The study presented here searched for the level of taxonomic resolution required to detect the effects of low-level chronic pollution on estuarine meiobenthic communities. Meiofauna from two sites, with special attention to harpacticoid copepods, was analysed at different taxonomic levels of aggregation using uni- and multivariate methods. Adaptation processes that could buffer biodiversity disruptions were also considered through the analysis of fitness-related and tolerance traits in the harpacticoid copepod Paronychocamptus nanus. Results showed that uni- and multivariate analyses could be inadequate when assessing subtle anthropogenic contamination. Instead, the assessment of inter-population differences in tolerance to the main source of stress rises as a required procedure if potential effects of this type of contamination are being investigated. Specifically, a 96 h acute toxicity test performed with populations from the affected site appears as a faster and reliable general tool to assess impacts of low-level chronic pollution in estuaries.

The southern sector of the Guadiana River basin (GRB) drains the central-western part of the Iberian Pyrite Belt, an area with many polymetallic sulfide deposits and residues of mining activities that under oxidizing conditions generate an acidic leachate with large quantities of sulfates, metals, and metalloids in solution. These acidic leachates seep into the fluvial system contaminating the surface water bodies and increasing the contamination risk for local populations and riparian habitats. The present study was carried out both in Portugal and Spain with the main aim of identifying the principal contamination sources that produce acid mine drainage (AMD) in the southern part of the GRB and to evaluate the seasonal variations of water quality affected by AMD. The physicochemical parameters determined in the field (temperature, electrical conductivity, pH, redox potential, and dissolved oxygen) are discussed and interpreted together with the hydrochemical analysis of surface water samples collected at 79 points of observation. The data show a strong seasonal variation of surface water quality with poorer water quality standards during the dry season. It is also possible to observe that there is a natural decrease in pollution levels with increasing distance from the pollution source (mining areas). Acidic leachates are gradually neutralized as they drain away from the mining areas depositing Fe-(Cu-Al) bearing secondary minerals. There is also an important contaminant load reduction in the estuary area as a result of the mixing process with seawater. This contributes to a loss of the metals in solution due to both dilution and precipitation, as a result of pH increase.

The present paper deals with an extensive review of literature concerning the platinum group elements (PGEs), and their impact on the environment. The increased number of cars and vehicles fitted with catalytic converters, has been linked with the wide spread in the environment of the PGEs, i.e. Pt, Pd and Rh. Numerous studies present compelling evidence that the catalytic converters, do not only minimize the pollution caused by the car exhaust fumes, but also they release in the environment particulate matter containing the above noble elements, which accumulate in the soil, and plants, or remain suspended in the air, being transported to large distances. Indeed, the concentration of these noble elements in the soil and plants has increased significantly during the last 10-15 years, especially along the road side of high ways. Assessment of the PGEs health risk was originally based on measuring the body fluid in Pt, Pd and Rh content of occupationally involved people, as well as of the general population. Recent results based on cellular studies show that the PGEs are related to respiratory sensitization, allergic reactions, dermatitis, urticaria, damage of the epithelial lung cells, asthma, rhinoconjuctivitis, lymphocyte proliferation and cytokine release and possibly to cancer. In spite of the progress attained, more work is necessary for an accurate health risk assessment.

