Background, aim, and scope Chlorinated volatile organic compounds (CVOCs), widely used in industry as solvents and chemical intermediates in the production of synthetic resins, plastics, and pharmaceuticals, are highly toxic to the environment and public health. Various studies reported that Fenton's oxidation could degrade a variety of chlorinated VOCs in aqueous solutions. In acidic conditions, ferrous ion catalyzes the decomposition of H₂O₂ to form a powerful •OH radical. In this study, wastewater from wash of ion-exchange resin containing typical CVOC, 1,2-dichloroethane, was treated using Fenton's oxidation. To reduce environmental load and processing costs of wastewater, Fenton process as a simple and efficient treatment method was applied to degrade 1,2-dichloroethane of wash water. Materials and methods The water samples were collected from three different washing stages of ion-exchange resin. The degradation of 1,2-dichloroethane and total organic carbon (TOC) of wash water of ion-exchange resin by Fenton process was studied with response surface method (RSM). Design of the experiments was conducted by central composite face, and factors included in three models were Fe²⁺ and H₂O₂ doses and treatment time. Relevant quadratic and interaction terms of factors were investigated. Results According to ANOVA, the model predicts well 1,2-dichloroethane reduction of all water samples and TOC reduction of samples 2 and 3. The Fe²⁺ and H₂O₂ doses used in the present study were most suitable when 1,2-dichloroethane concentration of the wash water is about 120 mg L⁻¹. In that case, Fenton's oxidation reduced 1,2-dichloroethane and TOC up to 100% and 87%, respectively, according to the RSM model. With 90-min reaction time and H₂O₂ dose of 1,200 mg L⁻¹, the required Fe²⁺ doses for 1,2-dichloroethane and TOC were 300 and 900 mg L⁻¹, respectively. The optimal H₂O₂/Fe²⁺ stoichiometric molar ratio was between 4-6. Then, concentration of Fe²⁺ was low enough and the amount of residual sludge can thus be reduced. It seems that most of TOC and part of 1,2-dichloroethane were removed by coagulation. Discussion Up to a certain extent, increase of Fe²⁺ and H₂O₂ doses improved the removal of 1,2-dichloroethane and TOC. High Fe²⁺ doses increased the formation of ferric-based sludge, and excessive H₂O₂ doses in sample 2 decreased the degradation of 1,2-dichloroethane. Excess amount of hydrogen peroxide may scavenge hydroxyl radicals, thus leading to loss of oxidative power. Also, the residual hydrogen peroxide of different samples increased with increasing H₂O₂ dose and H₂O₂/Fe²⁺ molar ratio and decreasing treatment time probably also due to scavenging reactions. Due to the saturated nature of 1,2-dichloroethane, the oxidation mechanism involves hydrogen abstraction before addition of hydroxyl radical, thus leading to lower rate constants than for direct hydroxyl radical attack, which for one increases the treatment time. Conclusions Complete removal of 1,2-dichloroethane was attained with initial concentration <120 mg L⁻¹. Also, TOC degraded effectively. Wash water with higher concentration of 1,2-dichloroethane requires longer treatment times and higher concentrations of Fe²⁺ and H₂O₂ for sufficient 1,2-dichloroethane removal. Recommendations and perspectives Due to the results achieved in this study, Fenton's oxidation could be recommended to be used for organic destruction of wash water of ion-exchange resin. Residual sludge, the main disadvantage in Fenton process, can be reduced by optimizing the ferrous dose or by using heterogeneous treatment where most of the reusable iron remains in the solid phase.

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.

