Lippe river

Heim, S., J. Schwarzbauer, A. Kronimus, R. Littke, C. Woda, and A. Mangini. 2004. Geochronology of anthropogenic pollutants in riparian wetland sediments of the Lippe River (Germany). Org. Geochem. 35 1409-1425. 

The areas of investigation are spatially restricted. Studies on river water or sediments focussed on selected areas of the Elbe and Rhine river systems comprising the Havel and Spree river (exclusively in the urban area of Berlin), the Elbe estuaiy (German Bight), the Teltow Canal, as well as the Lippe river and the middle Rhine river. Investigations on groundwater contamination were exclusively restricted to two small areas in North-Rhine/Westfalia (Fig. 9). 

The anthropogenic contribution to the organic load of the Lippe river (Germany) - Qualitative characterisation of low-molecular weight organic compounds ... 

Samples of river water were taken on August, 16-17, 1999 at 19 sampling sites on a longitudinal section of the Lippe river, North-Rhine Westphalia, Germany (see Fig. 1). They were scooped up from below the water surface at midstream and bottled in pre-cleaned glass flasks. Filled sample flasks were sealed free of air bubbles with glass stoppers and stored in the darkness at a temperature of approximately 4 °C. 

Identified organic compounds in Lippe river water samples... 

Fig. 1 Map showing the Lippe river system (North-Rhine Westphalia, Germany) with sampling locations (sites 1 to 19) and sewage treatment plants.

Tab. 1 Organic compounds in Lippe river water samples, sampling in August 1999 (site numbers see Figure 1)...

TXIB (2,2,4-trimethyl-l,3-pentanedioldi-fro-butyrate, No. 21 according to Table 1, chemical structure see Figure 2) appeared in most of the investigated Lippe river water samples (see Table 1). Its occurrence as contaminant in Elbe river water and sediments of the German Bight has been reported by Franke et al. (1995) and Schwarzbauer et al. (2000), respectively. According to a study of the Danish EPA (2001), TXIB has a relatively low water solubility (1-2 mg/L, estimated K0w 4.1) and a low toxicity. 

Two isomers of tris(chloropropyl) phosphate could be identified in the Lippe river water, to be precise mainly in samples from the lower reaches (see Table 1). Tris(l-chloro-2-propyl)phosphate (TCPP) was discovered by other authors in water, sediments and air samples (Kawagoshi et al., 1999 Fries and Piittmann, 2001 Ingerowski et al., 2001 Schwarzbauer et al., 2002). It is predominately used as a flame retardant in rigid polyurethane foam. Due to information of a manufacturer, almost 23.000 tons of TCPP were sold in Western Europe in 1998. Details about pathways of TCPP into aquatic environments have not been clarified so far. 

V-alkanes (No. 1) and n-carboxylic acids (No. 9) occur in all natural materials and are as well used for numerous industrial syntheses (see Table 2). Thus, their appearance in Lippe river water can be attributed to various sources. This is also the case for vanillin (see section Perfumes, odors and additives for cosmetics ). In contrast, di-zvo-propyldisulfide (No. 45) and dipropyltrisulfide (No. 46) which were detected in several water samples (see Table 1) are clearly related to natural sources. It is known that they are formed by blue-green algae (Microcystis flos-aquae) in fresh waters (Hofbauer and Juttner, 1988) and the industrial application is unknown. 

In order to get an idea about the input pathways of the detected compounds into the Lippe river, some tributaries and potential sources of organic contaminants were sampled. Random samples were taken from the Alme river and the Quabbe Brook which are located at the less densely populated upper reaches of the Lippe river. Additionally, the Seseke river was investigated, a dirty water course which is heavily polluted with sewage effluents. Analyses of effluents from the municipial sewage treatment plant (STP) in the city of Hamm and a pharmaceutical plant were also carried out. The compound spectra which was identified in the Lippe river (see Table 1) was used as a basis for investigating the source samples. The results are summarised in Table 3. 

Many of the organic contaminants which were found in Lippe river water were also present in the source samples (see Table 3). The sewage effluent sample and the Seseke river showed the best accordance with the compound spectrum of the Lippe river. However, also in the two tributaries from the rural upper reaches of the river, numerous specific contaminants like 9-methylacridine (No. 8), alkyl phosphates (Nos. 31, 32) and chlorinated alkyl phosphates (Nos. 34, 36) appeared. In the effluent of a pharmaceutical plant, only a few Lippe river contaminants like n-alkanes (No. 1), naphthalene (No. 3), TXIB (No. 21) and caffeine (No. 67) were detected (see Table 3). Therein, mainly structural relatives of androstanone like 3p-hydroxy-5p-androstan-17-one, 3a-hydroxy-5p-androstan-17-one and androstan-50-3,17-dione were present. These compounds are probably by-products of the synthesis of hormone preparations. Some polycyclic aromatic compounds, halogenated compounds and terpenoids were not detected in the source samples (see the underlined compounds in Table 3) and probably have another origin. Representative sampling of various input sources have to be carried out to prove the origin of these compounds. Hexachlorobutadiene (No. 38) and bis(chloropropyl)ethers (No. 44) appear exclusively at the lower reaches of the Lippe river (see Table 1), downstream the chemical plants in Marl. They are attributed to inputs of the chlorochemical industry (see section 3.1). Hence, this suggests their input by an industrial point source. 

Some of the organic compounds which were frequently detected in Lippe river water were also present in the effluent of a municipial sewage treatment plant and in Lippe river tributaries. These compounds are obviously typical sewage derived contaminants in the area of the Lippe... 

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