Background, aim and scope The use of sodium hypochlorite (HYP) in viticulture results in effluents which are contaminated with halogenated substances. These disinfection by-products (DBPs) can be quantified as group parameter 'adsorbable organic halogens' (AOX) and have not been determined in effluents of viticulture yet. The substances that are detected as AOX are unknown. The AOX can be composed of harmless substances, but even toxic contaminants. Thus, it is impossible to assess ecological impacts. The aim of this study is to determine the quantification of AOX and DBPs after the use of HYP. This will be helpful to reduce environmental pollution by AOX. Materials and methods The potential of HYP to generate AOX was determined in laboratory-scale experiments. Different model solutions were treated with HYP according to disinfection processes in viticulture and conditions of AOX formation in effluents were simulated. AOX were quantified using the flask-shaking method and identified DBPs were investigated by gas chromatography-mass spectrometry. Results Treatment with HYP resulted in the formation of AOX. The percentage conversion of HYP to AOX was up to 11%. Most important identified DBPs in viticulture are chloroform, dichloroacetic acid and trichloroacetaldehyde. In addition, the formation of carbon tetrachloride (CT), 1,1,1-trichloropropanone, 2,4-dichlorobenzoic acid and 2-chloro-/2,4-dichlorophenylacetic acid was investigated. It was demonstrated that reaction temperature, concentration of HYP and type of organic matter have important influence on the formation of chlorinated DBPs. Discussion The percentage conversion of HYP to AOX was similar to other published studies. Although a correlation of single compounds and AOX is difficult, chloroform was the predominant AOX. Generation of the volatile chloroform should be avoided due to possible adverse effects. The generation of dichloroacetic acid is of minor importance on account of biodegradation. Trichloroacetaldehyde and 1,1,1-trichloropropanone are weak mutagens and their formation should be avoided. Conclusions The generation of AOX and chlorinated DBPs can be minimised by reducing the concentrations of the organic materials in the effluents. The removal of organic matter before disinfection results in a decreased formation of AOX. HYP is an effective disinfectant; therefore, it should be used at low temperatures and concentrations to reduce the amount of AOX. If possible, disinfection should be accomplished by the use of no chlorine-containing agents. By this means, negative influences of HYP on the quality of wine can also be avoided. Recommendations and perspectives Our results indicate that HYP has a high potential to form AOX in effluents of viticulture. The predominant by-products are chloroform, dichloroacetic acid and trichloroacetaldehyde. In further research, wastewaters from a winery and the in- and outflows of two sewage treatment plants were sampled during vintage and analysed. These results will be discussed in a following paper.

Background, aim and scope Chlorine is an abundant element, commonly occurring in nature either as chloride ions or as chlorinated organic compounds (OCls). Chlorinated organic substances were long considered purely anthropogenic products; however, they are, in addition, a commonly occurring and important part of natural ecosystems. Formation of OCls may affect the degradation of soil organic matter (SOM) and thus the carbon cycle with implications for the ability of forest soils to sequester carbon, whilst the occurrence of potentially toxic OCls in groundwater aquifers is of concern with regard to water quality. It is thus important to understand the biogeochemical cycle of chlorine, both inorganic and organic, to get information about the relevant processes in the forest ecosystem and the effects on these from human activities, including forestry practices. A survey is given of processes in the soil of temperate and boreal forests, predominantly in Europe, including the participation of chlorine, and gaps in knowledge and the need for further work are discussed. Results Chlorine is present as chloride ion and/or OCls in all compartments of temperate and boreal forest ecosystems. It contributes to the degradation of SOM, thus also affecting carbon sequestration in the forest soil. The most important source of chloride to coastal forest ecosystems is sea salt deposition, and volcanoes and coal burning can also be important sources. Locally, de-icing salt can be an important chloride input near major roads. In addition, anthropogenic sources of OCls are manifold. However, results also indicate the formation of chlorinated organics by microorganisms as an important source, together with natural abiotic formation. In fact, the soil pool of OCls seems to be a result of the balance between chlorination and degradation processes. Ecologically, organochlorines may function as antibiotics, signal substances and energy equivalents, in descending order of significance. Forest management practices can affect the chlorine cycle, although little is at present known about how. Discussion The present data on the apparently considerable size of the pool of OCls indicate its importance for the functioning of the forest soil system and its stability, but factors controlling their formation, degradation and transport are not clearly understood. It would be useful to estimate the significance and rates of key processes to be able to judge the importance of OCls in SOM and litter degradation. Effects of forest management processes affecting SOM and chloride deposition are likely to affect OCls as well. Further standardisation and harmonisation of sampling and analytical procedures is necessary. Conclusions and perspectives More work is necessary in order to understand and, if necessary, develop strategies for mitigating the environmental impact of OCls in temperate and boreal forest soils. This includes both intensified research, especially to understand the key processes of formation and degradation of chlorinated compounds, and monitoring of the substances in question in forest ecosystems. It is also important to understand the effect of various forest management techniques on OCls, as management can be used to produce desired effects.

