ABSTRACTHalogenated benzenes (HBs) are hydrophobic organic chemicals belonging to persistent organic pollutants. Owing to their persistence, they represent a serious problem in environmental contamination, specifically of soils and sediments. One of the most important physical processes determining the fate of HBs in soils is adsorption to main soil components such as soil organic matter and soil minerals. Smectites, layered clay minerals of the 2:1 type, are common minerals in clay‐rich soils, of which montmorillonite (Mt) is a typical representative. This work focuses on a systematic modeling study of the adsorption mechanism of selected HBs interacting with the basal (001) surface, which is the dominant surface of Mt particles. The HB···Mt interactions were studied by means of a quantum chemical approach based on the density functional theory method. HBs were represented by five molecules, particularly C6F6, C6Cl3F3, C6Cl6, C6Br3Cl3, and C6Br6. In mixed HBs (C6Cl3F3 and C6Br3Cl3) Cl atoms are in 1,3,5 or rather 2,4,6 positions. The effect of a different cation type on adsorption was investigated for M+/M2+‐Mt models with cations from alkali group (M+: Li, K, Na, Rb, Cs) and alkaline earth metal group (M2+: Mg, Ca, Sr., Ba). The calculations were also performed on the gas phase HB···M+/M2+ complexes for comparison. Adsorption energies and distances of the main HB molecular plane from the Mt surface were calculated as a measure of the adsorption strength. The results showed that the strongest HB adsorption is for the Na+‐Mt and Ca2+‐Mt surfaces. The strongest affinity was observed for hexabromobenzene, while the weakest adsorption was found for hexafluorobenzene. The decomposition of the adsorption energy showed that its dominant component is dispersion energy and less important is the cation‐π interaction. The calculated adsorption energies showed a good correlation with experimentally determined log Kd values.

Background: Hydrophobic organic compounds (HOCs) are ubiquitous in the environment. Especially halogenated HOCs can pose a major threat to human and environmental health. They show high affinity toward organic matter (OM), and adsorption processes are extensively investigated. Contrary, adsorption to minerals is often considered negligible, and knowledge on HOC interactions with clay minerals (CM) is still scarce. Aims: We aimed to apply an optimized method for the straightforward and sensitive quantification of HOC-CM interactions in miniaturized systems to quantify hexachlorobenzene (HCB) adsorption to native bentonites and to evaluate the influence of different mineral characteristics on adsorption. Methods: HOC-CM interactions were studied in miniaturized batch adsorption experiments with HCB as HOC representative and 21 native bentonites as CM phases. Additionally, five of the bentonites were used as sorbents after wet size fractionation (<2 m) and homoionic cation exchange (Ca2+). Linear adsorption isotherms and solid-liquid distribution coefficients K-d were calculated after HCB analysis by solid-phase microextraction (SPME) coupled to GC-MS. Results: HCB adsorption to selected native bentonites showed a large variation over several orders of magnitude (log K-d 1.8-4.1). Size-fractionation and Ca2+-modification tended to slightly decrease the K-d values compared to the five corresponding native bentonites (log K-d: 1.9-3.8 vs. log K-d: 2.0-4.1). Most promising parameters for explaining adsorption strength by different CM characteristics were layer charge density (LCD) and cation exchange capacity (CEC). However, no single factor could be attributed to explain the observed variability of adsorption. The miniaturized batch adsorption method reduces the required amounts of purified CM and toxic chemicals while providing excellent sensitivity and reproducibility. Conclusions: HOC adsorption to native, smectite-rich bentonites is mostly moderate but can be as high as adsorption to pure OM phases for some bentonites. The variation in adsorption appears to be controlled by a combination of several factors that might include additional factors not previously considered, especially for the bentonites with the strongest adsorption of HCB.

