Locomotor behavior of Neocaridina palmata: a study with leachates from UV-weathered microplastics.

Weathering of plastics leads to the formation of increasingly smaller particles with the release of chemical compounds. The latter occurs with currently unknown environmental impacts. Leachate-induced effects of weathered microplastics (MPs) are therefore of increasing concern. To investigate the toxicity of the chemical mixtures from such plastics, we exposed the freshwater shrimp Neocaridina palmata to enriched leachates from unweathered and artificially weathered (UV-A/B light) MPs (≤1 mm) from recycled low-density polyethylene (LDPE-R) pellets and from a biodegradable, not fully bio-based starch blend (SB) foil. We analyzed the individual locomotor activity (moved distance and frozen events) on day 1, 3, 7 and 14 of exposure to five leachate concentrations equivalent to 0.40-15.6 g MPs L-1, representing the upper scale of MPs that have been found in the environment. The median moved distance did not change as a function of concentration, except for the unweathered SB treatment on day 14 that indicated hyperactivity with increasing concentrations. Significant impacts were solely detected for few concentrations and exposure days. Generally, no consistent trend was observed across the experiments. We further assessed the baseline toxicity of the samples in the Microtox assay and detected high bioluminescence inhibitions of the bacterium Aliivibrio fischeri. This study demonstrates that neither the recycled nor the biodegradable material are without impacts on test parameters and therefore cannot be seen as safe alternative for conventional plastics regarding the toxicity. However, the observed in vitro toxicity did not result in substantial effects on the behavior of shrimps. Overall, we assume that the two endpoints examined in the atyid shrimp N. palmata were not sensitive to chemicals leaching from plastics or that effects on the in vivo level affect other toxic endpoints which were not considered in this study.

Particle shape does not affect ingestion and egestion of microplastics by the freshwater shrimp Neocaridina palmata.

The ingestion of microplastics (MPs) is well documented for various animals and spherical MPs (beads) in many studies. However, the retention time and egestion of MPs have been examined less, especially for irregular MPs (fragments) which are predominantly found in the environment. Furthermore, the accumulation of such particles in the gastrointestinal tract is likely to determine whether adverse effects are induced. To address this, we investigated if the ingestion and egestion of beads are different to those of fragments in the freshwater shrimp Neocaridina palmata. Therefore, organisms were exposed to 20-20,000 particles L-1 of either polyethylene (PE) beads (41 µm and 87 µm) or polyvinyl chloride (PVC) fragments (<63 µm). Moreover, shrimps were exposed to 20,000 particles L-1 of either 41 µm PE and 11 µm polystyrene (PS) beads or the PVC fragments for 24 h, followed by a post-exposure period of 4 h to analyze the excretion of particles. To simulate natural conditions, an additional fragment ingestion study was performed in the presence of food. After each treatment, the shrimps were analyzed for retained or excreted particles. Our results demonstrate that the ingestion of beads and fragments were concentration-dependent. Shrimps egested 59% of beads and 18% of fragments within 4 h. Particle shape did not significantly affect MP ingestion or egestion, but size was a relevant factor. Medium- and small-sized beads were frequently ingested. Furthermore, fragment uptake decreased slightly when co-exposed to food, but was not significantly different to the treatments without food. Finally, the investigations highlight that the assessment of ingestion and egestion rates can help to clarify whether MPs remain in specific organisms and, thereby, become a potential health threat.

Enhanced in vitro toxicity of plastic leachates after UV irradiation.

