.d. o0.5 1 9 n.d. n.d. o0.5 o0.5 Tetrachorobenzenes (3 isomers) n.d. n.d. n.d. n.d. 1 n.d. n.d. n.d. n.d. Pentachlorobenzene 3 n.d. 1 o0.5 4 4 o0.5 n.d. o0.5 Hexachlorobenzene 25 2 3 1 6 3 1 o0.5 1 Methyltriclosan 250 n.d. 70 30 450 280 16 50 n.d. Bis(1-chloro-2-propyl)ether (1-Chloro-2-propyl-2-chloro-1-propyl)ether 26 7 n.d. n.d. n.d. n.d. n.d. n.d. n.d. Hexachloro-1,3-butadiene 13 10 n.d. n.d. n.d. n.d. n.d. n.d. n.d. Petachlorobutadiene (1 Isomer) 10 o0.5 n.d. n.d. n.d. n.d. n.d. n.d. n.d. Octachlorostyrene 6 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

Nitrogen containing compounds Bis(4-octylphenyl)amine 11 n.d. 8 6 o0.5 o0.5 n.d. n.d. n.d. N- Formylpiperidine n.d. n.d. n.d. 29 9 n.d. n.d. n.d. n.d. 3,6-Dichlorocarbazole n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

Fragrances 4-Oxoisophorone 7 n.d. o0.5 n.d. n.d. n.d. o0.5 5 n.d. HHCB o0.5 o0.5 o0.5 o0.5 o0.5 n.d. n.d. o0.5 o0.5 AHTN 23 1 o0.5 o0.5 2 1 n.d. n.d. o0.5

Metalorganic compounds Tetrabutyltin 25 o0.5 11 7 49 o0.5 n.d. n.d. n.d.

(c) August 2000 Chlorinated compounds Tetrachlorobenzyltoluenes o0.5 1 o0.5 n.d. 5 o0.5 o0.5 n.d. n.d. ARTICLE IN PRESS 3478 A. Kronimus et al. / Water Research 38 (2004) 3473–3484

Table 2 (continued)

Sampling location 1 2 3 4 5 6 7 8 9

Dichlorobenzenes (3 isomers) 7 66 8 4 32 o0.5 n.d. n.d. n.d. Trichlorobenzenes (3 isomers) o14 o1 o0.5 o0.5 n.d. 1 n.d. n.d. Tetrachorobenzenes (3 isomers) n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. Pentachlorobenzene 1 1 1 n.d. o0.5 o0.5 o0.5 n.d. n.d. Hexachlorobenzene 2 4 o0.5 n.d. 1 o0.5 o0.5 n.d. o0.5 Methyltriclosan 1 6 o0.5 n.d. 34 20 4 n.d. n.d. Bis(1-chloro-2-propyl)ether (1-Chloro-2-propyl-2-chloro-1-propyl)ether 3 49 n.d n.d n.d n.d n.d n.d n.d Hexachloro-1,3-butadiene 3 26 n.d. n.d. n.d. n.d. n.d. n.d. n.d. Petachlorobutadiene (1 Isomer) o0.5 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. Octachlorostyrene o0.5 n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

Nitrogen containing compounds Bis(4-octylphenyl)amine 3 o0.5 n.d. o0.5 5 6 o0.5 n.d. n.d. N- Formylpiperidine n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 3,6-Dichlorocarbazole n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

Fragrances 4-Oxoisophorone 6 n.d. 4 8 10 o0.5 o0.5 o0.5 o0.5 HHCB 5 o0.5 7 3 o0.5 o0.5 10 o0.5 0.5 AHTN 29 1 13 14 1 4 4 n.d. o0.5

Metalorganic compounds Tetrabutyltin 2 1 1 2 15 12 n.d. n.d. n.d.

