Degradation of a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) compound in different environments.

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) is a promising biodegradable bio-based material, which is designed for a vast range of applications, depending on its composite. This study aims to assess the degradability of a PHBV-based compound under different conditions. The research group followed different methodological approaches and assessed visual and mass changes, mechanical and morphological properties, spectroscopic and structural characterisation, along with thermal behaviour. The Ph-Stat (enzymatic degradation) test and total dry solids (TDS)/total volatile solids (TVS) measurements were carried out. Finally, the team experimentally evaluated the amount of methane and carbon dioxide produced, i.e., the degree of biodegradation under aerobic conditions. According to the results, different types of tests have shown differing effects of environmental conditions on material degradation. In conclusion, this paper provides a summary of the investigations regarding the degradation behaviour of the PHBV-based compound under varying environmental factors. The main strengths of the study lie in its multi-faceted approach, combining assessments of PHBV-based compound degradability under different conditions using various analytical tools, such as visual and mass changes, mechanical and morphological properties, spectroscopic and structural characterization, and thermal behavior. These methods collectively contribute to the robustness and reliability of the undertaken work.

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.

Passive dosing: Assessing the toxicity of individual PAHs and recreated mixtures to the microalgae Raphidocelis subcapitata.

Risk assessment of hydrophobic organic compounds (HOCs) is difficult because maintaining a well-defined exposure during aquatic toxicity testing is challenging due to the limited water solubility and various loss processes such as volatilization, biodegradation and sorption. Passive dosing techniques help to overcome these challenges by providing a well-controlled and solvent-free exposure. In this study, the algal growth inhibition test (DIN EN ISO 8692) was converted into a miniaturized passive dosing setting. For this purpose, biocompatible O-rings were used as substance reservoirs and loaded with polycyclic aromatic hydrocarbons (PAHs). The growth inhibition of the microalgae Raphidocelis subcapitata induced by single PAHs (log KOW 3.24-5.91) was investigated. In addition, recreated PAH mixtures were tested representing field compositions of the pore water North Sea sediments. Some of the single PAHs revealed strong growth inhibiting effects on the algal growth, while the recreated mixture compositions had slightly lower effect on the growth inhibition in the highest concentrations. Overall, the toxicity of the PAHs generally increased with the maximum chemical activities (amax) of the PAHs and the inhibition data could be fitted with one maximum chemical activity response curve. Therefore, the miniaturized passive dosing approach appears as a promising practical and economical method that can be used for toxicity testing of the different trophic levels to improve comprehensive risk assessment.

Equilibrium passive sampling: A novel approach to determine internal tissue concentrations of hydrophobic organic compounds in biota.

Equilibrium passive sampling has been applied in numerous abiotic environmental matrices. This approach was extended to biological material. In this work, a passive equilibrium sampling method for the measurement of HOCs in biota was developed as an innovative alternative because classical exhaustive extraction techniques are time-consuming and error-prone. The newly developed method is based on the well-proven SPME fiber method for sediment. Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were used as model lipophilic organic pollutants. Partition coefficients of PAHs and PCBs between the lugworm tissue and the PDMS sampling phase were determined. Polydimethylsiloxane (PDMS) coated glass fibers were directly inserted in homogenized lugworm tissue and glass fibers were analyzed using gas chromatography coupled to mass spectrometry. The method application on lugworms from tidal sand flats near Wilhelmshaven showed that the mean body residue values of PCBs (4 µg g-1) and PAHs (256 µg g-1) were about five times higher for PCBs and more than 22 times higher for PAHs compared to literature data for the North Sea area. This high level of contamination might be a consequence of the oil processing refinery located in direct proximity to the sampling site. This novel approach of applying the SPME method to biota will make biological monitoring more effective and holistic, because seasonally and area-wide changes in all environmental compartments can be recorded quickly.

Sediment Remediation Using Activated Carbon: Effects of Sorbent Particle Size and Resuspension on Sequestration of Metals and Organic Contaminants.