Plastics can release numerous chemicals and thereby, contribute to the chemical pollution in aquatic systems. To which extent environmental degradation processes influence the release of plastic chemicals, is currently unknown and subject of research. We therefore evaluated aqueous leachates of 12 differently formulated plastics (e.g., pre-production, post-industrial and recycled pellets as well as final products) using in vitro bioassays and chemical analysis via LC-HRMS nontarget approach. We weathered these plastics by UV irradiation (UV-C and UV-A/B) under laboratory conditions in dryness and a subsequent leaching period in ultrapure water ('atmospheric' weathering) or directly in water ('aquatic' weathering, UV-A/Baq). A dark control (DC) without UV light served as a reference treatment. Some plastics triggered several toxicological endpoints (low-density polyethylene recyclate (LDPE-R), starch blend (SB), bio-based polybutylene succinate (Bio-PBS) and polyvinyl chloride (PVC)), whereas others caused little to no effects (polyethylene terephthalate (PET), polystyrene (PS), polypropylene (PP) and LDPE). UV irradiation enhanced the plastics' toxicity, even for samples initially evaluated as toxicologically inconspicuous. The plastic samples caused oxidative stress (85%), baseline toxicity (42%), antiestrogenicity (40%) and antiandrogenicity (27%). Positive findings were measured after UV-C (63%) and UV-A/Baq (50%) treatments, followed by UV-A/B (48%) and DC (33%). Overall, we detected between 42 (DC) and 2896 (UV-A/Baq) chemical compounds. Our study demonstrates that differently formulated plastics leach toxic chemicals. UV exacerbates the plastics' toxicity by either generating active compounds and/or by facilitating their release. UV light even leads to the release of bioactive compounds from plastics of low chemical complexity. To prevent the exposure to plastic-associated chemicals, the application of chemicals could be reduced to a minimum, while on a regulatory level the evaluation of plastic eluates could be another focal point next to singular compounds.

Chemicals associated with biodegradable microplastic drive the toxicity to the freshwater oligochaete Lumbriculus variegatus.

Microplastics (MPs) as complex synthetic pollutants represent a growing concern for the aquatic environment. Previous studies examined the toxicity of MPs, but infrequently used a natural particle control such as kaolin. The cause of toxicity, either the physical structure of the particles or chemical components originating from the MPs, has rarely been resolved. Moreover, the ecotoxicological assessment of biodegradable plastics has received little attention. To narrow down the main driver for toxicity of irregular biodegradable MPs, we conducted a series of 28-days sediment toxicity tests with the freshwater oligochaete Lumbriculus variegatus and recorded the number of worms and dry weight as endpoints. Therefore, MPs containing several biodegradable polymers were either mixed with the sediment or layered on the sediment surface with concentrations from 1 to 8.4% sediment dw-1. Kaolin particles were evaluated in parallel as particle control. Furthermore, aqueous leachates and methanolic extracts as MP equivalents as well as solvent-treated, presumably pure MPs were investigated after mixing them into the sediment. Our results reveal that MP mixed with the sediment induced stronger adverse effects than layered MP. Kaolin particles caused no adverse effects. In contrast, they enhanced dry weight in both applications. The impact of aqueous leachates was comparable to the control without MPs, whereas methanolic extracts affected the worm number at the highest concentration with 100% mortality. Solvent-treated, presumably pure MP resulted in mostly higher worm numbers when compared to untreated MPs mixed into the sediment. This study demonstrates that MPs mixed into the sediment affect L. variegatus more than MPs that are layered on the sediment surface. Kaolin as a natural, fine-sized particle control created somewhat favorable conditions for the worm. The main driver for toxicity, however, proved to be chemicals associated with the plastic product and its previous content.

Post-treatment of ozonated wastewater with activated carbon and biofiltration compared to membrane bioreactors: Toxicity removal in vitro and in Potamopyrgus antipodarum.

Wastewater treatment plants are major point sources of (micro)pollutant emissions and advanced wastewater treatment technologies can improve their removal capacity. While abundant data on individual advanced treatment technologies is available, there is limited knowledge regarding the removal performance of ozonation combined with multiple post-treatments and stand-alone membrane bioreactors. This is especially true for the removal of in vitro and in vivo toxicity. Therefore, we investigated the removal of 40 micropollutants and toxicity by a pilot-scale ozonation with four post-treatments: non-aerated and aerated granular activated carbon and biological filtration. In addition, two stand-alone membrane bioreactors fed with untreated wastewater and one MBR operating with ozonated partial flow recirculation were analysed. Aqueous and extracted samples were analysed in vitro for (anti)estrogenic, (anti)androgenic and mutagenic effects. To assess in vivo effects, the mudsnail Potamopyrgus antipodarum was exposed in an on-site flow-through system. Multiple in vitro effects were detected in conventionally treated wastewater including estrogenic and anti-androgenic activity. Ozonation largely removed these effects, while anti-estrogenic and mutagenic effects increased suggesting the formation of toxic transformation products. These effects were significantly reduced by granular activated carbon being more effective than biological filtration. The membrane bioreactor performed similarly to the conventional treatment while the membrane bioreactor with ozonation had a comparable removal performance like ozonation. Conventionally treated wastewater increased the growth of P. antipodarum. Ozonation reduced the reproduction indicating a potential formation of toxic transformation products. In the post-treatments, these effects were compensated or remained unaffected. The effluents of the membrane bioreactors induced reproductive toxicity. Our results show that ozonation is effective in further reducing toxicity and micropollutant concentrations. However, the formation of toxicity requires a post-treatment. Here, ozonation coupled to granular activated carbon filtration seemed the most promising treatment process.