Background, aim and scope Ria de Aveiro (Portugal) is a shallow coastal lagoon of high economic and ecological importance. Hardly any data on its chemical pollution by polar organic pollutants are available in literature. This study focused on the presence and sources of a series of phenolic endocrine-disrupting compounds (EDCs) in this area, including parabens, alkylphenolic compounds and bisphenol-A (BPA). A number of possible sources of pollution are present in the area, including the large harbours present in the lagoon, the city of Aveiro and the rivers discharging into the area. A recently constructed submarine wastewater outfall, located a few kilometres from the lagoon inlet has also been suggested as a possible source of pollution to Ria de Aveiro in several publications. The aim of the current field study was to investigate the occurrence and main sources of phenolic endocrine disruptors in Ria de Aveiro. Materials and methods An extensive sampling campaign was performed, with surface water and wastewater grab samples taken at over 50 locations, in duplicate on different days. Samples were treated using solid phase extraction and analysed by liquid chromatography tandem mass spectrometry. Results and discussion Concentrations in lagoon water were generally low: not exceeding 20 ng/L for most analytes. Levels in river water exceeded those in the lagoon by a factor 3 to 500 (o-phenylphenol (PhP) and nonylphenoxy ethoxy acetic acids (A₉PEC), respectively), with concentrations up to 700 ng/L for BPA and 7,300 ng/L for A₉PEC. Samples from the harbours showed EDC levels similar to those in the rest of the lagoon, but in the city of Aveiro, elevated concentrations were observed for alkylphenol ethoxylates (A₉PEO), A₉PEC, PhP and BPA. Wastewater effluents showed low levels for parabens, whilst alkylphenolic compounds reached several micrograms per litre. The effluents are discharged into the ocean via a submarine outfall, but as marine water near the outfall showed slightly elevated concentrations only for A₉PEO, it does not seem to be a significant source of these EDCs for the area. Conclusions All the studied phenolic EDCs were detected in the study area, with high levels found in some of the rivers discharging into the lagoon, and generally low concentrations in the lagoon itself. The main sources for all investigated EDCs were the rivers Caster and Antuã which discharge into the lagoon. The city of Aveiro was identified as a secondary source. As the tidal water exchange volume is much larger than the freshwater input from the rivers, concentrations of phenolic EDCs remained low in the lagoon.

Background, aim and scope In an international project named MONARPOP (Monitoring Network in the Alpine Region for Persistent and other Organic Pollutants), selected chemicals in different environmental media were analysed in the years 2004 and 2005. Seventeen pesticides were chosen and analysed in humus and mineral soil in the German Alps. The samples were taken at different altitudes. Materials and methods In such a rather complex environmental datasets, it is often necessary to compare different sets of criteria and their influence on rankings. In the similarity analysis which is part of the theory of the Hasse diagram technique, we intend to calculate the similarity of different rankings. Furthermore, we perform a so-called dominance-dominance/dominance-separability method, followed by a sensitivity analysis, both subroutines in the newly developed PyHasse programme in order to find out if the concentration of the chemicals can be related to the altitudes at which the samples were taken. Results and discussion It can be demonstrated that the altitude has a considerable influence on the concentration of some organic chemicals in humus: The concentrations of some chemicals increase with the altitude. This increase shows certain irregularities for which several explication attempts including possible effects of atmospheric stratification phenomena in valleys have been made. Conclusion These results should be complemented in further studies with MONARPOP monitoring data from other Alpine countries, e.g. Austria, Switzerland, Italy and Slovenia.

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.

