Application of equilibrium passive sampling to assess the influence of anthropogenic activities and bioturbation on the distribution of hydrophobic organic chemicals in North Sea sediment cores.

The pollution state in the German Bight was investigated by determination of pollutant concentrations of sediment samples using equilibrium passive sampling. Polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAH) were determined in the pore water of North Sea sediment. The freely dissolved pore water concentration (Cfree) was measured applying Solid Phase Microextraction (SPME) by using PDMS-coated glass fibers. The obtained results show that the North Sea contamination level with the investigated pollutants is relatively low. However, the stations close to the sediment-dumping site were higher contaminated. A macrofauna analysis showed that bioturbation activities were mostly present in the upper sediment layers, but a direct bioturbation influence on the sediment concentration distribution could not be shown. Overall, the contamination load was below baseline toxicity, but considering that several other priority pollutants will also make a contribution to the baseline toxicity, it can be counted as relatively high.

Uptake and absorption of fluoranthene from spiked microplastics into the digestive gland tissues of blue mussels, Mytilus edulis L.

The present work intended to investigate the fate of contaminant-loaded microplastics if ingested by benthic filter feeder Mytilus edulis under laboratory conditions. In the course of a 7-day experiment the mussels were exposed to PVC microplastics in a size range ≤40 µm, in doses of 2000 particles L-1 (11.56 mg L-1). Particles were either virgin or loaded with one of four different nominal concentrations of the polycyclic aromatic hydrocarbon (PAH) fluoranthene (500, 125, 31.25 and 7.8125 µg g-1). Verification of fluoranthene concentrations on the particles provided evidence of the high absorptive capacity of PVC for this PAH, indicating that comparable particles may serve as considerable accumulation sites for high concentrations of hydrophobic contaminants in the aquatic environment. Analysis of digestive gland tissues via polarised light microscopy revealed the occurrence of particles and particle aggregates within stomach and intestines of all mussels treated with microplastics, thus making the xenobiotic bioavailable. Results of contaminant analysis in mussel tissues via equilibrium sampling point to a considerable capability of microplastics for the accumulation of hydrophobic contaminants from the environment and their potential to act as vehicles for the transport of theses contaminants into organismal tissues.

Comparison of In Situ and Ex Situ Equilibrium Passive Sampling for Measuring Freely Dissolved Concentrations of Parent and Alkylated Polycyclic Aromatic Hydrocarbons in Sediments.

Equilibrium passive sampling methods (EPSMs) allow quantification of freely dissolved contaminant concentrations (Cfree ) in sediment porewater. Polydimethylsiloxane (PDMS) is a convenient sampling polymer that can be equilibrated in field (in situ) or laboratory (ex situ) sediments to determine Cfree , providing reliable compound-specific PDMS-water partition coefficients (KPDMS-water ) are available. Polycyclic aromatic hydrocarbons (PAHs) are an important class of sediment contaminants comprised of parent and alkylated homologs. However, application of EPSM to alkylated PAHs is challenged by lack of KPDMS-water measurements. Our first objective was to obtain KPDMS-water for 9 alkylated PAHs and biphenyls using 3 different PDMS-coated fibers. Quantitative relationships were then established to define KPDMS-water for 18 parent and 16 alkyl PAHs included in the US Environmental Protection Agency's sediment quality benchmark method for benthic life protection based on additive toxic units. The second objective was to compare Cfree in porewater obtained using both in situ and ex situ EPSMs at 6 Baltic Sea locations. The results indicated that in situ and ex situ Cfree for alkyl PAHs generally agreed within a factor of 3. Further, all sites exhibited additive toxic units <1, indicating that PAHs pose a low risk to benthos. The results extend practical application of EPSMs for improved risk assessment and derivation of porewater-based remediation goals for PAH-contaminated sediments. Environ Toxicol Chem 2020;39:2169-2179. © 2020 SETAC.

Comparison of freely dissolved concentrations of PAHs in contaminated pot soils under saturated and unsaturated water conditions.

