Background, aim, and scope The occurrence and fate of pharmaceuticals in the aquatic environment is recognized as one of the emerging issues in environmental chemistry and as a matter of public concern. Existing data tend to focus on the concentrations of pharmaceuticals in the aqueous phase, with limited studies on their concentrations in particulate phase such as sediments. Furthermore, current water quality monitoring does not differentiate between soluble and colloidal phases in water samples, hindering our understanding of the bioavailability and bioaccumulation of pharmaceuticals in aquatic organisms. In this study, an investigation was conducted into the concentrations and phase association (soluble, colloidal, suspended particulate matter or SPM) of selected pharmaceuticals (propranolol, sulfamethoxazole, meberverine, thioridazine, carbamazepine, tamoxifen, indomethacine, diclofenac, and meclofenamic acid) in river water, effluents from sewage treatment works (STW), and groundwater in the UK. Materials and methods The occurrence and phase association of selected pharmaceuticals propranolol, sulfamethoxazole, meberverine, thioridazine, carbamazepine, tamoxifen, indomethacine, diclofenac, and meclofenamic acid in contrasting aquatic environments (river, sewage effluent, and groundwater) were studied. Colloids were isolated by cross-flow ultrafiltration (CFUF). Water samples were extracted by solid-phase extraction (SPE), while SPM was extracted by microwave. All sample extracts were analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) in the multiple reaction monitoring. Results and discussion Five compounds propranolol, sulfamethoxazole, carbamazepine, indomethacine, and diclofenac were detected in all samples, with carbamazepine showing the highest concentrations in all phases. The highest concentrations of these compounds were detected in STW effluents, confirming STW as a key source of these compounds in the aquatic environments. The calculation of partition coefficients of pharmaceuticals between SPM and filtrate (observed partition coefficients, [graphic removed] , [graphic removed] ), between SPM and soluble phase (intrinsic partition coefficients, [graphic removed] , [graphic removed] ), and between colloids and soluble phase (K coc) showed that intrinsic partition coefficients [graphic removed] are between 25% and 96%, and between 18% and 82% higher than relevant observed partition coefficients values, and are much less variable. Secondly, K coc values are 3-4 orders of magnitude greater than [graphic removed] values, indicating that aquatic colloids are substantially more powerful sorbents for accumulating pharmaceuticals than sediments. Furthermore, mass balance calculations of pharmaceutical concentrations demonstrate that between 23% and 70% of propranolol, 17-62% of sulfamethoxazole, 7-58% of carbamazepine, 19-84% of indomethacine, and 9-74% of diclofenac are present in the colloidal phase. Conclusions The results provide direct evidence that sorption to colloids provides an important sink for the pharmaceuticals in the aquatic environment. Such strong pharmaceutical/colloid interactions may provide a long-term storage of pharmaceuticals, hence, increasing their persistence while reducing their bioavailability in the environment. Recommendations and perspectives Pharmaceutical compounds have been detected not only in the aqueous phase but also in suspended particles; it is important, therefore, to have a holistic approach in future environmental fate investigation of pharmaceuticals. For example, more research is needed to assess the storage and long-term record of pharmaceutical residues in aquatic sediments by which benthic organisms will be most affected. Aquatic colloids have been shown to account for the accumulation of major fractions of total pharmaceutical concentrations in the aquatic environment, demonstrating unequivocally the importance of aquatic colloids as a sink for such residues in the aquatic systems. As aquatic colloids are abundant, ubiquitous, and highly powerful sorbents, they are expected to influence the bioavailability and bioaccumulation of such chemicals by aquatic organisms. It is therefore critical for colloids to be incorporated into water quality models for prediction and risk assessment purposes.