Background, aim, and scope The management of contaminated sites requires the investigation of different involved aspects (from socioeconomic to risk and technological issues) and the presentation of useful and condensed information to decision makers. For this purpose, indices are more and more recognized as effective and valuable tools. This paper presents specific indices created within the DEcision Support sYstem for REhabilitation of contaminated sites (DESYRE). Materials and methods DESYRE is a software which aids decision making for the rehabilitation of a large contaminated site (i.e., megasite) by the creation and comparison of different rehabilitation alternatives. The software is composed of six modules, each dealing with a specific aspect of the remediation process, ending with the decision module. In this module, scenarios (i.e., suitable solutions for the rehabilitation of the contaminated site including selected land use, socioeconomic benefits, remediation costs, time span, environmental impacts, technology set/s, and residual risk) are created and evaluated by means of suitable indices. Nine indices cover the socioeconomic, risk, technological, cost, time, and environmental impact aspects. Mathematical algorithms are used to calculate these indices by taking into account data collected during the analytical steps of the DESYRE system and elaborated through the support of the spatial analysis, which is embedded in the system. Results The case study of Porto Marghera, Venice, Italy is presented in order to document the effectiveness of developed indices in evaluating management solutions and presenting options to decision makers. For the purpose of this study, three different scenarios for the remediation of a part of the site of Porto Marghera (approximately 530 ha) are developed and compared. The three scenarios consider the industrial land use and deal with the contamination in soil caused by inorganic and organic compounds. The scenarios mainly differ for the number of the included remediation technologies and for the spatial distribution of the technologies on the considered area. Discussion Indices results allow the user to more easily evaluate the advantages and limits of each scenario in order to select the most appropriate one. For instance, the risk indices allow the user to identify scenarios with good performance in reducing the extension of risk areas and the risk magnitude. Equally, the technological indices support the achievement of efficient remedial solutions characterized by a limited number of technologies, applied to extended areas and with high performance. The environmental impact index allows users to estimate the wider effects on the environment of the selected solutions, while the socioeconomic index is the result of social and economic investigations of the regional and local conditions, which ends with the identification of the best land use (e.g., the industrial one for the Porto Marghera area). Conclusions The proposed nine DESYRE indices provide more complete information to investigate suitable management solutions. DESYRE indices facilitate the definition of a consensus among stakeholders and the achievement of a widely shared solution for contaminated site management, even at larger sites, such as Porto Marghera. Recommendations and perspectives Further improvements to the system may be adopted, e.g., the possibility to aggregate results of the different assessments into one synthetic index per scenario or the inclusion of a Group Decision Making procedure.