The suitability of lake sediment cores to reconstruct past inputs, regional pollution, and usage patterns of pesticides has been shown previously. Until now, no such data exist for lakes in eastern Germany. Therefore, ten sediment cores (length 1 m) of ten lakes in eastern Germany, the territory of the former German Democratic Republic (GDR), were collected and cut into 5-10 mm layers. In each layer, concentrations of trace elements (TEs) As, Cd, Cr, Cu, Ni, Pb, S, Zn, as well as of organochlorine pesticides (OCPs) were analyzed. A miniaturized solid-liquid extraction technique in conjunction with headspace solid-phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS) was used for the latter. Of OCPs, only transformation products of dichlorodiphenyltrichloroethane (DDT) were found. Congener ratios indicate a mainly aerial input. In the lakes’ profiles, several regional features and also responses to national policies and measures are visible. Dichlorodiphenyldichloroethane (DDD) concentrations reflect the history of DDT use in the GDR. TEs show a uniform progression over time. They follow a trans-regional pattern and are indicative of activity and policy making in West Germany before 1990 instead of those in the GDR. Lake sediments proved to be suitable to archive short- and long-range impacts of anthropogenic activity. Our data can be used to complement and validate other forms of environmental pollution long-term monitoring and check for the efficiency of pollution counter measures in the past.

The fate of chemical pollutants in the environment is determined by various factors including the type and strength of their interactions with reactive surfaces in soils and sediments. In the present work the interactions of hexachlorobenzene (HCB) with the surface of a common clay mineral belonging to the smectite group montmorillonite (MNT) is studied by means of the density functional theory method. The MNT net surface charge, induced by isomorphic substitutions, is systematically varied and compensated by Ca2+ cations. Based on the calculated electron densities, conclusions are drawn revealing the nature of their mutual interactions, the related stability of such surface complexes as well as possible molecular arrangements. It becomes apparent that the dominant contribution to the stability of HCB-MNT complexes arises from the cation-π interactions between the HCB molecule and the nearest compensating Ca2+ cation and thus besides the MNT net surface charge the type and size of the compensating cations are expected to play a crucial role in understanding the HCB adsorption on MNT. This systematic study aims to contribute to a better mechanistic understanding of the interactions between hydrophobic organic compounds and reactive mineral surfaces.

Due to their characteristic properties, mountain soils require adequate management if used for cropping or grazing, even if climatic conditions are favorable. This study provides a summary of a three-year field campaign that evaluated mountain soils in in northern Georgia for sustainable agricultural use. Soils in the Kazbegi study area, located on the northern slope of the Great Caucasian Ridge, were mapped in 2014 and 2015. The soils developed mainly on sediment fans and on glacial and fluvial sediments. They were characterized by a low to moderate yield potential, with high-yield soils found on volcanic plateaus. Despite the high diversity of terrestrial and semi-terrestrial soils, common to all of them was a high humus content. In the river valleys, Fluvisols (or at least soils with fluvic-properties) were widespread and in the valley depressions fens, e.g., Histosols, occurred as well. On volcanic substrates, medium to very deep Cambisols or Umbrisols were found, with moderate to good agricultural yield potentials. However, P-sorption, mainly on amorphous Al- and Fe-oxides, could lead to an increased need for fertilization. Cambisols were present on moraine, and primarily Regosols and Cambisols on the clay and silt-rich sedimentary rocks of the Jurassic, including a widely distributed coarse fraction. The cambic horizon was not visually apparent but was clearly detectable analytically. Depending on the slope inclination and exposure, even Leptosols occurred on the slopes and peaks of sedimentary or volcanic rocks. Based on these results, a synthetic soil map merging geological and geodetic data as well as data from field mapping was created to provide an instrument for land use management.