Thin-layer capping using activated carbon has been described as a cost-effective in situ sediment remediation method for organic contaminants. We compared the capping efficiency of powdered activated carbon (PAC) against granular activated carbon (GAC) using contaminated sediment from Oskarshamn harbor, Sweden. The effects of resuspension on contaminant retention and cap integrity were also studied. Intact sediment cores were collected from the outer harbor and brought to the laboratory. Three thin-layer caps, consisting of PAC or GAC mixed with clay or clay only, were added to the sediment surface. Resuspension was created using a motor-driven paddle to simulate propeller wash from ship traffic. Passive samplers were placed in the sediment and in the water column to measure the sediment-to-water release of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and metals. Our results show that a thin-layer cap with PAC reduced sediment-to-water fluxes of PCBs by 57% under static conditions and 91% under resuspension. Thin-layer capping with GAC was less effective than PAC but reduced fluxes of high-molecular weight PAHs. Thin-layer capping with activated carbon was less effective at retaining metals, except for Cd, the release of which was significantly reduced by PAC. Resuspension generally decreased water concentrations of dissolved cationic metals, perhaps because of sorption to suspended sediment particles. Sediment resuspension in treatments without capping increased fluxes of PCBs with log octanol-water partitioning coefficient (KOW ) > 7 and PAHs with log KOW of 5-6, but resuspension reduced PCB and PAH fluxes through the PAC thin-layer cap. Overall, PAC performed better than GAC, but adverse effects on the benthic community and transport of PAC to nontarget areas are drawbacks that favor the use of GAC. Environ Toxicol Chem 2022;41:1096-1110. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

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.

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.

Equilibrium sampling of HOCs in sediments and suspended particulate matter of the Elbe River.

BACKGROUND: Chemical quality of sediment and suspended particulate matter (SPM) is usually assessed by total chemical concentrations (Ctotal). However, the freely dissolved concentration (Cfree) is the ecologically more relevant parameter for bioavailability, diffusion and bioaccumulation. In recent studies, equilibrium sampling has been applied to determine Cfree of hydrophobic organic contaminants (HOCs) in the sediment pore water, whereas such data are missing for SPM. We applied solid-phase micro-extraction to measure and compare Cfree of PAHs and PCBs in pore water of sediments and SPM sampled along the German part of the river Elbe. Moreover, site-specific distribution ratios were evaluated and Cbio,lipid was predicted using Cfree. RESULTS: Cfree of PAHs remained largely constant while Cfree of PCBs varied along the Elbe River. The highest Ctotal of PCBs and PAHs were found at Prossen (km 13) and Meißen (km 96). PCB Ctotal even exceeded the environmental quality standard for sediment and SPM in Prossen. Site-specific distribution ratios (KD) revealed a stronger sorption for PAHs compared to PCBs, indicating a higher availability of PCBs. Equilibrium partitioning concentrations in lipids (Clip↔sed) showed a high correlation with actually measured lipid-normalised concentrations (Cbio,lipid) in bream. This indicates that PCB bioaccumulation in this benthic fish species is closely linked to the sediment contamination. CONCLUSIONS: In rivers, SPM functions as a transportation vehicle for HOCs along the stream until it eventually deposits to the sediment. This study demonstrates that due to weaker sorption of PAHs and PCBs to the SPM this matrix poses a higher risk to the aquatic environment compared to the sediment. The prediction of Cbio,lipid of PCBs was correct and shows that solid-phase micro-extraction is highly suited to predict lipid concentration, and thus a valuable tool for risk-assessment or sediment management.

Miniaturised Marine Algae Test with Polycyclic Aromatic Hydrocarbons - Comparing Equilibrium Passive Dosing and Nominal Spiking.