(d) March 2001 Chlorinated compounds Tetrachlorobenzyltoluenes 4 o0.5 o0.5 o0.5 n.d. o0.5 n.d. n.d. n.d. Dichlorobenzenes (3 isomers) 22 50 30 53 8 7 10 1 o0.5 Trichlorobenzenes (3 isomers) 6 13 o1 1 n.d. o1 o1.5 o0.5 n.d. Tetrachorobenzenes (3 isomers) 3 7 n.d. n.d. n.d. n.d. o1 n.d. o0.5 Pentachlorobenzene 4 3 o0.5 o0.5 n.d. o0.5 1 o0.5 o0.5 Hexachlorobenzene 18 6 2 o0.5 n.d. o0.5 1 1 1 Methyltriclosan 32 2 20 4 o0.5 2 o0.5 o0.5 n.d. Bis(1-chloro-2-propyl)ether (1-Chloro-2-propyl-2-chloro-1-propyl)ether 11 34 n.d. n.d. n.d. n.d. n.d. n.d. n.d. Hexachloro-1,3-butadiene 17 34 n.d. n.d. n.d. n.d. n.d. n.d. n.d. Petachlorobutadiene (1 Isomer) 9 7 n.d. n.d. n.d. n.d. n.d. n.d. n.d. Octachlorostyrene 1 o0.5 n.d. n.d. n.d. n.d. n.d. n.d. n.d.

Nitrogen containing compounds Bis(4-octylphenyl)amine n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. N- Formylpiperidine n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 3,6-Dichlorocarbazole n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

Fragrances 4-Oxoisophorone 8 1 24 4 2 2 20 4 n.d. HHCB 20 1 56 1 3 4 41 n.d. n.d. AHTN 90 2 45 4 2 2 15 n.d. n.d.

Metalorganic compounds Tetrabutyltin 11 4 34 35 4 4 n.d. n.d. n.d. n.d. (not detected) means the concentration was below detection limit (o0:1ngg1). o0:5 means the concentration was below limit of quantiﬁcation and above detection limit (0.1–0.5 ng g1). ARTICLE IN PRESS A. Kronimus et al. / Water Research 38 (2004) 3473–3484 3479

perfumes and after shaves (Geyer et al., 2000). These ] 450 -1 ~ fragrances were multiple detected in aquatic systems as 300 ~ well as in organisms (e.g. Dsikowitzkyet al., 2002 ; Franke et al., 1999; Schwarzbauer et al., 2000). Due to g [ng n 200 their ubiquitythere is concern about the toxicityof polycyclic musks (Balk and Ford, 1999). 100 4-oxoisophorone [Appendix, Structure 3], another synthetic fragrance detected, is characterized as an Methyltriclosa 0 almost ubiquitous contaminant released from diffusive 123456789 sources with maximum concentrations of about ] 60

-1 90 ng g1. The compound is an ingredient mainlyin perfumes (Papa and Sherman, 1981) and was formerly 40 reported as a contaminant in sediments of the Havel and Spree rivers (Ricking et al., 2003) as well as in water samples of the Lippe river (Dsikowitzky, 2002). 20 Noteworthy, there is no information available concerning fate and stabilityof 4-oxoisophorone in the 0

4-Oxoisophorone [ng g environment so far. Methyltriclosan [Appendix, Struc- 123456789 ture 5] was detected as an almost ubiquitous compound Sampling locations with concentrations up to 450 ng g1. This compound is a methylated transformation product of triclosan August '99 February '00 August '00 March '01 [Appendix, Structure 4], which was absent within the investigated samples. Triclosan is a common antiseptic Fig. 2. Concentrations of two selected municipal molecular used in toothpastes, detergents, socks, underwear, markers, i.e. Methyltriclosan (upper panel), in a longitudinal plastic products, shampoos, deodorants and soaps cross-section of the Lippe river at four occasions. For the (Adolfsson-Erici et al., 2002; Lindstro¨ m et al., 2002). location of sampling sites see Fig. 1. With respect to these speciﬁc applications and to its environmental stabilitytriclosan can be regarded as a municipal molecular marker. As an unambi- guous transformation product methyltriclosan can 300 also act successfullyas an anthropogenic marker of municipal efﬂuents. This metabolite was formerly 200 ~