Polychlorinated biphenyls (PCBs) were used as industrial chemicals due to their beneficial physicochemical properties in many applications until the recognition of their adverse effects. Although being banned for decades, PCBs are still ubiquitous in the environment due to their congener-specific high persistence and their ongoing remobilization from contaminated sites. While mining influenced water (MIW) was generally known to be a potential source of PCB contamination, hardly anything was known about concentrations, congener patterns, or PCB loads. For further elucidation of environmental risks, 14 MIW samples from five mine water effluents were analyzed for a set of 58 PCB congeners and biphenyl by a specifically optimized SPME-GC-MS method (LOD 0.004-0.58 ng L-1). As a result, 53 mono- to heptachlorinated congeners could be detected in concentrations of 0.01-25.9 ng L-1 per congener, of which mainly tri- but also di- and tetrachlorinated PCBs were identified in higher concentrations. Total PCB concentrations (0.02-0.12 mg m(-3)) and annual loads (0.1-0.7 kg PCBs a(-1) per mine) show the relevance of MIW as an additional point source for PCB release to the environment. Implementation of water treatment is recommended to achieve a decrease in these contaminant loads in agreement with worldwide efforts to eliminate PCBs.

Over decades, persistent organic pollutants (POPs) and trace metals like mercury (Hg) have reached the remotest areas of the world such as Antarctica by atmospheric transport. Once deposited in polar areas, low temperatures, and limited solar radiation lead to long environmental residence times, allowing the toxic substances to accumulate in biota. We investigated the load of polychlorinated biphenyls (PCBs) and dichlorodiphenyltrichloroethane (DDTs) and metabolites (DDEs, DDDs) in embryos from failed eggs of the smallest seabird breeding in Antarctica, the Wilson's storm-petrel ( Oceanites oceanicus ) at King George Island (Isla 25 de Mayo). We compared samples of different developmental stages collected in 2001, 2003, and 2014 to 2016 to investigate changes in pollutant concentrations over time. We detected eight PCBs including the dioxin-like (dl) congeners PCB 105 and 118 (ΣPCBs: 59-3403 ng g −1 ww) as well as 4,4’-DDE, and 4,4’-DDD (ΣDDX: 19-1035 ng g −1 ww) in the embryos. Samples from the years 2001 and 2003 showed higher concentrations of PCBs than those from 2014 to 2016. Concentrations of DDX was similar in both time intervals. Furthermore, we determined Hg concentrations in egg membranes from 1998 to 2003, and 2014 to 2016. Similar to PCBs, Hg in egg membranes were higher in 1998 than in 2003, and higher in 2003 than in the years 2014 to 2016, suggesting a slow recovery of the pelagic Antarctic environment from the detected legacy pollutants. Embryos showed an increase in pollutant concentrations within the last third of their development. This finding indicates that contaminant concentrations may differ among developmental stages, and it should be taken into account in analyses on toxic impact during embryogenesis.

Hexachlorobenzene (HCB), a representative of hydrophobic organic chemicals (HOC), belongs to the group of persistent organic pollutants (POPs) that can have harmful effects on humans and other biota. Sorption processes in soils and sediments largely determine the fate of HCB and the risks arising from the compound in the environment. In this context, especially HOC–organic matter interactions are intensively studied, whereas knowledge of HOC adsorption to mineral phases (e.g., clay minerals) is comparatively limited. In this work, we performed batch adsorption experiments of HCB on a set of twelve phyllosilicate mineral sorbents that comprised several smectites, kaolinite, hectorite, chlorite, vermiculite, and illite. The effect of charge and size of exchangeable cations on HCB adsorption was studied using the source clay montmorillonite STx-1b after treatment with nine types of alkali (M + : Li, K, Na, Rb, Cs) and alkaline earth metal cations (M 2+ : Mg, Ca, Sr, Ba). Molecular modeling simulations based on density functional theory (DFT) calculations to reveal the effect of different cations on the adsorption energy in a selected HCB-clay mineral system accompanied this study. Results for HCB adsorption to minerals showed a large variation of solid–liquid adsorption constants K d over four orders of magnitude (log K d 0.9–3.3). Experiments with cation-modified montmorillonite resulted in increasing HCB adsorption with decreasing hydrated radii of exchangeable cations (log K d 1.3–3.8 for M + and 1.3–1.4 for M 2+ ). DFT calculations predicted (gas phase) adsorption energies (− 76 to − 24 kJ mol −1 for M + and − 96 to − 71 kJ mol −1 for M 2+ ) showing a good correlation with K d values for M 2+ -modified montmorillonite, whereas a discrepancy was observed for M + -modified montmorillonite. Supported by further calculations, this indicated that the solvent effect plays a relevant role in the adsorption process. Our results provide insight into the influence of minerals on HOC adsorption using HCB as an example and support the relevance of minerals for the environmental fate of HOCs such as for long-term source/sink phenomena in soils and sediments.