In this study the miniaturised Marine Algae Test (mMAT) using passive dosing was developed based on the ISO EN DIN10253 to investigate the growth inhibition of the marine diatom Phaeodactylum tricornutum caused by polycyclic aromatic hydrocarbons (PAHs). Risk assessment of hydrophobic organic compounds (HOCs) like PAHs in aquatic toxicity tests is very difficult due to their low aqueous solubilities, losses via sorption to the wells and volatilisation. However, passive dosing can overcome these challenges. In this study biocompatible silicone O-rings were used as PAH reservoir. Individual PAHs at saturation were tested using passive dosing and in comparison with nominal spiking. Additionally, a recreated mixture of PAHs reflecting the field composition of the sediment pore water was tested with passive dosing. PAHs revealed strong growth inhibiting effects on algal growth in passive dosing tests, while nominal spiking had only slightly growth inhibiting effects in the highest concentration. The recreated PAH mixture revealed slightly inhibiting effects using passive dosing when tested with a factor of 5000 of the field concentration. This study demonstrates the superiority of passive dosing to spiking and further the successful implementation of passive dosing in the marine algae test maintaining a constant concentration for HOCs with a log KOW > 4.6.

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.

Assessing PCB pollution in the Baltic Sea - An equilibrium partitioning based study.

Sediment cores and bottom water samples from across the Baltic Sea region were analyzed for freely dissolved concentrations (Cfree), total sediment concentrations (CT) and the dissolved aqueous fraction in water of seven indicator PCBs. Ex-situ equilibrium sampling of sediment samples was conducted with polydimethylsiloxane (PDMS) coated glass fibers that were analyzed by automated thermal desorption GC-MS, which yielded PCB concentrations in the fiber coating (CPDMS). Measurements of CPDMS and CT were then applied to determine (i) spatially resolved freely dissolved PCB concentrations; (ii) baseline toxicity potential based on chemical activities (a); (iii) site specific mixture compositions; (iv) diffusion gradients at the sediment water interface and within the sediment cores; and (vi) site specific distribution ratios (KD). The contamination levels were low in the Gulf of Finland and moderate to elevated in the Baltic Proper, with the highest levels observed in the western Baltic Sea. The SPME method has been demonstrated to be an appropriate and sensitive tool for area surveys presenting new opportunities to study the in-situ distribution and thermodynamics of hydrophobic organic chemicals at trace levels in marine environments.

Combining Passive Sampling with Toxicological Characterization of Complex Mixtures of Pollutants from the Aquatic Environment.

The combination of polymer-based passive sampling to collect complex environmental mixtures of pollutants, the transfer of these mixtures into bioassays, and their related toxicological characterization is still in its infancy. However, this approach has considerable potential to improve environmental hazard and risk assessment for two reasons. First, the passive sampler collects a broad range of chemicals representing the fraction of compounds available for diffusion and (bio)uptake, excluding a large part of the matrix; thus, extensive sample cleanup which could discriminate certain compounds can be avoided. Second, the toxicological characterization of samples using bioassays is complementary to chemical (target) analysis within environmental monitoring because it captures all chemicals exerting the same mode of toxic action and acting jointly in mixtures, thus providing a comprehensive picture of their overall combined effects. The scientific literature describes a range of examples from the water phase where passive sampling is usually carried out in the kinetic uptake regime for most chemicals although some may already have reached equilibrium. The composition of the chemical mixture changes from the water phase to the passive sampling material because of kinetic effects and polymer/water partition coefficients which depend on the chemicals' hydrophobicity. In contrast, only a few applications in sediment and biota have been described, but amongst these some pioneering studies have demonstrated the feasibility and potential of this combined approach. This chapter gives an overview of what has been carried out in this research area, focusing on opportunities and challenges, and points out desirable future developments with a focus on the importance of choosing a suitable combination of sampling and dosing to transfer (or re-establish) the environmental mixture into the bioassay.

Polymers as Reference Partitioning Phase: Polymer Calibration for an Analytically Operational Approach To Quantify Multimedia Phase Partitioning.