Passive sampling (PS, equally used for passive sampler) methods have successfully been applied in situ to quantify the bioavailability of hydrophobic organic compounds in air, water and sediments. However, very little is known on the applicability of PS in unsaturated soils. Here, we present the results of a greenhouse experiment in which we applied in situ PS methods in pots. Low density polyethylene (LDPE) and polydimethylsiloxane (PDMS) fibres with a newly developed PS holder were used to analyse freely dissolved polycyclic aromatic hydrocarbon (PAH) concentrations (Cfree) in a skeet shooting range soil and an uncontaminated control soil under water saturated and unsaturated conditions for up to nine months. A short exposure time of three months was not sufficient for the PDMS samplers to reach distribution equilibrium with the surrounding soil. Under saturated water conditions, the in situ results agreed well with measurements obtained from the conventional ex situ soil suspension method. They were in accordance with similar comparisons made in previous studies on sediments, as well as with model predictions. However, for unsaturated water conditions, the results differed considerably from the ex situ Cfree values, in particular for the light molecular weight (LMW) PAHs such as phenanthrene, fluoranthene, and pyrene. The results of the two in situ PS methods were in good agreement with each other under both soil water conditions, indicating that dissipation mechanisms, such as degradation or volatilization, led to a substantial decrease in Cfree under unsaturated conditions, especially for the LMW PAHs (log10KOW < 5.85) over a period of six months or more. Thus, in their current state of development, in situ PS methods can be used in soils under water-saturated conditions. However, an adequate method to correct for non-equilibrium conditions needs to be developed before they can be applied to unsaturated conditions, mainly for LMW PAHs.

Toward understanding the impacts of sediment contamination on a native fish species: transcriptional effects, EROD activity, and biliary PAH metabolites.

BACKGROUND: Both frequency and intensity of flood events are expected to increase as a result of global climate change in the upcoming decades, potentially resulting in increased re-suspension of sediments in fluvial systems. Contamination of these re-suspended sediments with legacy contaminants, including dioxins and dioxin-like compounds (DLCs), as well as polycyclic aromatic hydrocarbons (PAHs) is of great ecotoxicological concern. DLCs, and to some extent also PAHs, exhibit their toxicity through activation of the aryl hydrocarbon receptor (AhR). However, interactions of DLCs with pathways other than those known to be mediated through the AhR are not fully understood to date. METHODS: This study aimed to investigate molecular and biochemical effects in roach (Rutilus rutilus) during a 10 days exposure to suspensions of three natural sediments that differed in the level of DLC contamination. Concentrations of biliary PAH metabolites and hepatic 7-ethoxyresorufin-O-deethylase activity were quantified in exposed fish. Furthermore, the abundance of transcripts of several genes related to energy metabolism, response to oxidative stress, and apoptosis, as well as cytochrome P450 1A (cyp1a) was quantified. RESULTS: Biliary PAH metabolites and activation of the AhR were confirmed as suitable early warning biomarkers of exposure to suspended sediments containing DLCs and PAHs that corresponded well with analytically determined concentrations of those contaminants. Although the abundances of transcripts of superoxide dismutase (sod), protein kinase c delta (pkcd), and ATP-binding cassette transporter c9 (abcc9) were altered by the treatment compared with unexposed control fish, none of these showed a time- or concentration-dependent response. The abundance of transcripts of pyruvate carboxylase (pc) and transferrin variant d (tfd) remained unaltered by the treatments. CONCLUSIONS: We have shown that contaminated sediments can become a risk for fish during re-suspension events (e.g., flooding and dredging). We have also demonstrated that roach, which are native to most European freshwater systems, are suitable sentinel species due to their great sensitivity and ecological relevance. Roach may be particularly suitable in future field studies to assess the toxicological concerns associated with the release of DLCs and PAHs during sediment re-suspension.

Cross-Species Extrapolation of Uptake and Disposition of Neutral Organic Chemicals in Fish Using a Multispecies Physiologically-Based Toxicokinetic Model Framework.