A new enzymatic method assessing the impact of wastewater treatment plant effluents on the assimilative capacity of small rivers.

Microorganisms play an important role in maintaining a good water quality in rivers by degrading organic material, including toxic substances. In the present study, we analyzed the potential impact of municipal wastewater treatment plant (WWTP) effluents as a major stress factor on the assimilative capacity of small rivers. It was the aim to develop a new bioassay for assessing such impacts in the receiving rivers by measuring the activity of extracellular enzymes (exoenzymes) in bacteria. Therefore, we established a specific in-vitro assay to detect inhibitory effects of solid phase-enriched water samples on ß-glucosidase (BGL) activity of the actinobacterium Cellulomonas uda as a proxy for the microbial decomposition of organic substances and thus for the assimilative capacity of surface waters. We found significant reductions of BGL activity in the WWTP effluents and in the receiving waters directly downstream as well as a relative quick recovery over the further course of the water bodies. The new bioassay offers a promising tool for the assessment of the assimilative capacity in surface waters and a potential impact of WWTP effluents on this key ecosystem function. Abbreviations WWTP wastewater treatment plant BGL ß-glucosidase EU-WFD European Water Framework Directive FAU Formazin Attenuation Units PE population equivalents REF relative enrichment factor; SPE solid phase extraction MTBE methyl-tert-buthyl-ether DMSO dimethyl-sulfoxide NPG 4-nitrophenol-ß-d-glucopyranoside DOC dissolved organic carbon.

Ecotoxicological characterization of the antiepileptic drug carbamazepine using eight aquatic species: baseline study for future higher tier tests.

Ecotoxicological effects of the antiepileptic drug carbamazepine (CBZ) were investigated in one primary producer (Desmodesmus subspicatus) and seven invertebrate species (Daphnia magna, Daphnia pulex, Ceriodaphnia dubia, Gammarus fossarum, Potamopyrgus antipodarum, Lumbriculus variegatus and Chironomus riparius) using OECD and US EPA guidelines for chronic toxicity testing. The present data set was used to conduct a hazard assessment for CBZ including confirmatory data. While most of our results were in accordance with previous studies, published effect data for C. dubia and D. pulex could not be confirmed, even though they have previously been considered to be the most sensitive invertebrate species to CBZ exposure. The non-biting midge, C. riparius, was the most sensitive test organism in the present study. From an EC10 of 406 µg/L and a no observed effect concentration (NOEC) of 400 µg/L, a predicted no effect concentration (PNEC) of 8 µg/L was calculated. With regard to realistic predicted and measured environmental concentrations, the environmental risk can be considered as low for CBZ when the assessment is based on laboratory-based effect data. To conduct a refined and more realistic assessment, this study provides foundational data for two future, higher tier studies: one multiple-stressor experiment and one mesocosm study.

What you extract is what you see: Optimising the preparation of water and wastewater samples for in vitro bioassays.

