Pilot survey of a broad range of priority pollutants in sediment and fish from the Ebro river basin (NE Spain)

Priority organic pollutants were investigated in sediments and fish collected along the Ebro river basin (NE Spain) to evaluate their occurrence, transport and bioavailability. Sediments were collected in 18 sites and two species of fish were captured in nine sites according to the availability in each area. The sampling sites covered industrial, urban and agricultural areas. Four methods were used to detect 20 organochlorine compounds (OCs), 8 polycyclic aromatic hydrocarbons, 3 organotin compounds, 2 alkylphenols and 40 polybrominated diphenyl ethers (PBDEs) from purified extracts. The contamination pattern was site specific and no downstream increase in concentration of pollutants was observed but rather a generalized low level diffuse pollution. Target compounds were detected in sediments at 0.01 to 2331 microg/kg dry weight, and only OCs and PBDEs were accumulated in benthopelagic fish. Toxicological assessment was performed according to predicted environmental levels and revealed sites where adverse effects could occur.     

Biodegradation studies of selected priority acidic pesticides and diclofenac in different bioreactors

The biodegradation of selected priority acidic pesticides MCPP, MCPA, 2,4-D, 2,4-DP and bentazone and the acidic pharmaceutical diclofenac was investigated using a membrane bioreactor (MBR) and a fixed-bed bioreactor (FBBR). A pilot plant MBR was fed with raw water spiked with the selected compounds. The experiment was repeated every week during four weeks to enhance the adaptation of microorganisms. In order to further study the biodegradability of these compounds, degradation studies in a FBBR were carried out. All the samples were analysed by solid phase extraction-gas chromatography-mass spectrometry (SPE-GC-MS). The results indicate that in the MBR compounds except for bentazone were eliminated within the first day of the experiment at rates ranging from 44% to 85%. Comparing these results with the degradation rates in the FBBR showed that in the latter only MCPP, MCPA 2,4-D and 2,4-DP were degraded after a much longer adaptation phase of microorganisms.     

Distribution of endocrine disruptors in the Llobregat River basin (Catalonia, NE Spain)

The Llobregat basin is a Mediterranean fluvial system with major agricultural, urban and industrial impacts. We combined chemical quantification by liquid chromatography–mass spectrometry with electrospray interface (LC-ESI-MS) and the recombinant yeast assay (RYA) assays to estimate the loads of endocrine disrupting compounds (EDCs) along the basin. Chemical analysis revealed maximum concentrations (at μg l⁻¹ level) of alkylphenols at the lower course of the Llobregat River, which correlated with high levels of estrogenic activity detected by RYA. Analysis by RYA and LC-ESI-MS of influent and effluent waters from four sewage treatment plants (STP) discharging into the basin showed the removal of 80–95% of EDCs by STP treatment. Chemical analysis data and RYA data showed a quasi-linear correlation, demonstrating the complementariness of both methods. Our data suggest that the concentrations of the analysed compounds were enough to explain the total estrogenicity of water and STP samples from the Llobregat basin.     

Local changes in the composition and community structure of suprabenthic peracarid crustaceans on the bathyal Mediterranean: influence of environmental factors

Deep-water assemblages of suprabenthic peracarids were analyzed in the SW Balearic Islands (Algerian Basin, southwestern Mediterranean) between 249 and 1,622 m depth; the patterns of species composition, possible zonation, and trophic structure found in this area were compared with those exhibited by peracarids in the mainland side of the Catalan Sea slope (northwestern Mediterranean). One hundred and four peracarid species (plus one leptostracan) were identified on the Balearic Islands slope, amphipods being the most diversified taxon (45 species). On the Balearic slope, two distinct depth assemblages were distinguished: one at the upper slope (US), between 249 and 402 m depth and the second at the deep slope, between 543 and 1,620 m depth. A remarkable species substitution occurred at depths between 402 and 638 m. In the Catalan Sea, in addition to the US assemblage occupying depths between 208 and 408 m, a second boundary of faunal change was found around 1,250 m. Suprabenthos biomass increased from 242 to approximately 500 m. Suprabenthos attained the highest biomass values (100 g wet weight/10,000 m²) at intermediate depths between 504 and 1,211 m, as also occurred with the associated zooplankton collected with suprabenthos (peak biomass between 502 m and 898 m). Suprabenthos biomass did not show any significant correlation with any environmental water-column variable. In contrast, zooplankton (especially small fish and decapod crustaceans) showed a significant positive correlation with fluorometry and turbidity at different levels of the water column. The feeding guilds of species showed important differences between the two areas only on the US, with a higher abundance of deposit feeders in the Catalan Sea (20.4%) than in the Balearic Islands (4.2%). The low contribution of deposit feeders in the SW Balearic Islands may ultimately be a consequence of the lack of river discharges in this area.Communicated by S.A. Poulet, Roscoff     

Survey of organotin compounds in rivers and coastal environments in Portugal 1999-2000

In the period from April 1999 to May 2000, organotin pollution, namely butyl and phenyltins, was investigated in coastal and continental waters (46 stations), estuarine sediments (15 stations) and mussels (Mytilus galloprovincialis) (13 stations) throughout Portugal. Sampling points were chosen in areas of specific industrial, agricultural and harbor activities. Butyltins (BTs) were the only tin species identified of which tributyltin (TBT) was found in the whole area. Concentrations of TBT in river water ranged from 3 to 30 ng L(-1) (as Sn), marine sediment ranged from 4 to 12 microg kg(-1) (as Sn), whereas concentrations in mussel tissue ranged from 2.5 to 490 microg kg(-1) (as Sn). Given that some water samples appeared to be contaminated by higher monobutyltin (MBT) and dibutyltin (DBT) concentrations, the role of biological degradation and direct inputs from agricultural and industrial applications areas are discussed. The study compares depleted butyltin pollution in sediments and mussels of the Portuguese coastline associated with antifouling paints with previously reported levels. Inputs in river waters are more related to (i) PVC leaching and (ii) industrial sources, in some cases discharged by municipal wastewaters.     

