Distribution of hydrophobic organic contaminants in marine sediment fines-An alternative normalization strategy?

The necessary normalization of contaminant concentrations, in order to be able to compare contaminant content in sediments with different sediment properties, is currently not standardized within environmental monitoring and assessment programs. Therefore, this study investigates an alternative normalization strategy for hydrophobic organic contaminants (HOCs) by removing the coarse and chemically inert sediment fraction using an improved, half-automated wet-sieving method. We compare the results to commonly used TOC normalization (2.5% total organic carbon [TOC], OSPAR). Simultaneously, the study provides a comprehensive overview of HOC concentrations in sediment fines (<63 µm) for the German Exclusive Economic Zone and therefore gathers information about the more bioavailable and mobile part of the sediment that particularly accumulates HOCs due to its high surface area. We analyzed bulk sediment samples and their corresponding fine grain fractions from 25 stations in the German Exclusive Economic Zone for 41 HOCs including polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and organochlorine pesticides. The results indicate that the wet-sieving procedure is capable of physically normalizing the concentrations of the investigated HOCs and is useful for the comparison of concentrations in different sediment types. The wet-sieving procedure is more time consuming than the normalization to the TOC content. However, it offers the possibility of lowering the detection limits (LODs) through the analytical sample preparation procedure used, as sieving concentrates the contaminants. Therefore, a higher number of results >LOD were detected in sediment fines, leading to more informative data sets. In contrast to the commonly used normalization to 2.5% TOC, the statistical analyses carried out (principal component analysis with subsequent cluster analysis) additionally indicate that physical normalization allows better differentiation of sampling sites by contaminant sources and geographic location rather than their sediment characteristics. Integr Environ Assess Manag 2023;19:1348-1360. © 2023 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Seasonal variability, long-term distribution (2001-2014), and risk assessment of polar organic micropollutants in the Baltic Sea.

From 2001 to 2014, 13 surveys were conducted in the Baltic Sea, to determine its pollution of 50 micropollutants. The investigations focused mostly on the German western Baltic Sea; in 2008, one survey covered the entire Baltic Sea. Various groups of herbicides (such as triazines, phenoxyacetic acid, phenylurea), perfluoroalkyl substances, pharmaceuticals, and industrial products were analyzed during these surveys. The highest concentrations (median 1 to 4 ng/L) were observed for atrazine, simazine, chloridazone, 2,4-dichlorophenoxyacetic acid, benzotriazole, primidone, and carbamazepine. Most micropollutants exhibited a relatively homogenous spatial distribution, though some herbicides show elevated concentrations in certain regions (e.g., Odra estuary), indicating a riverine input. The data set was analyzed, both for seasonal influences and long-time trends. Some herbicides exhibited higher concentrations during summertime. Both upward- and downward-directed time trends could be identified for some herbicides and perfluorinated compounds. For most of the detected compounds, a low-risk quotient was calculated. Only the occurrence of carbendazim could potentially pose a higher risk to the Baltic Sea.

Using the HPTLC-bioluminescence bacteria assay for the determination of acute toxicities in marine sediments and its eligibility as a monitoring assessment tool.

For an integrated ecological risk assessment of marine sediment contamination, the determination of target-compound concentrations by e.g. mass spectrometric methods is not sufficient to explain sediment toxicity. Due to the presence of a multitude of environmental contaminants in this complex matrix causing a mixed toxicity, the identification and assessment of main toxicants is a challenge. One approach in identifying main toxicants is the application of effect-directed analysis (EDA). In this study, an EDA approach was developed using high performance thin layer chromatography (HPTLC) coupled to bioluminescence bacteria detection with Aliivibrio fischeri for the determination of marine sediments acute toxicity. In a first attempt, the HPTLC separation was optimized with a fast, two-step gradient to separate main hydrophobic organic contaminant (HOC) classes found in marine sediments. An easy-to-use evaluation script for the resulting bioluminescence inhibition images was programed using R. The developed method was applied to sediment extracts of two different sample sets: (i) Fourteen marine sediment samples from the German Bight representing a wide range of contaminant loads and sediment properties and (ii) sediment samples from a core representing temporal trends of contamination. Results from the HPTLC-bioluminescence bacteria assay were compared to HOC concentrations determined by GC-MS/MS. A correlation of the determined inhibition Γ-values for the PAH inhibition zone to PAH concentrations showed a very good agreement (R2 = 0.91). The results of this study were used to evaluate the suitability of the EDA approach to be used as an assessment tool for marine sediments.

Bioavailability and distribution of PAHs and PCBs in the sediment pore water of the German Bight and Wadden Sea.

The freely dissolved concentration (Cfree) was measured for PAHs and PCBs in sediments of the German Bight and Wadden Sea. Ex-situ Solid Phase Microextraction (SPME) was applied using Polydimethlysiloxane (PDMS) coated glass fibers followed by automated thermal desorption and GC-MS analysis. This study provides the first dataset on the spatial distribution of Cfree for PAHs and PCBs in the German Bight and the Wadden Sea. We found elevated PCB concentrations in the Wadden Sea and especially in the Weser estuary. Sandy North Sea sediments were rather less contaminated, except for some former dumping sites. The sorption strength of PAHs was generally stronger, while PCBs in the Wadden Sea sediments were only weakly bound. This SPME method is a rapid and sensitive tool to study Cfree of hydrophobic organic chemicals to improve todays sediment risk assessment.

Accelerated solvent extraction (ASE) for purification and extraction of silicone passive samplers used for the monitoring of organic pollutants.

Silicone passive samplers have gained an increasing attention as single-phased, practical and robust samplers for monitoring of organic contaminants in the aquatic environment in recent years. However, analytical challenges arise in routine application during the extraction of analytes as silicone oligomers are co-extracted and interfere severely during chemical analyses (e.g. gas chromatographic techniques). In this study, we present a fast, practical pre-cleaning method for silicone passive samplers applying accelerated solvent extraction (ASE) for the removal of silicone oligomers prior to the water deployment (hexane/dichloromethane, 100 °C, 70 min). ASE was also shown to be a very fast (10 min) and efficient extraction method for non-polar contaminants (non-exposed PRC recoveries 66-101 %) sampled by the silicone membrane. For both applications, temperature, extraction time and the solvent used for ASE have been optimized. Purification of the ASE extract was carried out by silica gel and high-pressure liquid size exclusion chromatography (HPLC-SEC). The silicone oligomer content was checked by total reflection X-ray fluorescence spectroscopy (TXRF) in order to confirm the absence of the silicone oligomers prior to analysis of passive sampler extracts. The established method was applied on real silicone samplers from the North- and Baltic Sea and showed no matrix effects during analysis of organic pollutants. Internal laboratory standard recoveries were in the same range for laboratory, transport and exposed samplers (85-126 %).