Background Veterinary pharmaceuticals can enter the environment when excreted after application and burden terrestrial and aquatic ecosystems. However, knowledge about the basic process of sorption in soils and sediments is limited, complicating regulatory decisions. Therefore, batch equilibrium studies were conducted for the widely used antiparasitics abamectin, doramectin, ivermectin, and moxidectin to add to the assessment of their environmental fate. Results We examined 20 soil samples and six sediments from Germany and Morocco. Analysis was based on HPLC-fluorescence detection after derivatization. For soils, this resulted in distribution coefficients K D of 38–642 mL/g for abamectin, doramectin, and ivermectin. Moxidectin displayed K D between 166 and 3123 mL/g. Normalized to soil organic carbon, log K OC coefficients were 3.63, 3.93, 4.12, and 4.74 mL/g, respectively, revealing high affinity to organic matter of soils and sediments. Within sediments, distribution resulted in higher log K OC of 4.03, 4.13, 4.61, and 4.97 mL/g for the four substances. This emphasizes the diverse nature of organic matter in both environmental media. The results also confirm a newly reported log K OW for ivermectin which is higher than longstanding assumptions. Linear sorption models facilitate comparison with other studies and help establish universal distribution coefficients for the environmental risk assessment of veterinary antiparasitics. Conclusions Since environmental exposure affects soils and sediments, future sorption studies should aim to include both matrices to review these essential pharmaceuticals and mitigate environmental risks from their use. The addition of soils and sediments from the African continent (Morocco) touches upon possible broader applications of ivermectin for human use. Especially for ivermectin and moxidectin, strong sorption further indicates high hydrophobicity and provides initial concern for potential aquatic or terrestrial ecotoxicological effects such as bioaccumulation. Our derived K OW estimates also urge to re-assess this important regulatory parameter with contemporary techniques for all four substances. Graphic abstract

Purpose Organochlorine pesticides (OCPs) like lindane and DDT have been used extensively after World War II until the 1990s. Still, residues of these pesticides can be found in agricultural soils all over the world, especially in developing countries. Often, they occur in extensive areas and elevated concentrations so that food safety is jeopardized. Hence, simple, cheap, and fast analytical methods are needed for a straight-forward assessment of risks. A miniaturized solid–liquid extraction combined with solid-phase microextraction (SPME) based on a proven ISO method is presented. Methods The performance of the method is evaluated by extracting three different soils which were spiked with HCH and DDT congeners, and trifluralin, and aged for 35 days. The results are compared with those of a modified quick, easy, cheap, efficient, rugged, and safe (QuEChERS) method. For further validation, both methods are applied to three environmental soil samples. Results Validation results show limits of detection and quantification as well as recovery rates in good agreement with standard requirements. The new method was found to be quicker than QuEChERS, which requires time-consuming preparation of reagents. Conclusion Merits include low time and sample volume requirements (0.5 g) and the possibility to extract many samples simultaneously, which allows the screening of large sample sizes to determine the pollution status of whole landscape regions. However, access to an automated SPME apparatus is assumed. The authors can recommend this method as a cheap and fast alternative where SPME is available.