Background, aim and scope The biocide triclosan (TCS) is commonly used in personal care, acrylic, plastic, and textiles products. TCS has been detected in surface water in several countries, and its ecological impact is largely unknown. In this work, the toxicity of TCS in zebrafish (Danio rerio), embryos and adults was studied. Several lethal and sub-lethal endpoints were analysed in organisms exposed to TCS such as mortality, embryo development and behaviour, hatching, micronuclei and biochemical markers (cholinesterase (ChE), glutathione S-transferase (GST) and lactate dehydrogenase (LDH)). Materials and methods Embryo/larvae assay followed the OECD guideline on Fish Embryo Toxicity Test. Embryos were exposed at nominal concentrations of 0.1, 0.3, 0.5, 0.7 and 0.9 mg/l of TCS for 6 days and were inspected daily with the help of a stereomicroscopy for mortality, developmental parameters (otolith formation, eye and body pigmentation, somite formation, heart beat, tail circulation, detachment of the tail-bud from the yolk sac) and hatching. A similar test was run to obtain larvae for ChE, GST and LDH analysis. The adult test followed the OECD Guideline TG 203 in semi-static conditions. Adult zebrafish of similar length and age were exposed to nominal concentrations of 0.1, 0.2, 0.3, 0.4 and 0.5 mg/l of TCS for 96 h and were inspected daily for mortality and behaviour alterations. A second test was run to obtain organs for biomarkers analysis: Heads, muscles and gills were isolated and snap-frozen in eppendorfs and used for ChE, LDH and GST determinations, respectively. Adult zebrafish testing also comprised a third test for micronucleus analysis in which the nominal concentrations of 0, 0.175 and 0.350 mg/l were used. Peripheral blood was obtained by cardiac puncture and used for the analysis. Results TCS showed acute toxicity for embryo/larvae (96 h LC₅₀ = 0.42 mg/l) and delayed hatching. Moreover, embryo toxicity was evident: Delay on the otolith formation and eye and body pigmentation were found, and malformations were also evident, including spine malformations, pericardial oedema and undersize. Biomarkers levels were affected: ChE and LDH activity were increased in larvae exposed to 0.25 mg/l, and GST activity was increased in larvae exposed to 0.25 and 0.35 mg/l. TCS also demonstrated acute toxicity to adult zebrafish (96 h LC₅₀ = 0.34 mg/l). However, TCS did not change biomarkers levels and did not elicit a micronucleus in adults. Discussions Despite the fact that similar 96 h LC₅₀ values have been found for D. rerio embryos and adults (0.42 and 0.34 mg/l, respectively), the embryo assay was much more informative, showing important effects at several levels, including teratogenic response, hatching delay and alteration of biomarker levels. TCS does not seem to be genotoxic for adult fish or to interfere with biomarkers levels at the concentrations tested. Conclusions TCS has deleterious effects on zebrafish adults and during early stages, (including embryotoxicity, hatching delay and alterations of biomarkers levels). The range of endpoints used on the embryo test allows an integrated analysis that contributes to a better understanding of the toxicity and mode of action of TCS. Recommendations and perspectives Future works should focus on a deeper investigation of TCS modes of action on zebrafish early-life stages. As embryo testing was revealed to be so informative, a refinement of the test could be made, including other endpoints such as different biochemical markers as well as DNA microarrays to assess a gene expression level for the effect of exposure to TCS. In the perspective of risk assessment, these endpoints should be explored in order to assess their usefulness as early warning signs and links should be sought between these short-term tests and effects of long-term exposures as it is observed in more realistic scenarios.

Background, aim and scope Each year, large quantities of pharmaceuticals are consumed worldwide for the treatment and prevention of human and animal diseases. Although the drugs and the metabolites observed in the wastewaters and in the environment are present at concentrations several orders of magnitude lower than the concentrations required to exert their effects in humans or animals, their long-term impact on the environment is commonly not known. In this study, the occurrence of six antihistamines, which are used for the relief of allergic reactions such as hay fever, was determined in sewage treatment plants wastewaters and in recipient river waters. Materials and methods The occurrence of the antihistamines cetirizine, acrivastine, fexofenadine, loratadine, desloratadine and ebastine in sewage treatment plants wastewaters and in recipient river waters was studied. The analytical procedure consisted of solid-phase extraction of the water samples followed by liquid chromatography separation and detection by a triple-quadrupole mass spectrometer in the multiple reaction mode. Results Cetirizine, acrivastine and fexofenadine were detected in both influent and effluent wastewater samples at