identiﬁed in lakes and rivers in Switzerland (Lindstro¨ m ] -1 et al., 2002). 80

In order to visualize the contribution of municipal g [ng sewage efﬂuents as revealed bythe marker compounds 40 introduced, Fig. 2 illustrates the spatial and temporal occurrence of 4-oxoisophorone and methyltriclosan. 0 Emissions along the longitudinal transect are character- 123456789 Ssampling locations ized bya high variation and slightlyhigher concentra- Tetrachlorobenzyltoluenes Hexachlorobenzene tions downstream of Hamm-Nordheringen. With Tetrabutyltin respect to the seasonal variations no preferential trends were observed. Fig. 3. Concentrations of three selected industrial derived anthropogenic markers in samples from August 1999. For the 3.2. Industrial and agricultural markers locations of sampling sites see Fig. 1.

PCBs were detected as ubiquitous contaminants. Since PCBs are used in a wide field of applications they are not suitable as anthropogenic markers. In contrast, isomeric mixture named ‘Ugilec 141’. The contamina- the PCB substituents TCBT [Appendix, Structure 6] can tion of sediments from the Lippe river with Ugilec 141 is serve as anthropogenic markers because of their higher evident bycomparing the elution patterns of TCBTs in specifitydue to their limited technical applications. In all the isomeric mixture with those in the sediments (Fig. 4). sampling campaigns TCBTs were detected downstream The application of Ugilec 141 in Germanyis restricted from sampling location 7 (Fig. 1) only, with concentra- to the usage as a hydraulic fluid in coal mining industry. tions of up to 2400 ng g1 (see Fig. 3). In Europe, An isomer-specific determination of more than 70 TCBTs are commerciallyavailable mainlyas a technical isomers of Ugilec 141 was performed by Ehmann and ARTICLE IN PRESS 3480 A. Kronimus et al. / Water Research 38 (2004) 3473–3484

1.000.000 effluents of this plant and a subsequent transport ‘Ugilec 141’ through the Seseke river into the Lippe river is evident 800.000 from the analytical data. As a third set of industrial marker compounds several 600.000 chlorinated compounds were detected some of which are characterized byhigh source specificities. Bis(1-chloro-2- 400.000 Ion current propyl)ether [Appendix, Structure 8] and (1-chloro-2- propyl-2-chloro-1-propyl)ether [Appendix, Structure 9] 200.000 were quantified cumulativelyas theywere chromtogra-

0 phicallynot fullyseparable. These dichlorinated ha- 240.000 loethers were detected at sampling locations 1 and 2 Sediment sample exclusivelywith concentrations ranging from 7 to 200.000 34 ng g1. It has to be noted that (1-chloro-2-propyl-2- 160.000 chloro-1-propyl)ether listed as priority pollutant by the EPA is toxic for aquatic species and seems to 120.000 have mutagenic and cancerogenic properties (McGregor