The assessment of water quality is crucial for safeguarding drinking water resources and ecosystem integrity. To this end, sample preparation and extraction is critically important, especially when investigating emerging contaminants and the toxicity of water samples. As extraction methods are rarely optimised for bioassays but rather adopted from chemical analysis, this may result in a misrepresentation of the actual toxicity. In this study, surface water, groundwater, hospital and municipal wastewater were used to characterise the impacts of common sample preparation techniques (acidification, filtration and solid phase extraction (SPE)) on the outcomes of eleven in vitro bioassays. The latter covered endocrine activity (reporter gene assays for estrogen, androgen, aryl-hydrocarbon, retinoic acid, retinoid X, vitamin D, thyroid receptor), mutagenicity (Ames fluctuation test), genotoxicity (umu test) and cytotoxicity. Water samples extracted using different SPE sorbents (Oasis HLB, Supelco ENVI-Carb+, Telos C18/ENV) at acidic and neutral pH were compared for their performance in recovering biological effects. Acidification, commonly used for stabilisation, significantly altered the endocrine activity and toxicity of most (waste)water samples. Sample filtration did not affect the majority of endpoints but in certain cases affected the (anti-)estrogenic and dioxin-like activities. SPE extracts (10.4 × final concentration), including WWTP effluents, induced significant endocrine effects that were not detected in aqueous samples (0.63 × final concentration), such as estrogenic, (anti-)androgenic and dioxin-like activities. When ranking the SPE methods using multivariate Pareto optimisation an extraction with Telos C18/ENV at pH 7 was most effective in recovering toxicity. At the same time, these extracts were highly cytotoxic masking the endpoint under investigation. Compared to that, extraction at pH 2.5 enriched less cytotoxicity. In summary, our study demonstrates that sample preparation and extraction critically affect the outcome of bioassays when assessing the toxicity of water samples. Depending on the water matrix and the bioassay, these methods need to be optimised to accurately assess water quality.

Ecotoxicological impacts of surface water and wastewater from conventional and advanced treatment technologies on brood size, larval length, and cytochrome P450 (35A3) expression in Caenorhabditis elegans.

Anthropogenic micropollutants and transformation products (TPs) negatively affect aquatic ecosystems and water resources. Wastewater treatment plants (WWTP) represent major point sources for (micro)pollutants and TPs in urban water cycles. The aim of the current study was to assess the removal of micropollutants and toxicity during conventional and advanced wastewater treatment. Using wild-type and transgenic Caenorhabditis elegans, the endpoint reproduction, growth, and cytochrome P450 (CYP) 35A3 induction (via cyp-35A3::GFP) were assessed. Samples were collected at four WWTPs and a receiving surface water. One WWTP included the advanced treatments: ozonation followed by granular activated carbon (GAC) or biological filtration (BF), respectively. Relevant micropollutants and WWTP parameters (n = 111) were included. Significant reproductive toxicity was detected for one WWTP effluent (31-83% reduced brood size). Three of four effluents significantly promoted the growth of C. elegans larvae (49-55% increased lengths). This effect was also observed for the GAC (34-41%) and BF (30%) post-treatments. Markedly, significant cyp-35A3::GFP induction was detected for one effluent before and after ozonation, being more pronounced for the ozonated samples (5- and 7.4-fold above controls). While the advanced treatments decreased the concentrations of most micropollutants, the observed effects may be attributed to effects of residual target compounds and/or compounds not included in the target chemical analysis. This highlights the need for an integrated assessment of (advanced) wastewater treatment covering both biological and chemical parameters.

Small but with big impact? Ecotoxicological effects of a municipal wastewater effluent on a small creek.

Municipal wastewater treatment plants (WWTPs) discharge micropollutants like pharmaceuticals, pesticides, personal care products or endocrine disrupting chemicals but also nutrients. Both can adversely influence the freshwater ecosystem and may finally affect the ecological conditions. Many studies focus on the potential impact of large WWTPs even if smaller ones are more common, often less efficient and discharge into small creeks or the upper reaches of rivers. As a result, the receiving waters are characterized by relatively high shares of treated wastewater. Thus, the primary objective of this study was to investigate the ecotoxicological effects of a small WWTP on freshwater amphipods and mollusks in a small creek using an active and passive monitoring approach, accompanied by laboratory experiments (LE). In vitro assays with recombinant yeasts and the microtox assay with Aliivibrio fischeri were performed in parallel to determine the endocrine potential and the baseline toxicity. The evaluation of the effects of the analysed WWTP was possible due to its shutdown during our study and the application of the same in vivo and in vitro assays before and after the shutdown. During the operation of the WWTP the discharge of treated wastewater caused significantly higher mortalities and lower reproduction of the anaylsed invertebrates in the active and passive montoring as well as in the LEs. Furthermore, the amphipod species assemblage in the creek was affected downstream of the WWTP effluent. Besides, the endocrine activity and baseline toxicity were significantly higher downstream of the effluent. After the shutdown of the WWTP, the in vitro activity levels and adverse in vivo effects in the receiving water recovered quickly with no significant differences downstream of the former WWTP effluent compared to the upstream station. Furthermore, the previously disturbed amphipod species assemblage recovered significantly with a shift in favor of Gammarus fossarum downstream of the effluent. These biological results are consistent with a marked decline by 81.5% for the detected micropollutants in the receiving creek after the shutdown which points to a prominent role of micropollutants for the observed effects.