Effect-Directed Analysis of Key Toxicants in European River Basins. A Review (9 pp)

Background, Aim and Scope Extensive monitoring programs on chemical contamination are run in many European river basins. With respect to the implementation of the European Union (EU) Water Framework Directive (WFD), these programs are increasingly accompanied by monitoring the ecological status of the river basins. Assuming an impact of chemical contamination on the ecological status, the assignment of effects in aquatic ecosystems to those stressors that cause the effects is a prerequisite for taking political or technical measures to achieve the goals of the WFD. Thus, one focus of present European research is on toxicant identification in European river basins in order to allow for a reduction of toxic pressure on aquatic ecosystems according to the WFD. Main Features: An overview is presented on studies that were performed to link chemical pollution in European river basins to measurable ecotoxic effects. This includes correlation-based approaches as well as investigations that apply effect-directed analysis (EDA) integrating toxicity testing, fractionation and non-target chemical analysis. Effect-based key toxicants that were identified in European surface waters are compiled and compared to EU priority pollutants. Further needs for research are identified. Results: Studies on the identification of effect-based key toxicants focused on mutagenicity, aryl hydrocarbon receptor-mediated effects, endocrine disruption, green algae, and invertebrates. The identified pollutants include priority pollutants and other well-known environmental pollutants such as polycyclic aromatic hydrocarbons, polychlorinated dibenzo-p-dioxins, furans, and biphenyls, nonylphenol, some pesticides and tributyltin, but also other compounds that were neither considered as environmental pollutants before nor regulated such as substituted phenols, natural or synthetic estrogens and androgens, dinaphthofurans, 2-(2-naphthalenyl)benzothiophene, and N-phenyl-2-naphthylamine. Discussion: Individual studies at specific sites in a European river basin demonstrated the power of combined biological and chemical analytical approaches and, particularly, of effect-directed analysis. However, the available information on effect-based key toxicants is very limited with respect to the entirety of rivers possibly at risk due to chemical contamination and with respect to toxicological endpoints considered at a specific site. A relatively broad basis of information exists only for estrogenicity and aryl hydrocarbon, receptor-mediated effects. Conclusions: The development of tools and strategies for an identification of key toxicants on a broader scale are a challenging task for the next years. Since investigations dealing with toxicant identification are too labor and cost-intensive for monitoring purposes, they have to be focused on the key sites in a river basin. These should include hot spots of contamination, particularly if there is evidence that they might pose a risk for downstream areas, but may also involve accumulation zones in the lower reach of a river in order to get an integrated picture on the contamination of the basin. Perspectives: While EDA is almost exclusively based on measurable effects in in vitro and in vivo biotests to date, an increasing focus in the future should be on the integration of EDA into Ecological Risk Assessment and on the development of tools to confirm EDA-determined key toxicants as stressors in populations, communities and ecosystems. Considering these requirements and applied in a focused way, toxicant identification may significantly help to implement the Water Framework Directive by providing evidence on the main stressors and possible mitigation measures in order to improve the ecological status of a river ecosystem.     

Short-term impact of olive mill wastewater (OMWW) applications on the physico-chemical and microbiological soil properties of an olive grove in Argentina

The purpose of this work was to investigate the effects of spreading olive oil mill wastewater (OMWW) on soil biochemical parameters and olive production in an organically managed olive orchard. The experiment was carried out with three different doses of OMWW (80, 160 and 500 m³ ha^?1) and a control (untreated soil). Three samplings were done at 10, 30 and 90 days after the administration of the byproduct. OMWW application differentially modified the biochemical properties of the soil analyzed. Organic matter, organic carbon, total nitrogen and extractable phosphorus soil contents increased proportionally with each increasing dose. The values of these parameters decreased gradually with time. Total microbial activity was altered and the OMWW 500 m³ ha^?1 treatment proved to be the most active when compared with the other applied doses. OMWW agricultural application also modified the structure of soil microbial communities, particularly affecting Gram positive and negative bacteria, while fungal biomass did not show consistent changes. Although there was a salinity increase in the treated soil, especially at the highest dose, the productive parameters analyzed (fruit and oil tree^?1) were not affected. In light of the obtained results, we consider that low dose of OMWW could be considered an alternative farming practice for semiarid regions.     

New indexes for compound prioritization and complexity quantification on environmental monitoring inventories

Introduction  

Lists of compounds resulting from environmental monitoring may be conveniently represented in a very general way using Pareto distributions, after ranking them on descending order according to their concentration or hazard quotient expressed as percentages, depending on whether the objective of the monitoring is focussed on mass load occurrence or risk assessment respectively.