On the borderline of dissolved and particulate organic matter: partitioning and bioavailability of polycyclic aromatic hydrocarbons.

The functionality of dissolved organic matter (DOM) was studied by assessing the availability of polycyclic aromatic hydrocarbons (PAHs) spiked in pore water samples separated from sediments by water extraction and centrifugation with or without subsequent filtration. The purpose was to compare the effects of traditionally defined DOM (0.45-µm cut off) and larger colloidal material present in the separated pore water samples on the partitioning and bioavailability of PAHs. The tested PAHs included phenanthrene (Phe), fluoranthene (Flu), pyrene (Pyr) and benzo[a]pyrene (BaP). Bioavailability of the selected PAHs was tested with two ecologically different organisms: pelagic filter feeder Daphnia magna and sediment-dwelling deposit feeder Lumbriculus variegatus. Sorption to DOM (i.e. in filtered samples) was clearly higher for BaP than for the other PAH. This was also reflected in significantly reduced bioavailability for both model organisms in the filtered samples compared to DOM-free conditions. For the other PAHs the sorption was significant only in the unfiltered samples indicating the importance of larger colloidal material. Thus, the bioavailability of PAHs was also more effectively reduced by the colloidal material. This holds true for both the model organisms, indicating that the ecological differences i.e. filter feeder vs. deposit feeder do not affect in this respect. It appears that considering only traditionally defined DOM, material that may be present in environmental samples and is important for the speciation and bioavailability of contaminants is ignored.

Characterizing field sediments from three European river basins with special emphasis on endocrine effects - A recommendation for Potamopyrgus antipodarum as test organism.

The assessment of endocrine disrupting potentials of field sediments has until now been mostly limited to classical chemical analysis, in vitro assays and in vivo bioassays performed with vertebrates. There is an urgent need for easy, cheap and reproducible invertebrate tests which may be applied in certain monitoring activities. Since the mudsnail Potamopyrgus antipodarum is known to be tolerant to natural stressors, but also sensitive to endocrine disrupting chemicals, it is very likely that this organism could be suitable for the assessment of endocrine effects of e.g. field sediments. Within this study the endocrine potential of sediments in three European river basins was assessed. The yeast estrogen screen (YES) and a sediment contact test with P. antipodarum were performed. Furthermore, analyses of physico-chemical properties and concentrations of heavy metals, PAHs, organotins, natural steroids and alkylphenols were done. In the sediment contact test, the reproduction of the snail was promoted by a part of the sediments. This phenomenon could not be explained by their physico-chemical properties. However, at some of those sites a high estrogenic activity was detected in the YES, leading to the assumption that endocrine disrupting compounds could be responsible for those effects. This assumption could be confirmed to some extent with partially high concentrations of xeno-estrogens (e.g. nonylphenol) at the certain sites. Our study demonstrates the applicability of the test with P. antipodarum for a variety of sediments and once again points out the need of suitable in vivo biotests for the risk assessment of field sediments.

Predicting the bioavailability of sediment-associated spiked compounds by using the polyoxymethylene passive sampling and tenax extraction methods in sediments from three river basins in Europe.

This study presents the bioavailability of four spiked compounds to Lumbriculus variegatus, in sediment samples from three river basins in Europe: the Elbe, the Llobregat, and the Scheldt. Twenty sediment samples differing in physical and chemical properties were spiked with chlorpyrifos, pyrene, tetrachloribiphenyl, and tetrabromo diphenyl ether. The main focus of this study was to compare the suitability of two chemical approaches-the rapidly desorbing fraction method based on the Tenax extraction and the freely dissolved chemical concentration method based on polyoxymethylene passive sampling-for predicting the bioavailability of sediment-associated hydrophobic compounds. It appears that accessible concentration estimated by Tenax extraction does not result in equal freely dissolved concentrations based on polyoxymethylene passive sampling results. The present data show that freely dissolved concentration in pore water mainly determines the uptake by organisms and, therefore, the polyoxymethylene passive sampling method was a successful approach to estimating the bioavailability of sediment-associated lipophilic contaminants (log octanol-water partitioning coefficient >6). The sediment characteristics or river basin differences had only a minor effect on the bioavailability estimates. Overall, passive samplers have not been tested to a sufficient extent in various chemicals or exposure matrixes. For this reason, bioassays are still needed in the risk assessment process in order to verify results based on passive sampling methods.

Comparative sorption and desorption of benzo[a]pyrene and 3,4,3',4'-tetrachlorobiphenyl in natural lake water containing dissolved organic matter.

The sorption and desorption of two model compounds, benzo[a]pyrene (BaP) and 3,4,3',4'-tetrachlorobiphenyl (TCBP), were studied in natural lake water with high dissolved organic matter (DOM) content using the equilibrium dialysis and Tenax extraction methods. The sorption of TCBP was lower and reached steady value more slowly than did BaP. Tenax extraction revealed at least two differently desorbing fractions for both model compounds, which also supported the conclusion that DOM-HOC associations may involve several mechanisms. The rapidly desorbing fraction may be attributed to freely dissolved and loosely sorbed compound, whereas the more strongly sorbed fraction may indicate the presence of specific binding sites. The data indicated that the association between hydrophobic organic contaminants (HOC) and DOM is not simply absorption that is solely driven by the lipophilicity of the sorbates. Although contact time had a rather negligible effect on the sorption of BaP, the proportion of desorption resistant fraction increased with time, whereas the desorption of TCBP was less affected by contact time. Steric factors may be the cause of the lower sorption and smaller desorption resistant fraction of TCBP. The results indicate potential differences in the behavior of PAHs and PCBs in the aquatic environment.

Dissolved organic matter in pore water of freshwater sediments: effects of separation procedure on quantity, quality and functionality.

Pore water was separated either with or without water extraction prior to centrifugation (7600 or 20,000 x g) in order to investigate the effects of separation procedure on the amount and properties of dissolved organic matter (DOM i.e. the material passing through a 0.45-microm filter) in three freshwater sediments. On the basis of solubility in alkaline, organic matter was concluded to compose of humic substances in two (S1 and S3) and of humin (S2) in one of the sediments. DOM in the samples was quantified by total organic carbon measurement. Specific UV-absorption (SUVA) and high performance size exclusion chromatography (HPSEC) analyses were used to characterize DOM. Sorption of pyrene was used as a measure for functionality of DOM. Both water extraction and centrifugation speed were shown to affect the properties of DOM; however, the effects were sediment dependent. Water extraction increased the amount of DOM separated from the two sediments that had humic character (S1 and S3). In most cases water extraction increased SUVA and shifted the molecular size distribution of DOM towards larger sizes. The separation procedure had also an effect on the functionality of DOM. In water extracted samples of S2 and S3 the sorption of pyrene was higher than in the corresponding samples separated without water extraction, whereas in S1 similar effect was not found. Generally, centrifugation speed had smaller effects on the properties of DOM than water extraction. The fact that the effects of separation procedure on DOM depend on the sediment characteristics complicates the comparison between samples and evaluation of functionality in field conditions.