The persistent organic pollutant hexachlorobenzene (HCB) and all 11 further chlorobenzenes were hydrodechlorinated at environmentally relevant concentrations in miniaturized reaction systems, catalyzed by low concentrated Pd(0)-nanoparticles, to examine differences in dechlorination rates and pathways. Using solid-phase microextraction coupled to gas chromatography-mass spectrometry allowed the simultaneous extraction and detection of reactants, intermediate products and fully dechlorinated benzene, regardless of their different physicochemical properties. Dechlorination of HCB with formation of intermediates mainly proceeded via pentachlorobenzene, 1,2,3,4-tetrachlorobenzene, 1,2,3-trichlorobenzene, 1,2-dichlorobenzene, and monochlorobenzene to benzene. Specific catalytic activities of Pd(0)-nanoparticles (100-3400 L g(-1) min(-1)) differed depending on chlorination degree of chlorobenzenes and position of chlorine atoms. An inductive effect is assumed to favor a removal of the vicinal chlorine atom. The presented method permits the facile determination and comparison of nanomaterials' specific catalytic activities and allows the elucidation of dehalogenation pathways. It further enables to specifically examine formed intermediates to assess their toxicity and biodegradability.

In the near future, phosphorus (P) recycling will gain importance in terms of decreasing primary resources. Sewage sludge (SSL) is an adequate secondary P-resource for P-fertilizer production but it is also a sink for heavy metals and organic pollutants. The present study is an investigation on thermochemical P-recycling of SSL. Various temperatures and amendments were tested regarding their performance to remove heavy metals and polycyclic aromatic hydrocarbons (PAH) and simultaneous increase of the plant-availability of P. The investigations were carried out on two types of SSL originating from wastewater treatment plants with chemical P-precipitation and enhanced biological P-removal, respectively. The results show that thermochemical treatment with chlorine donors is suitable to remove the majority of heavy metals and that a combination of a gaseous chlorine donor (HCl) and sodium additives leads to both high heavy metal removal and high plant availability of P. Furthermore, plant experiments show that almost all investigated thermochemical treatments can significantly reduce the bioavailability and plant uptake of heavy metals. Furthermore, PAHs are secondarily formed during low-temperature treatments (400-500 degrees C), but can be significantly reduced by using sodium carbonate as an additive. (C) 2018 Elsevier Ltd. All rights reserved.

The performance of aqueous exposure bioconcentration fish tests according to Organisation for Economic Co‐operation and Development (OECD) guideline 305 requires the possibility of preparing stable aqueous concentrations of the test substances. For highly hydrophobic organic chemicals (HOCs; octanol–water partition coefficient [log KOW] > 5), testing via aqueous exposure may become increasingly difficult. A solid‐phase desorption dosing system was developed to generate stable concentrations of HOCs without using solubilizing agents. The system was tested with hexachlorobenzene (HCB), o‐terphenyl (oTP), polychlorinated biphenyl (PCB) 153, and dibenz[a,h]anthracene (DBA) (log KOW 5.5–7.8) in 2 flow‐through fish tests with rainbow trout (Oncorhynchus mykiss). The analysis of the test media applied during the bioconcentration factor (BCF) studies showed that stable analyte concentrations of the 4 HOCs were maintained in the test system over an uptake period of 8 wk. Bioconcentration factors (L kg−1 wet wt) were estimated for HCB (BCF 35 589), oTP (BCF 12 040), and PCB 153 (BCF 18 539) based on total water concentrations. No bioconcentration could be determined for DBA, probably because of the rapid metabolism of the test item. The solid‐phase desorption dosing system is suitable to provide stable aqueous concentrations of HOCs required to determine the bioconcentration in fish and represents a viable alternative to the use of solubilizing agents for the preparation of test solutions. Environ Toxicol Chem 2017;36:906–916. © 2016 The Authors. Environmental Toxicology and Chemistry Published by Wiley Periodicals, Inc. on behalf of SETAC.