concentration levels ranging from about 80 to 220 ng/L, while loratadine, desloratadine and ebastine could not be detected in any samples. During sewage treatment, the concentration of the antihistamines dropped by an average of 16-36%. Furthermore, elevated concentrations of antihistamines were observed in samples collected during the season of most intensive plant pollen production, i.e. in May. In the river water samples, the relative pattern of occurrence of cetirizine, acrivastine and fexofenadine was similar to that in the wastewater samples; although the concentration of the compounds was substantially lower (4-11 ng/L). The highest concentrations of the studied drugs were observed near the discharging point of the sewage treatment plant. Discussion The highest concentrations of antihistamines in STP wastewaters correlate with the outbreak of allergic reaction caused by high amounts of plant pollens in the air. The analysis results of the river water samples show that the antihistamines are carried far away from the effluent discharge points. They may account for a part of the mix of pharmaceuticals and of pharmaceutical metabolites that occur downstream of STPs. Conclusions Antihistamines are poorly degraded/eliminated under the biological treatment processes applied in the wastewater treatment plants and, consequently, they are continuously being discharged along with other drugs to the aquatic environment. Recommendations and perspectives As a huge quantity and variety of drugs and their metabolites are continuously discharged to rivers and the sea, the compounds should be considered as contaminants that may possess risks to the aquatic ecosystem. Further studies are urgently needed on the environmental fate of the antihistamines and other pharmaceuticals in the aquatic environment. These studies should be concerned with the stability of the compounds, their transformation reactions and the identity of the transformation products, the distribution of drugs and their uptake and effects in organisms. On the basis of these studies, the possible environmental hazards of pharmaceuticals may be assessed.

Background, aim, and scope Unsaturated esters are emitted to the atmosphere from biogenic and anthropogenic sources, including those from the polymer industry. Little information exists concerning the atmospheric degradation of unsaturated esters, which are mainly initiated by OH radicals. Limited information is available on the degradation of alkenes by Cl atoms and almost no data exists for the reactions of unsaturated esters with Cl atoms. This data is necessary to assess the impact of such reactions in maritime environments where, under circumstances, OH radical- and Cl atom-initiated oxidation of the compounds can be important. Rate coefficients for the reactions of chlorine atoms with vinyl acetate, allyl acetate, and n-butyl acrylate have been determined at 298 ± 3 K and atmospheric pressure. The kinetic data have been used in combination with that for structurally similar compounds to infer the kinetic contributions from the possible reaction channels to the overall reaction rate. Materials and methods The decay of the organics was followed using in situ Fourier transform infrared spectroscopy and the rate coefficients were determined using a relative kinetic method and different hydrocarbon reference compounds. Results The following room temperature rate coefficients (in cm³ molecule⁻¹ s⁻¹) were obtained: k ₁ (Cl + CH₃C(O)OCH=CH₂) = (2.68 ± 0.91) x 10⁻¹⁰, k ₂ (Cl + CH₃C(O)OCH₂CH=CH₂) = (1.30 ± 0.45) x 10⁻¹⁰, and k ₃ (Cl + CH₂=CHC(O)O(CH₂)₃CH₃) = (2.50 ± 0.78) x 10⁻¹⁰, where the uncertainties are a combination of the 2σ statistical errors from linear regression analyses and a contribution to cover uncertainties in the rate coefficients of the reference hydrocarbons. Discussion This is the first kinetic study of the title reactions under atmospheric conditions. The kinetic data were analyzed in terms of reactivity trends and used to estimate the atmospheric lifetimes of the esters and assess their potential importance in the marine atmosphere. Conclusions Although reaction with OH radicals is the major atmospheric sink for the unsaturated esters studied, reaction with Cl atoms can compete in the early morning hours in coastal areas where the Cl concentration can reach peak values as high as 1 x 10⁵ atoms cm⁻³. The calculated residence times show that the chemistry of unsaturated esters will impact air quality locally near their emission sources. Recommendations and perspectives The reactions need to be studied over the range of temperatures and pressures generally encountered in the marine atmosphere. In addition, product studies should also be performed as a function of temperature since this will allow degradation mechanisms to be derived, which are representative for the wide range of conditions occurring in marine environments. Inclusion of the kinetic and product data in tropospheric numerical models will allow an assessment of potential environmental impacts of the esters for different marine pollution scenarios.