Polymers are increasingly applied for the enrichment of hydrophobic organic chemicals (HOCs) from various types of samples and media in many analytical partitioning-based measuring techniques. We propose using polymers as a reference partitioning phase and introduce polymer-polymer partitioning as the basis for a deeper insight into partitioning differences of HOCs between polymers, calibrating analytical methods, and consistency checking of existing and calculation of new partition coefficients. Polymer-polymer partition coefficients were determined for polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and organochlorine pesticides (OCPs) by equilibrating 13 silicones, including polydimethylsiloxane (PDMS) and low-density polyethylene (LDPE) in methanol-water solutions. Methanol as cosolvent ensured that all polymers reached equilibrium while its effect on the polymers' properties did not significantly affect silicone-silicone partition coefficients. However, we noticed minor cosolvent effects on determined polymer-polymer partition coefficients. Polymer-polymer partition coefficients near unity confirmed identical absorption capacities of several PDMS materials, whereas larger deviations from unity were indicated within the group of silicones and between silicones and LDPE. Uncertainty in polymer volume due to imprecise coating thickness or the presence of fillers was identified as the source of error for partition coefficients. New polymer-based (LDPE-lipid, PDMS-air) and multimedia partition coefficients (lipid-water, air-water) were calculated by applying the new concept of a polymer as reference partitioning phase and by using polymer-polymer partition coefficients as conversion factors. The present study encourages the use of polymer-polymer partition coefficients, recognizing that polymers can serve as a linking third phase for a quantitative understanding of equilibrium partitioning of HOCs between any two phases.

Strategies for Transferring Mixtures of Organic Contaminants from Aquatic Environments into Bioassays.

Mixtures of organic contaminants are ubiquitous in the environment. Depending on their persistence and physicochemical properties, individual chemicals that make up the mixture partition and distribute within the environment and might then jointly elicit toxicological effects. For the assessment and monitoring of such mixtures, a variety of cell-based in vitro and low-complexity in vivo bioassays based on algae, daphnids or fish embryos are available. A very important and sometimes unrecognized challenge is how to combine sampling, extraction and dosing to transfer the mixtures from the environment into bioassays, while conserving (or re-establishing) their chemical composition at adjustable levels for concentration-effect assessment. This article outlines various strategies for quantifiable transfer from environmental samples including water, sediment, and biota into bioassays using total extraction or polymer-based passive sampling combined with either solvent spiking or passive dosing.

Equilibrium passive sampling as a tool to study polycyclic aromatic hydrocarbons in Baltic Sea sediment pore-water systems.

Solid Phase Microextraction (SPME) was applied to provide the first large scale dataset of freely dissolved concentrations for 9 polycyclic aromatic hydrocarbons (PAHs) in Baltic Sea sediment cores. Polydimethylsiloxane (PDMS) coated glass fibers were used for ex-situ equilibrium sampling followed by automated thermal desorption and GC-MS analysis. From the PAH concentrations in the fiber coating we examined (i) spatially resolved freely dissolved PAH concentrations (Cfree); (ii) baseline toxicity potential on the basis of chemical activities (a); (iii) site specific mixture compositions; (iv) diffusion gradients at the sediment water interface and within the sediment cores and (v) site specific distribution ratios. Contamination levels were low in the northern Baltic Sea, moderate to elevated in the Baltic Proper and highest in the Gulf of Finland. Chemical activities were well below levels expected to cause narcosis to benthos organisms. The SPME method is a very sensitive tool that opens new possibilities for studying the PAHs at trace levels in marine environments.

Passive sampling methods for contaminated sediments: scientific rationale supporting use of freely dissolved concentrations.

Passive sampling methods (PSMs) allow the quantification of the freely dissolved concentration (Cfree ) of an organic contaminant even in complex matrices such as sediments. Cfree is directly related to a contaminant's chemical activity, which drives spontaneous processes including diffusive uptake into benthic organisms and exchange with the overlying water column. Consequently, Cfree provides a more relevant dose metric than total sediment concentration. Recent developments in PSMs have significantly improved our ability to reliably measure even very low levels of Cfree . Application of PSMs in sediments is preferably conducted in the equilibrium regime, where freely dissolved concentrations in the sediment are well-linked to the measured concentration in the sampler via analyte-specific partition ratios. The equilibrium condition can then be assured by measuring a time series or a single time point using passive samplers with different surface to volume ratios. Sampling in the kinetic regime is also possible and generally involves the application of performance reference compounds for the calibration. Based on previous research on hydrophobic organic contaminants, it is concluded that Cfree allows a direct assessment of 1) contaminant exchange and equilibrium status between sediment and overlying water, 2) benthic bioaccumulation, and 3) potential toxicity to benthic organisms. Thus, the use of PSMs to measure Cfree provides an improved basis for the mechanistic understanding of fate and transport processes in sediments and has the potential to significantly improve risk assessment and management of contaminated sediments.