Introduction Within the last decade, numerous studies have investigated the role of environmental history on tolerance to stress of many organisms. This study aims to assess if Manila clams Ruditapes philippinarum may react differently to cadmium exposure and trematode parasite infection (Himasthla elongata) depending on their origin and environmental history in Arcachon Bay (France). Materials and methods Clams were exposed to Cd (15 µg L⁻¹) and parasites (25 cercariae per clam), alone or in combination, at 15°C under controlled laboratory conditions for 7 days. Metal accumulation and success of parasite infestation were examined, also physiological parameters such as metallothionein response and hemocyte counts and activities (phagocytosis, oxidative burst, viability, and adhesion). Results and Discussion Sensitivity of Manila clams to both stressors differed from one site to another, suggesting local adaptation of populations. Clams from the more parasitized site presented better resistance to trematodes than the others in terms of first line defense, i.e., avoidance of infection. On the other hand, clams that adapted to chronic Cd contamination showed better detoxification mechanisms, both in a faster transfer of metal from gills to visceral mass and in a higher metallothionein baseline, than clams which had never experienced Cd contamination. Finally, hemocyte concentration and viability differed between clam origin site, highlighting the fact that populations living in different environments may adapt their physiological and biochemical responses to environmental stressors. Conclusion It is therefore important to be cautious when extrapolating results from field studies of one species and one site, if the life history of the organisms is not taken into account.

Introduction and background Primary producers play critical structural and functional roles in aquatic ecosystems; therefore, it is imperative that the potential risks of toxicants to aquatic plants are adequately assessed in the risk assessment of chemicals. The standard required macrophyte test species is the floating (non-sediment-rooted) duckweed Lemna spp. This macrophyte species might not be representative of all floating, rooted, emergent, and submerged macrophyte species because of differences in the duration and mode of exposure; sensitivity to the specific toxic mode of action of the chemical; and species-specific traits (e.g., duckweed's very short generation time). Discussion and perspectives These topics were addressed during the workshop entitled “Aquatic Macrophyte Risk Assessment for Pesticides” (AMRAP) where a risk assessment scheme for aquatic macrophytes was proposed. Four working groups evolved from this workshop and were charged with the task of developing Tier 1 and higher-tier aquatic macrophyte risk assessment procedures. Subsequently, a SETAC Advisory Group, the Macrophyte Ecotoxicology Group (AMEG) was formed as an umbrella organization for various macrophyte working groups. The purpose of AMEG is to provide scientifically based guidance in all aspects of aquatic macrophyte testing in the laboratory and field, including prospective as well as retrospective risk assessments for chemicals. As AMEG expands, it will begin to address new topics including bioremediation and sustainable management of aquatic macrophytes in the context of ecosystem services.

Background, aim, and scope This review deals with publications concerning the mode of action of Bt proteins and their potential synergism with extrinsic factors. The aim was to assess the impact of those factors especially regarding selectivity and efficacy of Bt toxins and to discuss possible gaps in current risk assessment of genetically engineered plants expressing Bt toxins. Main features The review shows that several extrinsic factors are able to influence the selectivity and efficacy of Bt toxins. The findings are seen as being relevant for risk assessment in Bt plants. This conclusion is derived by discussing current state of knowledge about the mode of action of Bt proteins, unexpected effects on non-target organism, and the way how modified Bt toxins are expressed in genetically engineered plants. Results Several publications have been identified that show that certain factors and synergism can impact efficacy and selectivity of Bt toxins. These extrinsic factors are various and include other Bt toxins or parts from the spore of Bacillus thuringiensis as well as certain enzymes, environmental stress, non-pathogenic microorganisms, and infectious diseases. Discussion Research on the underlying mechanism of observed synergism might help to explain some of the effects found in non-target organisms. In general, possible synergism of Bt toxins with extrinsic factors can be relevant for risk assessment of genetically engineered Bt plants since they expose a modified Bt toxin to the environment under various conditions and over a long period of time. Conclusions Risk assessment of genetically engineered plants should put into question the general assumption of a high selectivity and a linear dose-response relationship in the toxicity of Bt proteins. Both selectivity and efficacy can be influenced by synergism, which can provoke unexpected and undesired effects in non-target organisms. Perspectives It is suggested that systematic research be promoted on synergism between Bt toxins and potential extrinsic factors that could impact the spectrum of susceptible organisms. This research should become a prerequisite for risk assessment of Bt plants.