With the aim to refine water analysis in fish bioconcentration studies, automated solid-phase microextraction (SPME) was used as an alternative approach to conventional solvent extraction (liquid-liquid extraction [LLE]) for the extraction of 3 hydrophobic organic chemicals (HOCs; log KOW 5.5-7.8) from flow-through studies with rainbow trout (Oncorhynchus mykiss). The results showed that total concentrations extracted by SPME combined with internal standards and LLE are equal. The results further verify the possibility of simultaneous extraction of total and freely dissolved HOC concentrations by SPME. Freely dissolved concentrations allow the assessment of sorption and bioavailability of HOCs in bioconcentration studies and their potential impact on resulting bioconcentration factors (BCFs). Reduction in freely dissolved water concentrations can result in an underestimation of BCFs if they are calculated based on total water concentrations. For polychlorinated biphenyl (PCB) 153, a significant increase in BCF value was observed when freely dissolved concentrations were taken into account. However, log BCF values calculated based on freely dissolved concentrations did not correlate linearly with log KOW values above 5 to 6. This pointed to further influences besides a reduction in freely dissolved water concentrations by sorption to organic matter. The results can aid in assessment of the factors that influence bioconcentration systems and also give important information regarding the possible replacement of LLE by SPME for water analysis of highly HOCs in fish bioconcentration studies. Environ Toxicol Chem 2017;36:2887-2894. © 2017 The Authors. Environmental Toxicology and Chemistry Published by Wiley Periodicals, Inc. on behalf of SETAC.

A prototype for the automated thin-film microextraction of pharmaceuticals from aqueous solutions has been developed and is presented here for the first time. With a software-controlled setup, extraction methods for ivermectin and iohexol have been developed. The widely used antiparasitic agent ivermectin is non-polar and has a high tendency to sorb to surfaces. In contrast to this, the nonionic but polar iodinated X-ray contrast agent iohexol is freely water soluble. With these two substances, a wide range of polarity is covered. Sorption kinetics and thermodynamics of ivermectin and iohexol were studied. With the presented passive sampling approach, it was possible to extract up to 96.2% ivermectin with a C18-phase within 1 h and up to 74.6% of iohexol with a PS-DVB phase within 36 h out of water. Using abamectin as internal standard, it was possible to quantitatively follow dissipation of ivermectin in a simulated surface water experiment. Predominantly, the newly developed prototype can be used for automated and time-resolved extraction of xenobiotics from waterbodies under field conditions, for the extraction of substances under laboratory conditions as an alternative to the elaborate solid-phase extraction, and for the automated control of chemical reaction kinetics.

Recent studies have shown that kaolinite clay modified with biosorbents are promising low cost adsorbents for the removal of metals from aqueous solution because the resultant composites have higher adsorption capacities, and hence a better aqueous metal ions removal efficiencies. However, some clay properties suggest that not all such modifications enhance adsorption capacity. In this study, bentonite (BEN) clay was calcined after modification with Carica papaya seeds or pine cone to obtain C. papaya-modified bentonite (CPB) and pine cone-modified bentonite (PCB). The efficiencies of these adsorbents for the removal of Pb(II), Cu(II) and Cd(II) ions from aqueous solutions were studied as a function of pH, time, sorbate concentration and temperature. X-ray diffraction results showed that CPB and PCB had lattice structure as BEN, but reductions in the surface areas of CPB and PCB were observed. Adsorption results showed that pH did not significantly affect removal of aqueous metal ions between pH 3 and 7. The adsorption fitted pseudo-second order (r(2) >= 0.966) and intra-particle diffusion models and indicated mainly surface phenomena involving sharing of electrons between the adsorbent surfaces and the metal ion species. Unlike Cu(II) and Cd(II), Pb(II) adsorption reduced in CPB and PCB indicating that not all calcined biomass-clay composites have enhanced aqueous metal adsorption efficiency. However, undesired properties such as adsorbent bleeding were removed and mechanical strength enhanced while easier separation of the adsorbents from solution as compared to the raw bentonite was observed. (C) 2016 Elsevier Ltd. All rights reserved.