Ion current 80.000 et al., 1988). Since bischloropropylethers are known by-products from various technical syntheses, e.g. the 40.000 aqueous chlorination of propene (De Leer, 1985), 0 the potential sources of these contaminants are chemical plants which perform technical organochlorine Retention time syntheses. Fig. 4. Ion chromatograms of TCBT in the technical formula- Additionally, hexachloro-1,3-butadiene (HCBD) [Ap- tion ‘Ugilec 141’ (50 ng injected, m=z ¼ 283) and in the pendix, Structure 10] and one pentachlorobutadiene sediment (m=z ¼ 283) of location 6 from February2000. isomer were identified. These compounds were detected almost exclusivelyin samples from locations 1 and 2 with concentrations up to 34 ng g1. In two cases HCBD was detected upstream of location 2, but with concentrations below the limit of quantification. This substance Ballschmitter (1989). The biodegradabilityof TCBTs by is environmentallyrelevant as a by-productfrom the comparison with PCBs is discussed elsewhere (van technical synthesis of volatile chlorinated organics like Haelst et al., 1995). tri- and tetrachloroethene. Anaerobic transformation ‘Ugilec T’, a mixture of trichlorobenzenes and experiments revealed 15 metabolites of HCBD including Ugilec 141, is in Germanyexclusivelyused as a one pentachlorobutadiene isomer (Booker and Pavlos- dielectric fluid in transformers. The emission of TCBT tathis, 2000). from coal mining activities or transformers can be Octachlorostyrene [Appendix, Structure 11] was differentiated byanalysingaccompanied trichloroben- detected exclusivelyin samples from locations 1 and 2 zenes. Since the distribution patterns of trichloroben- with concentrations up to 6 ng g1. The occurrence of zenes do not correlate with those of Ugilec 141, the octachlorostyrene (OCS) in lacustrine sediments was TCBT contaminations can be clearlydeclared as correlated with electrolytical chlorine production using effluents from coal mining industry(see Table 2). This graphite anodes (Kaminskyand Hites, 1984 ). The observation is in accordance with coal mining activities formation of OCS in electrolytical processes other than in the Ruhr Basin, which is partiallydrained bythe chlorine gas production are also conceivable (e.g. Lippe river. manganese production). Therefore, OCS can be used Tetrabutyltin [Appendix, Structure 7] was detected as a marker compound to prove effluents from chemical downstream of sampling location 6, which is situated industry. close to the Seseke river (a tributaryto the Lippe river) Considering the spatial distribution of the chlorinated discharging into the Lippe river (see Figs. 1,3). marker compounds (bischloropropylethers, chlorinated Organotins are well known contaminants, especiallyof butadienes and OCS) a significant contribution of the aquatic environment (e.g. Hattori et al., 1984). effluents from chlorochemical industryhas to be stated Mono-, di- and tributyltins used as hydrophobation for samples from locations 1 and 2. This corresponds additives, plastic stabilizers and biozides are the with a settlement of several chemical plants nearby most important class of organotins, whereas tetrabutyl- sampling location 2. Significant temporal variations tin is the synthetic precurser. Considering a large were not observed. organotin producing plant situated nearbya small Further chlorinated compounds detected in Lippe tributaryof the Seseke river, contaminations from river sediments could not be attributed clearlyto distinct ARTICLE IN PRESS A. Kronimus et al. / Water Research 38 (2004) 3473–3484 3481 emission sources. Within the group of chlorinated reaches. As illustrated in Fig. 5 the mass spectral benzenes, tri-, tetra- and pentachlorinated isomers did properties of bis(4-octylphenyl)amine are restricted not show significant distribution patterns. In contrast, mainlyto the loss of pentylmoieties. This fragmentation samples from the upper areas (sampling locations 8 reflects the structure of the branched side chains as the and 9) were significantlyless contaminated bydichlor- result of the synthesis pathway. The technical synthesis obenzenes. is performed byreaction of di- iso-butylene with Hexachlorobenzene (HCB) [Appendix, Structure 12] diphenylamin forming a 4,40-alkylsubstituted dipheny- occurred ubiquitous in the sediment samples ana- lamin with a methyl substitution at the 3-position of lysed. This compound was used as a pesticide in the the side chain. Bis(4-octylphenyl)amine is used as a past. However, this application is prohibited since high-temperature antioxidant additive in lubricants several years in Germany. A striking fact is that in with concentrations between 0.5% and 2%. There samples from locations 1 and 2 hexachlorobenzene is no information about the pathways into aquatic reached concentrations up to 16 times higher than at systems yet. local concentration maximums in upstream samples (see 3,6-Dichlorocarbazole was detected in onlyone Fig. 3). These increasing concentrations correlate with sample from the first campaign. Origin and environ- the appearance of OCS, HCB and bischloropropy- mental pathwayof this chlorinated carbazole are lethers. Hence a significant proportion of the HCB unknown. Its identification is based on the comparison contamination in the samples 1 and 2 can be attributed of mass spectral and GC properties with those of to chemical industrial effluents. Due to its environ- reference material. The occurrence of all three nitrogen mental persistence the occurrence of HCB upstream containing compounds were not reproducible through sampling location 2 can be interpreted as residues of all sampling campaigns. Although there were only former application of HCB as herbicide, representing surface sediments sampled, each sample did not contain agricultural effluents. particulate matter deposited during one season only. In contrast to the municipal marker compounds the Generallylow sedimentation rates in riverine systems industrial ones are discharged from point sources and implythin seasonal sediment layerswhich prevent are spatiallyrestricted. The spatial occurrence of sampling of sediments deposited during one season effluents from each industrial branch were reproducible exclusively. Consequently the unreproducibility of the through all sampling campaigns. time dependent occurrences might be caused bydegra- dation or remobilization processes. Additionallycon- taminated particulate matter is not necessarilydeposited 3.3. Nitrogen containing compounds homogeneously due to the irregularly hydrodynamic conditions within a riverine system. Therefore, there In addition to the marker compounds three nitrogen might occur concentration gradients within metre scaled containing compounds were identified and quantified, sedimentation areas which result in a limited sampling which are still unnoticed riverine contaminants. reproducibility. 1-Formylpiperidine [Appendix, Structure 13] was detected in sediment samples taken during the first two sampling campaigns only. It is used in multiple ways, e.g. as a solvent, a complexing agent with lewis acids, a 4. Conclusions formylation agent of organometallic compounds and as a phase transfer agent. Due to these different technical It has been shown that the source specific emission applications, the origin of 1-formylpiperidine is not situations regarding organic compounds within a clarified so far. This compound was also detected in riverine system can be gathered comprehensively by a sediments from the Havel and Spree rivers, Germany single investigation. Point source emissions derived from (Ricking et al., 2003). three different industrial branches were identified and Two nitrogen organic compounds were identified, localized reproduciblyregardless of seasonal influences. which were formerlynot described as riverine contami- Hence, qualitativelyand spatiallyunknown point nants, namely3,6-dichlorocarbazole [Appendix, Struc- sources within anyriverine systemcan be identified ture 14] and bis(4-octylphenyl)amine [Appendix, and localized with assistance of relativelyfew samples. Structure 15]. The mass spectra of these substances The identification of so far unknown compounds like and the synthesis pathway of 3,6-dichlorocarbazole are bis(4-octylphenyl)amine and 3,6-dichlorocarbazole re- presented in Fig. 5. veals the importance of non-target-screening approaches Bis(4-octylphenyl)amine was detected in samples in environmental sciences. taken during the first three sampling campaigns only. The spatiallydifferentiated data revealed bythe The concentrations were up to 30 ng g1. Interestingly, sediment analyses show that sediments are an essential there are lower concentration levels within the upper media in environmental sciences in order to estimate the ARTICLE IN PRESS 3482 A. Kronimus et al. / Water Research 38 (2004) 3473–3484