Integrated Evaluation Concept to Assess the Efficacy of Advanced Wastewater Treatment Processes for the Elimination of Micropollutants and Pathogens.

A multidisciplinary concept has been developed to compare advanced wastewater treatment processes for their efficacy of eliminating micropollutants and pathogens. The concept is based on (i) the removal/formation of selected indicator substances and their transformation products (TPs), (ii) the assessment of ecotoxicity via in vitro tests, and (iii) the removal of pathogens and antibiotic resistant bacteria. It includes substances passing biological wastewater treatment plants regulated or proposed to be regulated in the European Water Framework Directive, TPs formed in biological processes or during ozonation, agonistic/antagonistic endocrine activities, mutagenic/genotoxic activities, cytotoxic activities, further activities like neurotoxicity as well as antibiotics resistance genes, and taxonomic gene markers for pathogens. At a pilot plant, ozonation of conventionally treated wastewater resulted in the removal of micropollutants and pathogens and the reduction of estrogenic effects, whereas the in vitro mutagenicity increased. Subsequent post-treatment of the ozonated water by granular activated carbon (GAC) significantly reduced the mutagenic effects as well as the concentrations of remaining micropollutants, whereas this was not the case for biofiltration. The results demonstrate the suitability of the evaluation concept to assess processes of advanced wastewater treatment including ozonation and GAC by considering chemical, ecotoxicological, and microbiological parameters.

Spoilt for choice: A critical review on the chemical and biological assessment of current wastewater treatment technologies.

The knowledge we have gained in recent years on the presence and effects of compounds discharged by wastewater treatment plants (WWTPs) brings us to a point where we must question the appropriateness of current water quality evaluation methodologies. An increasing number of anthropogenic chemicals is detected in treated wastewater and there is increasing evidence of adverse environmental effects related to WWTP discharges. It has thus become clear that new strategies are needed to assess overall quality of conventional and advanced treated wastewaters. There is an urgent need for multidisciplinary approaches combining expertise from engineering, analytical and environmental chemistry, (eco)toxicology, and microbiology. This review summarizes the current approaches used to assess treated wastewater quality from the chemical and ecotoxicological perspective. Discussed chemical approaches include target, non-target and suspect analysis, sum parameters, identification and monitoring of transformation products, computational modeling as well as effect directed analysis and toxicity identification evaluation. The discussed ecotoxicological methodologies encompass in vitro testing (cytotoxicity, genotoxicity, mutagenicity, endocrine disruption, adaptive stress response activation, toxicogenomics) and in vivo tests (single and multi species, biomonitoring). We critically discuss the benefits and limitations of the different methodologies reviewed. Additionally, we provide an overview of the current state of research regarding the chemical and ecotoxicological evaluation of conventional as well as the most widely used advanced wastewater treatment technologies, i.e., ozonation, advanced oxidation processes, chlorination, activated carbon, and membrane filtration. In particular, possible directions for future research activities in this area are provided.

Are in vitro methods for the detection of endocrine potentials in the aquatic environment predictive for in vivo effects? Outcomes of the Projects SchussenAktiv and SchussenAktivplus in the Lake Constance Area, Germany.