The adsorption efficiency of a new hybrid clay adsorbent for polynuclear aromatic hydrocarbons (PAHs) is compared with known modified clay adsorbents. The new hybrid clay adsorbent (HYCA) showed far higher adsorption capacities for the adsorption of various PAH molecules compared with sodium dodecyl sulfate modified and humic acid modified Bentonite clay adsorbents. With the new hybrid clay adsorbent (HYCA), the adsorption of some of the larger PAH molecules was complete in the first 1 h as compared with approximate to 62% and approximate to 76% observed for both humic acid modified and sodium dodecyl sulfate modified Bentonite clay adsorbents respectively. In 24 h adsorption of the PAHs was complete for all adsorbents with HYCA adsorbent showing better efficiency in the removal of the PAH molecules from aqueous solutions. No significant change was observed with increase in time up to 48 h. The adsorption was observed to be more spontaneous with HYCA adsorbent than with either modified Bentonite adsorbents. The enthalpy of adsorption did not follow any specific order and were not consistent for all PAH molecules considered.

In a search for new aqueous-phase systems for catalyzing reactions of environmental and industrial importance, we prepared novel biogenerated palladium (Pd) nanocatalysts using a "green" approach based on microorganisms isolated from high-alpine sites naturally impacted by heavy metals. Bacteria and fungi were enriched and isolated from serpentinite-influenced ponds (Totalp region, Parsenn, near Davos, Graubünden, Switzerland). Effects on growth dynamics were monitored using an automated assay in 96-well microtiter plates, which allowed for simultaneous cultivation and on-line analysis of Pd(II)- and Ni(II)-mediated growth inhibition. Microorganisms from Totalp ponds tolerated up to 3 mM Pd(II) and bacterial isolates were selected for cultivation and reductive synthesis of Pd(0) nanocatalysts at microbial interfaces. During reduction of Pd(II) with formate as the electron donor, Pd(0) nanoparticles were formed and deposited in the cell envelope. The Pd(0) catalysts produced in the presence of Pd(II)-tolerant Alpine Pseudomonas species were catalytically active in the reductive dehalogenation of model polychlorinated dioxin congeners. This is the first report which shows that Pd(0) synthesized in the presence of microorganisms catalyzes the reductive dechlorination of polychlorinated dibenzo-p-dioxins (PCDDs). Because the "bioPd(0)" catalyzed the dechlorination reactions preferably via non-lateral chlorinated intermediates, such a pathway could potentially detoxify PCDDs via a "safe route". It remains to be determined whether the microbial formation of catalytically active metal catalysts (e.g., Zn, Ni, Fe) occurs in situ and whether processes involving such catalysts can alter the fate and transport of persistent organic pollutants (POPs) in Alpine habitats.

An important aim of the European Community Regulation on chemicals and their safe use is the identification of (very) persistent, (very) bioaccumulative, and toxic substances. In other regulatory chemical safety assessments (pharmaceuticals, biocides, pesticides), the identification of such (very) persistent, (very) bioaccumulative, and toxic substances is of increasing importance. Solid-phase microextraction is especially capable of extracting total water concentrations as well as the freely dissolved fraction of analytes in the water phase, which is available for bioconcentration in fish. However, although already well established in environmental analyses to determine and quantify analytes mainly in aqueous matrices, solid-phase microextraction is still a rather unusual method in regulatory ecotoxicological research. Here, the potential benefits and drawbacks of solid-phase microextraction are discussed as an analytical routine approach for aquatic bioconcentration studies according to OECD TG 305, with a special focus on the testing of hydrophobic organic compounds characterized by log KOW > 5.