Background, aim, and scope Phosphorus loss from terrestrial to the aquatic ecosystems contributes to eutrophication of surface waters. To maintain the world's vital freshwater ecosystems, the reduction of eutrophication is crucial. This needs the prevention of overfertilization of agricultural soils with phosphorus. However, the methods of risk assessment for the P loss potential from soils lack uniformity and are difficult for routine analysis. Therefore, the efficient detection of areas with a high risk of P loss requires a simple and universal soil test method that is cost effective and applicable in both industrialized and developing countries. Materials and methods Soils from areas which varied highly in land use and soil type were investigated regarding the degree of P saturation (DPS) as well as the equilibrium P concentration (EPC₀) and water-soluble P (WSP) as indicators for the potential of P loss. The parameters DPS and EPC₀ were determined from P sorption isotherms. Results Our investigation of more than 400 soil samples revealed coherent relationships between DPS and EPC₀ as well as WSP. The complex parameter DPS, characterizing the actual P status of soil, is accessible from a simple standard measurement of WSP based on the equation [graphic removed] . Discussion The parameter WSP in this equation is a function of remaining phosphorous sorption capacity/total accumulated phosphorous (SP/TP). This quotient is independent of soil type due to the mutual compensation of the factors SP and TP. Thus, the relationship between DPS and WSP is also independent of soil type. Conclusions The degree of P saturation, which reflects the actual state of P fertilization of soil, can be calculated from the easily accessible parameter WSP. Due to the independence from soil type and land use, the relation is valid for all soils. Values of WSP, which exceed 5 mg P/kg soil, signalize a P saturation between 70% and 80% and thus a high risk of P loss from soil. Recommendations and perspectives These results reveal a new approach of risk assessment for P loss from soils to surface and ground waters. The consequent application of this method may globally help to save the vital resources of our terrestrial and aquatic ecosystems.

Background, aims, and scope Heavy metal contaminants in environment, especially in drinking water, are always of great concern due to their health impact. Due to the use of heavy metals as catalysts during plastic syntheses, particularly antimony, human exposure to metal release from plastic bottles has been a serious concern in recent years. The aim and scope of this study were to assess metal contaminations leaching out from a series of recycling plastic bottles upon treatments. Methodology In this study, leaching concentrations of 16 metal elements were determined in 21 different types of plastic bottles from five commercial brands, which were made of recycling materials ranging from no. 1 to no. 7. Several sets of experiments were conducted to study the factors that could potentially affect the metal elements leaching from plastic bottles, which include cooling with frozen water, heating with boiling water, microwave, incubating with low-pH water, outdoor sunlight irradiation, and in-car storage. Results Heating and microwave can lead to a noticeable increase of antimony leaching relative to the controls in bottle samples A to G, and some even reached to a higher level than the maximum contamination level (MCL) of the US Environmental Protection Agency (USEPA) regulations. Incubation with low-pH water, outdoor sunlight irradiation, and in-car storage had no significant effect on antimony leaching relative to controls in bottle samples A to G, and the levels of antimony leaching detected were below 6 ppb which is the MCL of USEPA regulations. Cooling had almost no effect on antimony leaching based on our results. For the other interested 15 metal elements (Al, V, Cr, Mn, Co, Ni, Cu, As, Se, Mo, Ag, Cd, Ba, Tl, Pb), no significant leaching was detected or the level was far below the MCL of USEPA regulations in all bottle samples in this study. In addition, washing procedure did contribute to the antimony leaching concentration for polyethylene terephthalate (PET) bottles. The difference of antimony leaching concentration between washing procedure involved and no washing procedure involved (AC) was larger than zero for samples A to G. This interesting result showed that higher antimony concentration was detected in experiments with no washing procedures compared with those experiments with washing procedures. Our study results indicate that partial antimony leaching from PET bottles comes from contaminations on the surface of plastic during manufacturing process, while major antimony leaching comes from conditional changes. Conclusion The results revealed that heating and microwaving enhance antimony leaching significantly in PET plastic bottles. Plastic bottle manufacturers should consider the contaminations during manufacturing process and washing bottles before first use was strongly recommended to remove those contaminants.