Many studies about endocrine pollution in the aquatic environment reveal changes in the reproduction system of biota. We analysed endocrine activities in two rivers in Southern Germany using three approaches: (1) chemical analyses, (2) in vitro bioassays, and (3) in vivo investigations in fish and snails. Chemical analyses were based on gas chromatography coupled with mass spectrometry. For in vitro analyses of endocrine potentials in water, sediment, and waste water samples, we used the E-screen assay (human breast cancer cells MCF-7) and reporter gene assays (human cell line HeLa-9903 and MDA-kb2). In addition, we performed reproduction tests with the freshwater mudsnail Potamopyrgus antipodarum to analyse water and sediment samples. We exposed juvenile brown trout (Salmo trutta f. fario) to water downstream of a wastewater outfall (Schussen River) or to water from a reference site (Argen River) to investigate the vitellogenin production. Furthermore, two feral fish species, chub (Leuciscus cephalus) and spirlin (Alburnoides bipunctatus), were caught in both rivers to determine their gonadal maturity and the gonadosomatic index. Chemical analyses provided only little information about endocrine active substances, whereas the in vitro assays revealed endocrine potentials in most of the samples. In addition to endocrine potentials, we also observed toxic potentials (E-screen/reproduction test) in waste water samples, which could interfere with and camouflage endocrine effects. The results of our in vivo tests were mostly in line with the results of the in vitro assays and revealed a consistent reproduction-disrupting (reproduction tests) and an occasional endocrine action (vitellogenin levels) in both investigated rivers, with more pronounced effects for the Schussen river (e.g. a lower gonadosomatic index). We were able to show that biological in vitro assays for endocrine potentials in natural stream water reasonably reflect reproduction and endocrine disruption observed in snails and field-exposed fish, respectively.

Effects of test media on reproduction in Potamopyrgus antipodarum and of pre-exposure population densities on sensitivity to cadmium in a reproduction test.

Molluscan species can be affected by various anthropogenic substances. Yet, these effects are disregarded in chemical risk assessment as molluscs are unrepresented in standard OECD guidelines. The project "validation of a mollusc reproduction test" (Federal Environment Agency, code 371165417) deals with the development of a test method with the mudsnail Potamopyrgus antipodarum for OECD purposes. In this context, the influence on reproduction of both, different media and varying snail density, has been observed in independent experiments. Further, the impact of density on the outcome of subsequent cadmium (Cd) toxicity in a test has been investigated to refine the existing methodology. First, adult snails were kept in different test media for 12 weeks. Second, snail density was increased for 4 weeks to induce stress. Snails from each density scenario were used for another 4 weeks in a reproduction test at an equal density with 12 µg Cd/L, respectively. Significant differences in reproduction between medium groups were noted after 4 and 8, but not 12, weeks. Further, reproduction was significantly altered by snail density in the beakers but after subsequent 4 weeks at a constant density, no differences were observed between control groups. Cd reduced reproduction and this effect increased with snail density in the pre-exposure period, demonstrating that a previous stress factor may result in increased sensitivity to chemicals and underlines the need for more standardized breeding conditions to minimize effect variations. Based on the outcome of this study, an acclimatization period of 12 weeks must be guaranteed for specimens transferred to another medium. Further, 4 weeks of acclimatization are necessary after density stress. An additional 12 weeks density experiment showed that medium volume in each replicate can be decreased by half to save on chemicals, water and space during tests.

Reproductive toxicity of bisphenol A and cadmium in Potamopyrgus antipodarum and modulation of bisphenol A effects by different test temperature.

An OECD initiative for the development of mollusc-based toxicity tests for endocrine disrupters and other chemicals has recommended three test species with respective test designs for further standardisation. Preparing a subsequent pre-validation study we performed a reproduction test with Potamopyrgus antipodarum, determining the concentration range of the selected test substances, bisphenol A (BPA) and cadmium (Cd). At 16 °C, the recommended test temperature, the number of embryos in the brood pouch was increased by BPA and decreased by Cd (NOEC: 20 µg BPA/L and 1 µg Cd/L). Coinstantaneous BPA tests at 7 °C and 25 °C demonstrated a temperature dependency of the response, resulting in lower NOECs (5 µg/L respectively). As expected, reproduction in control groups significantly varied depending on temperature. Additional observations of the brood stock showed seasonal fluctuations in reproduction under constant laboratory conditions. The recommended temperature range and test conditions have to be further investigated.

Before the curtain falls: endocrine-active pesticides--a German contamination legacy.

