Anthropogenic Organic Contaminants in Sediments of the Lippe River, Germany Alexander Kronimus*, Jan Schwarzbauer, Larissa Dsikowitzky, Sabine Heim, Ralf Littke
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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 anthro- pogenic 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 anthro- pogenic 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 À1 À1 applied. Main focus was to identifyand to distinguish d34-hexadecane (5.0 ng mL ), d10-anthracene (5.0 ng mL ) À1 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 minÀ1 to 300C; Helium carrier gas flow was were composited of clayand silt. Samples taken near the 1.5 mL sÀ1. 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 gÀ1 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