Passive equilibrium sampler for in situ measurements of freely dissolved concentrations of hydrophobic organic chemicals in sediments.

In this study, an equilibrium passive sampling device is introduced that facilitates the in situ measurement of hydrophobic organic chemicals bioavailability in sediments in terms of freely dissolved concentrations. The new field sampler allows SPME fibers and silicone hollow fibers to be immersed and equilibrated in situ, whereas an automated liner exchanger (ALEX) facilitates the quantitative transfer of analytes to the GC without the use of extraction solvents. The sampler was developed for environmental monitoring as follows: (1) It is of very solid construction and can be reused practically ad infinitum. (2) Fibers with varying surface to volume ratios can be exposed in parallel in order to confirm that equilibrium was reached between sampler and sediment. (3) The equilibrium times allow a temporal resolution that is suited for monitoring of both long-term trends and seasonal effects. The automated thermal desorption reduced sample treatment to a minimum and ensured cost- and time-efficient measurements while minimizing potential error sources after the sampling. The sampler is applicable in a multitude of aquatic environments, especially where currents are low and sediments are muddy and well-mixed, e.g. by bioturbation. Examples for such environments are mud flats, harbor basins, river banks, and lakes.

Matrix solid-phase microextraction for measuring freely dissolved concentrations and chemical activities of PAHs in sediment cores from the western Baltic Sea.

Sediment-pore water partitioning of polycyclic aromatic hydrocarbons (PAHs) was studied in sediment cores of a dumping area in the western Baltic Sea and compared to a reference site. Freely dissolved concentrations (C(free)) of nine PAHs were measured in sediment samples using solid-phase microextraction (SPME), a cost and time-efficient method with detection limits in the lower ng L(-1) range. Elevated levels of C(free) were measured at the dumping site, where concentration peaks in the core correlated with the presence of the dumped material, which was conspicuous in its color and consistency. Sediment concentrations of PAHs were three orders of magnitude higher at the dumping site than at the reference site, whereas C(free) was only one order of magnitude greater. Chemical activities of the PAHs in the sediment cores were calculated from C(free) to predict the baseline toxic potential of the contaminant mixture. Finally, gradients in C(free) and chemical activity were used to determine the direction of diffusion within the sediment and to obtain a spatial characterization of the PAH exposure. C(free) and chemical activity are important exposure parameters for the prediction of bioconcentration and toxicity in sediment organisms, and their measurement should be included in risk-assessment and pollution-management strategies.

Ecotoxicity assessment of natural attenuation effects at a historical dumping site in the western Baltic Sea.

During the late 1950s and early 1960s of the past century, industrial waste material highly enriched in various contaminants (heavy metals, PAHs) was dumped in the inner Mecklenburg Bay, western Baltic Sea. Large-scale shifts in the spatial distribution of heavy metals in surface sediments were mapped by geochemical monitoring in the mid-1980s and 12 years later in 1997. A further study in 2001 was designed to investigate the small-scale spatial distribution of contaminants inside, on top of, and around the historical dumping ground and to examine possible effects to benthic organisms (Arctica islandica, microbiological toxicity tests). The site is located within an area characterized by a discontinuous deposition of fine sediments, but net sedimentation rate of about 3mm/y led ultimately to a gradual coverage of the dumped material. During the first decades after the dumping, about half of the originally dumped material was already spread over the surrounding area as a result of sediment dynamics and re-suspension processes. Recent sediments of the historical dump site are still significantly enriched in heavy metals and PAHs. Microbiological toxicity test results were positive, though uptake of contaminants in mussels was found to deviate only slightly from that of a non-contaminated reference station due to a gradual dilution and decrease in bioavailability of the contaminants.