The European Parliament recently approved a new EU regulation aimed at eliminating the use of pesticides that have unwanted endocrine-disrupting properties. The test criteria for these chemicals are slated to be finalized by 2013. For this reason, in this review, we have evaluated the meta data of lists and databanks that address pesticides with potentially endocrine-disrupting properties, and have checked which of the 250 active ingredients currently in use in Germany are affected. Azoles, dithio-carbamates/carbamates, and pyrethroids were most frequently rated as endocrine-active ingredients. In Germany, assessments have shown that total environmental pesticide emission is equivalent to approximately 0.1% of total pesticide use.Courtyard drainage and field runoff are regarded to constitute the most important sources of pesticide emission into the aquatic environment. In addition, in several investigations of drinking- and groundwater contamination, various pesticide-active ingredients and their metabolites were confirmed to be contaminants. Water suppliers recorded the following pesticides or their metabolites as being most frequently detected in drinking water: atrazine, desethylatrazine, diuron, simazine, isoproturon,and its dichlobenil metabolite 2,6-dichlorobenzamide. Surface water contamination results mainly from substances that are no longer approved by EU pesticide regulation. The most frequently detected pesticides in streaming waters that are still authorized were bentazone, diuron, glyphosate, isoproturon, MCPA, mecoprop,metamitron, pendimethalin, and tebuconazole. Pesticide residues in comestible goods of herbal origin are periodically detected in all EU member countries. The European Commission recently published results showing that 54% of all monitoring samples were devoid of positive findings. Of samples showing detectable residues, 42% were below, and 4.4% exceeded the EUMRLs. Monitoring data over a 10-year period revealed that the percentage of foodstuff without detectable pesticide residues has continuously decreased from 64 to 51.5%. In Germany, herbal samples mainly contained residues of maneb, iprodion,procymidone and deltamethrin. Notwithstanding these detections, chronic health risk evaluations indicated that there were no violations of ADI values. However,for carbaryl, methomyl, and procymidone, ARfDs were exceeded substantially for intake of grapefruit and bell peppers. As a result, the EU withdrew the methomyl authorization in 2008 and revised procymidone guideline values.

A critical analysis of the biological impacts of plasticizers on wildlife.

This review provides a critical analysis of the biological effects of the most widely used plasticizers, including dibutyl phthalate, diethylhexyl phthalate, dimethyl phthalate, butyl benzyl phthalate and bisphenol A (BPA), on wildlife, with a focus on annelids (both aquatic and terrestrial), molluscs, crustaceans, insects, fish and amphibians. Moreover, the paper provides novel data on the biological effects of some of these plasticizers in invertebrates, fish and amphibians. Phthalates and BPA have been shown to affect reproduction in all studied animal groups, to impair development in crustaceans and amphibians and to induce genetic aberrations. Molluscs, crustaceans and amphibians appear to be especially sensitive to these compounds, and biological effects are observed at environmentally relevant exposures in the low ng l(-1) to microg l(-1) range. In contrast, most effects in fish (except for disturbance in spermatogenesis) occur at higher concentrations. Most plasticizers appear to act by interfering with the functioning of various hormone systems, but some phthalates have wider pathways of disruption. Effect concentrations of plasticizers in laboratory experiments coincide with measured environmental concentrations, and thus there is a very real potential for effects of these chemicals on some wildlife populations. The most striking gaps in our current knowledge on the impacts of plasticizers on wildlife are the lack of data for long-term exposures to environmentally relevant concentrations and their ecotoxicity when part of complex mixtures. Furthermore, the hazard of plasticizers has been investigated in annelids, molluscs and arthropods only, and given the sensitivity of some invertebrates, effects assessments are warranted in other invertebrate phyla.

A critical evaluation of the environmental risk assessment for plasticizers in the freshwater environment in Europe, with special emphasis on bisphenol A and endocrine disruption.

Bisphenol A (BPA) and the phthalates di-butyl phthalate (DBP), di-ethylhexyl phthalate (DEHP), di-isodecyl phthalate (DIDP) and di-isononyl phthalate (DINP) are high production volume plasticizers and are regularly detected in aquatic ecosystems due to their continuous release into the environment. These compounds are listed as priority substances in the European Union and therefore subject to an environmental risk assessment (ERA). Final ERA reports are available for DBP, DIDP and DINP, while the process is still ongoing for BPA and DEHP. The current approach critically reviews the exposure and especially the effect analyses in the reports or drafts, considering also potential endocrine effects of the plasticizers.