Background, aim, and scope The chemical substance 2,4,7,9-tetramethyl-5-decyne-4,7-diol (TMDD) is a non-ionic surfactant used as an industrial defoaming agent and in various other applications. Its commercial name is Surynol 104® and the related ethoxylates are also available as Surfynol® 420, 440, 465 and 485 which are characterized by different grades of ethoxylation of TMDD at both hydroxyl functional groups. TMDD and its ethoxylates offer several advantages in waterborne industrial applications in coatings, inks, adhesives as well as in paper industries. TMDD and its ethoxylates can be expected to reach the aquatic environment due its widespread use and its physico-chemical properties. TMDD has previously been detected in several rivers of Germany with concentrations up to 2.5 µg/L. In the United States, TMDD was also detected in drinking water. However, detailed studies about its presence and distribution in the aquatic environment have not been carried out so far. The aim of the present study was the analysis of the spatial and temporal concentration variations of TMDD in the river Rhine at the Rheingütestation Worms (443.3 km). Moreover, the transported load in the Rhine was investigated during two entire days and 7 weeks between November 2007 and January 2008. Materials and methods The sampling was carried out at three different sampling points across the river. Sampling point MWL1 is located in the left part of the river, MWL2 in the middle part, and MWL4 in the right part. One more sampling site (MWL3) was run by the monitoring station until the end of 2006, but was put out of service due to financial constrains. The water at the left side of the river Rhine (MWL1) is influenced by sewage from a big chemical plant in Ludwigshafen and by the sewage water from this city. The water at the right side of the river Rhine (MWL4) is largely composed of the water inflow from river Neckar, discharging into Rhine 14.9 km upstream from the sampling point and of communal and industrial wastewater from the city Mannheim. The water from the middle of the river (MWL2) is largely composed of water from the upper Rhine. Water samples were collected in 1-L bottles by an automatic sampler. The water samples were concentrated by use of solid-phase extraction (SPE) using Bond Elut PPL cartridges and quantified by use of gas chromatography-mass spectrometry (GC-MS). The quantification was carried out with the internal standard method. Based on these results, concentration variations were determined for the day profiles and week profiles. The total number of analyzed samples was 219. Results The results of this study provide information on the temporal concentration variability of TMDD in river Rhine in a cross section at one particular sampling point (443.3 km). TMDD was detected in all analyzed water samples at high concentrations. The mean concentrations during the 2 days were 314 ng/L in MWL1, 246 ng/L in MWL2, and 286 ng/L in MWL4. The variation of concentrations was low in the day profiles. In the week profiles, a trend of increasing TMDD concentrations was detected particularly in January 2008, when TMDD concentrations reached values up to 1,330 ng/L in MWL1. The mean TMDD concentrations during the week profiles were 540 ng/L in MWL1, 484 ng/L in MWL2, and 576 ng/L in MWL4. The loads of TMDD were also determined and revealed to be comparable in all three sections of the river. The chemical plant located at the left side of the Rhine is not contributing additional TMDD to the river. The load of TMDD has been determined to be 62.8 kg/d on average during the entire period. By extrapolation of data obtained from seven week profiles the annual load was calculated to 23 t/a. Discussion The permanent high TMDD concentrations during the investigation period indicate an almost constant discharge of TMDD into the river. This observation argues for effluents of municipal wastewater treatment plants as the most likely source of TMDD in the river. Another possible source might be the degradation of ethoxylates of TMDD (Surfynol® series 400), in the WWTPs under formation of TMDD followed by discharge into the river. TMDD has to be considered as a high-production-volume (HPV) chemical based on the high concentrations found in this study. In the United States, TMDD is already in the list of HPV chemicals from the Environmental Protection Agency (EPA). However, the amount of TMDD production in Europe is unknown so far and also the biodegradation rates of TMDD in WWTPs have not been investigated. Conclusions TMDD was found in high concentrations during the entire sampling period in the Rhine river at the three sampling points. During the sampling period, TMDD concentrations remained constant in each part of the river. These results show that TMDD is uniformly distributed in the water collected at three sampling points located across the river. ‘Waves' of exceptionally high concentrations of TMDD could not be detected during the sampling period. These results indicate that the effluents of WWTPs have to be considered as the most important sources of TMDD in river Rhine. Recommendations and perspectives Based also on the occurrence of TMDD in different surface waters of Germany with concentrations up to 2,500 ng/L and its presence in drinking water in the USA, more detailed investigations regarding its sources and distribution in the aquatic environment are required. Moreover, the knowledge with respect to its ecotoxicity and its biodegradation pathway is scarce and has to be gained in more detail. Further research is necessary to investigate the rate of elimination of TMDD in municipal and industrial wastewater treatment plants in order to clarify the degradation rate of TMDD and to determine to which extent effluents of WWTPs contribute to the input of TMDD into surface waters. Supplementary studies are needed to clarify whether the ethoxylates of TMDD (known as Surfynol 400® series) are hydrolyzed in the aquatic environment resulting in formation of TMDD similar to the well known cleavage of nonylphenol ethoxylates into nonylphenols. The stability of TMDD under anaerobic conditions in groundwater is also unknown and should be studied.

Background, aim and scope For reliable environmental risk assessment of pollutants, knowledge on the effects at different levels of biological organisation is needed. During the early days of biomarker research in environmental studies approximately two decades ago, biochemical biomarkers were considered as the most promising tool for such purposes. Among these, three enzymes have often been studied: catalase (CAT), glutathione S-transferase (GST) and cholinesterase (ChE). However, despite their intensive research, their measurements in invertebrates have not been commonly applied in environmental risk assessment (ERA) or for regulatory purposes. Main features In the present review, we summarise our past experiences in biochemical biomarker research in two crustacean species: water flea Daphnia magna and terrestrial isopod Porcellio scaber. This is to orientate their use and to provide recommendations for the use of novel biomarkers in environmental studies, such as proteomic or genomic responses. Results and discussion We assessed the intrinsic properties of biochemical biomarkers CAT, GST and ChE in the D. magna and the isopod P. scaber. It was found that they are not in agreement with the expectations that were previously given for their use in environmental studies. To advance their use in environmental risk assessment, we suggest that based on their properties, their role should be more specifically defined. ERA includes several distinct steps, among them hazard identification, effect assessment and finally risk characterisation, each of which requires a different type of toxicity data. We recommend that the use of biochemical markers is most appropriate for hazard identification because this is a procedure whose purpose is to characterise the potential hazard of the substance in question and is more flexible in terms of using different tools. Furthermore, our results imply that biochemical markers are not always more sensitive than whole-organism responses, as was anticipated. Their sensitivity depends on the mode of action, duration of exposure and test species. Therefore, we suggest that combining both a battery of biomarkers from different levels of biological organisation and an array of biomarkers within a single level could identify hazard adequately. Conclusions The lesson learnt from biochemical biomarkers in environmental studies utilizing crustacean model species is that, for successful application of each group of biomarkers, their intrinsic properties are needed to be known before an (eco)toxicity study is designed. We suggest that a substantial body of experience obtained with biochemical biomarkers should be exploited to new emerging biomarkers in environmental studies in order to facilitate their application. Recommendations and perspectives The future of biomarkers lies in a combination of traditional biochemical and new-generation biomarkers. The latter are not only a potential replacement for existing biomarkers but will also provide new knowledge which might encourage renewed research and development of traditional biomarkers. For research purposes, complete ecotoxicity information should include contributions from molecular fingerprint of an organism, as well as whole organism, population and ecosystem responses. Still, the type of biomarkers used for routine purposes will depend on their reproducibility, their ease of use, robustness, affordability of the methodology and the type of chemicals, organisms and ecosystem of interest.