Fig. 5. Mass spectrum and molecular structure of bis(4-octylphenyl)amine (A) and the mass spectrum as well as the synthetic pathway of 3,6-dichlorocarbazole (B).

conditions of surface waters. The particularlyhigh subsequent studybyrelating the analyticalresults with deviations of quantitative analytical data of persistent ecotoxicological data. compounds in samples derived from different sampling campaigns indicate that signiﬁcant quantities of contaminants adsorbed to particulate matter might be remobilized and bioaccumulated. However, riverine sediments are not considered bythe water framework Acknowledgements directive of the European Union, although tri-, penta- and hexachlorobenzene, as well as hexachlorobutadiene, The research work was supported bythe Deutsche compounds which were identiﬁed as sediment contami- Forschungsgemeinschaft (DFG), Bonn, Germany. We nants bythe present investigation, are listed as priority thank the Landesumweltamt Nordrheinwestfalen (LUA pollutants within this directive. NRW) and the Emschergenossenschaft Lippeverband, The analytical results revealed by the present study on Germanyfor their help and their useful advice. We also their own can, of course, not serve as an ecotoxicological thank the reviewers of this paper for their detailed, risk assessment. This will be performed within a critical and gainful annotations. ARTICLE IN PRESS A. Kronimus et al. / Water Research 38 (2004) 3473–3484 3483

Appendix

O OH O Cl O

O Cl Cl O 132 4

O Cl Sn

CH3 Cl Cl Cl2 Cl2 56 7

Cl Cl Cl Cl Cl Cl Cl Cl O O Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl

8 9 10 11

H Cl O H Cl Cl N N N

Cl Cl H C C H Cl 11 5 5 11 Cl Cl

12 13 14 15

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