Background, aim, and scope Polybrominated diphenyl ethers (PBDEs) and their metabolites are toxic to animals, and concentrations of the PBDEs metabolites can exceed those of the parent materials. But no information was available on concentrations of PBDEs metabolites in the lower Yangtze River in the region around Jiangsu Province of China, which is heavily urbanized and industrialized area. The aims of this study were to determine whether PBDEs and their methoxylated PBDEs (MeO-PBDEs) were accumulated in Coilia sp. in this area and to investigate the potential sources for these two kinds of brominated organic pollutants. Materials and methods Samples of four species of anchovy were collected from eight sites in the lower Yangtze River, Taihu Lake, and Hongzehu Lake. Concentrations of 13 PBDEs congeners and eight methoxylated PBDEs were determined by use of organic solvent extraction, followed by gas chromatography and mass spectrometry. Results and discussion The frequencies of detection for PBDEs and MeO-PBDEs were 92% and 53%, respectively. Concentrations of ∑PBDEs ranged from not detected (ND) to 77 ng/g lipids (ND-3.8 ng/g wet weight). Concentrations of ∑MeO-PBDEs in anchovy ranged from ND to 48 ng/g lipids (ND-8.2 ng/g wet weight). The PBDE concentrations in anchovy from the Yangtze River Delta were similar to or less than those reported for other species from other locations around the world, while the concentrations of MeO-PBDEs were comparable to or slightly less than those reported in other studies. This is the first report of MeO-PBDEs in biota of China. Conclusions The results of this study as well as those of other studies suggest that PBDEs in anchovy are primarily of synthetic origin and released by human activities, while MeO-PBDEs in anchovy are primarily from nature as natural products from the sea instead of metabolism of PBDEs in anchovy.

Background, aim, and scope The aim of the study was to identify the impact of polychlorinated dibenzo-p-dioxin and furan (PCDD/F) emission sources on ambient air concentrations in the Malopolska Region, southern Poland. Three sites were selected: the city center of Krakow (Aleje), an industrial area (Nova Huta), and a rural site (Zakopane). In order to investigate the annual variations of PCDD/F sources, summer and winter time samples were taken. Materials and methods Ambient air particulate matter (PM10) was collected using an Anderson High-Volume sampler during June and December 2002 in the three mentioned sites. Analysis of PCDD/Fs was based on isotope dilution using high-resolution gas chromatography-high-resolution mass spectrometry for quantification. Results and discussion Total concentrations of 2,3,7,8-PCDD/Fs in air particulate phase from Malopolska region ranged from 0.6 to 37 pg m⁻³ (0.04-3.2 pg WHO₉₈-TEQ per cubic meter, 0.037-2.9 pg I-TEQ per cubic meter). Higher PCDD/F concentrations were measured at all three sites during winter. A linear correlation among PCDD/F concentrations, benzo(a)pyrene (B(a)P) and PM10 concentrations, was found in Aleje and Zakopane, which suggested that all compounds were originating from the same source, solid fuel domestic heating. Instead, PCDD/F levels in Nova Huta did not correlate with the seasonality of B(a)P or PM10 levels and 2,3,7,8-PCDD/F congener patterns for this site were significantly different from the other sites. Conclusions Domestic solid fuel combustion is likely the main PCDD/F source in winter in this part of Poland for urban and rural sites. PCDD/F fingerprints in the industrial site remained almost identical during summer and winter, confirming the yearly prevalence of the emissions from the nearby metal industry. Recommendations and perspectives PCDD/F concentrations found in Malopolska Region are in the upper range of ambient air concentrations of PCDD/Fs reported worldwide. However, further research is needed in order to study the impact of the deposition of these PCDD/F emissions on the region. A more extended study is being conducted in the area to analyze soil samples, such as sink of atmospheric deposition, and spruce needles, as indicator of PCDD/F availability.