Introduction Isotope ratios of lead (²⁰⁷Pb/²⁰⁶Pb and ²⁰⁸Pb/²⁰⁶Pb) in Japanese women's hair of the twentieth century were measured to evaluate lead contamination of human proximate environment of those days. Materials and Methods The historic hair samples (n = 40) were collected in 1980s by staffs of Department of Human Ecology, University of Tokyo, from Japanese women who cut their hair in 1910s to 1968 by themselves for hair piece or needle pad and who had stored it by the time of collection. Additional five contemporary hair samples (one from male and four from females) were also included. The hair samples were digested with HNO₃, diluted with water to Pb concentration of 10 µg/kg, and isotope ratios were measured by inductively coupled plasma mass spectrometry. Results and Discussion Isotope ratios as well as Pb concentration in the hair samples of the twentieth century varied to a considerable extent depending on the period of hair cut. The oldest hair samples (1910-1920s) had the highest concentration and the most distinct isotope ratios from those of Japanese domestic Pb indicating serious contamination of proximate environment of people of those days with Pb originated from mines in other regions of the world, probably through the usage of Pb-containing face powder. The concentration and isotope ratios of Pb decreased thereafter indicating less serious contamination of proximate environment of Japanese which, in turn, should have affected by environmental contamination of mid-twentieth century due to industrial activities and leaded gasoline. Contemporary Pb level was quite low (<1 mg/kg); however, isotope ratios were close to those in 1960s when hair concentration was assumed to be strongly affected by leaded gasoline.

Background, aim, and scope In this study, a suite of sublethal stress biomarkers were analyzed in juveniles of the sentinel species, the Pacific oyster Crassostrea gigas, with a view to using them as pollution monitoring tools. The aim of this work was (1) to study baseline seasonal variations of biomarkers in different body compartments of C. gigas in the reference site and, after selecting biomarkers presenting no seasonal variations, (2) to compare responses of these biomarkers between contaminated and reference sites. Materials and methods Juvenile oysters were transplanted from Bouin (France), a reference site, to three different sites in Marennes-Oleron Bay (France), located in another water body and next to different contamination sources. Animals were exposed in situ for 3 months in summer, autumn, and winter. The following biomarkers were measured: superoxide dismutase (SOD) and glutathione peroxidase (GPx) in gills and digestive gland and lysozyme and phenoloxidase (PO) in plasma. Results No significant seasonal variations for SOD in gills and digestive gland, GPx in gills, and PO in plasma were observed in the reference site. Significant differences in enzyme activity were observed between contaminated and reference sites for SOD in gills and digestive gland and PO in plasma, depending on the body compartment, the season, and/or the site. Conclusions In conclusion, these data suggest the potential application of these biomarkers in C. gigas to provide ecologically relevant information and, therefore, to be used as biomarkers in coastal pollution monitoring.

Introduction Arsenic is a well known water contaminant that causes toxicological and carcinogenic effects. In this work magnetite nanoparticles were examined as possible arsenic sorbents. The objective of this work was to develop a sorption kinetics model, which could be used to predict the amount of arsenic adsorbed by magnetite nanoparticles in the presence of naturally occurring species using a first-order rate equation, modified to include adsorption, described by a Langmuir isotherm. Discussion Arsenate and arsenite adsorption to magnetite nanoparticles was studied, including the effect of naturally occurring species (sulfate, silica, calcium magnesium, dissolved organic matter, bicarbonate, iron, and phosphate) on adsorption. Conclusion The model accurately predicts adsorption to magnetite nanoparticles used in a batch process to remove arsenic from spiked Houston, TX tap water, and contaminated Brownsville, TX groundwater.