The potential to bioconcentrate is generally considered to be an unwanted property of a substance. Consequently, chemical legislation, including the European REACH regulations, requires the chemical industry to provide bioconcentration data for chemicals that are produced or imported at volumes exceeding 100 tons per annum or if there is a concern that a substance is persistent, bioaccumulative, and toxic. For the filling of the existing data gap for chemicals produced or imported at levels that are below this stipulated volume, without the need for additional animal experiments, physiologically-based toxicokinetic (PBTK) models can be used to predict whole-body and tissue concentrations of neutral organic chemicals in fish. PBTK models have been developed for many different fish species with promising results. In this study, we developed PBTK models for zebrafish (Danio rerio) and roach (Rutilus rutilus) and combined them with existing models for rainbow trout (Onchorhynchus mykiss), lake trout (Salvelinus namaycush), and fathead minnow (Pimephales promelas). The resulting multispecies model framework allows for cross-species extrapolation of the bioaccumulative potential of neutral organic compounds. Predictions were compared with experimental data and were accurate for most substances. Our model can be used for probabilistic risk assessment of chemical bioaccumulation, with particular emphasis on cross-species evaluations.

Towards science-based sediment quality standards-Effects of field-collected sediments in rainbow trout (Oncorhynchus mykiss).

Sediments can act as long-term sinks for environmental pollutants. Within the past decades, dioxin-like compounds (DLCs) such as polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs) have attracted significant attention in the scientific community. To investigate the time- and concentration-dependent uptake of DLCs and PAHs in rainbow trout (Oncorhynchus mykiss) and their associated toxicological effects, we conducted exposure experiments using suspensions of three field-collected sediments from the rivers Rhine and Elbe, which were chosen to represent different contamination levels. Five serial dilutions of contaminated sediments were tested; these originated from the Prossen and Zollelbe sampling sites (both in the river Elbe, Germany) and from Ehrenbreitstein (Rhine, Germany), with lower levels of contamination. Fish were exposed to suspensions of these dilutions under semi-static conditions for 90 days. Analysis of muscle tissue by high resolution gas chromatography and mass spectrometry and of bile liquid by high-performance liquid chromatography showed that particle-bound PCDD/Fs, PCBs and PAHs were readily bioavailable from re-suspended sediments. Uptake of these contaminants and the associated toxicological effects in fish were largely proportional to their sediment concentrations. The changes in the investigated biomarkers closely reflected the different sediment contamination levels: cytochrome P450 1A mRNA expression and 7-ethoxyresorufin-O-deethylase activity in fish livers responded immediately and with high sensitivity, while increased frequencies of micronuclei and other nuclear aberrations, as well as histopathological and gross pathological lesions, were strong indicators of the potential long-term effects of re-suspension events. Our study clearly demonstrates that sediment re-suspension can lead to accumulation of PCDD/Fs and PCBs in fish, resulting in potentially adverse toxicological effects. For a sound risk assessment within the implementation of the European Water Framework Directive and related legislation, we propose a strong emphasis on sediment-bound contaminants in the context of integrated river basin management plans.

Limited waterborne acute toxicity of native polycyclic aromatic compounds from coals of different types compared to their total hazard potential.

Coals contain native polycyclic aromatic compounds (PACs), which include polycyclic aromatic hydrocarbons (PAHs), and heterocyclic aromatic compounds (NSO-PACs) in considerably varying amounts up to 2500 mg/kg. Whereas PAC bioavailability and toxicity from coals are generally considered to be low, few studies have considered potential variations arising from the composition of different coal types including native PAC content. In the present study, fine particles of different coal types exhibiting variable properties were systematically investigated regarding their PAC bioavailability. PAH content reached up to 79 mg/kg EPA-PAH and 865 mg/kg total PAH. Determination of the toxic potential of extracted PACs in bioassays showed inhibition of Caenorhabditis elegans reproduction (up to 94%) and increased mortality of Danio rerio embryos (up to 100%) after exposure to extracts from lignite, sub-bituminous, and bituminous coals. Anthracite extracts showed no effects. Contact assays using whole coal samples revealed no toxicity to D. rerio embryos in any of the coal samples, suggesting low bioavailability of PACs. In contrast, C. elegans reproduction was inhibited by direct coal contact; however, the observed toxicity probably resulted from other coal effects. The results suggest that despite the high toxic potential of PACs present, their bioavailability from different coal types is very limited and independent of coal properties and native PAH content.