Pesticides in the Ebro River basin: Occurrence and risk assessment.

In this study, 50 pesticides were analyzed in the Ebro River basin in 2010 and 2011 to assess their impact in water, sediment and biota. A special emphasis was placed on the potential effects of both, individual pesticides and their mixtures, in three trophic levels (algae, daphnia and fish) using Risk Quotients (RQs) and Toxic Units (TUs) for water and sediments. Chlorpyrifos, diazinon and carbendazim were the most frequent in water (95, 95 and 70% of the samples, respectively). Imazalil (409.73 ng/L) and diuron (150 ng/L) were at the highest concentrations. Sediment and biota were less contaminated. Chlorpyrifos, diazinon and diclofenthion were the most frequent in sediments (82, 45 and 21% of the samples, respectively). The only pesticide detected in biota was chlorpyrifos (up to 840.2 ng g(-1)). Ecotoxicological risk assessment through RQs showed that organophosphorus and azol presented high risk for algae; organophosphorus, benzimidazoles, carbamates, juvenile hormone mimic and other pesticides for daphnia, and organophosphorus, azol and juvenile hormone mimics for fish. The sum TUsite for water and sediments showed values < 1 for the three bioassays. In both matrices, daphnia and fish were more sensitive to the mixture of pesticide residues present.

Managing the effects of multiple stressors on aquatic ecosystems under water scarcity. The GLOBAQUA project.

Water scarcity is a serious environmental problem in many European regions, and will likely increase in the near future as a consequence of increased abstraction and climate change. Water scarcity exacerbates the effects of multiple stressors, and thus results in decreased water quality. It impacts river ecosystems, threatens the services they provide, and it will force managers and policy-makers to change their current practices. The EU-FP7 project GLOBAQUA aims at identifying the prevalence, interaction and linkages between stressors, and to assess their effects on the chemical and ecological status of freshwater ecosystems in order to improve water management practice and policies. GLOBAQUA assembles a multidisciplinary team of 21 European plus 2 non-European scientific institutions, as well as water authorities and river basin managers. The project includes experts in hydrology, chemistry, biology, geomorphology, modelling, socio-economics, governance science, knowledge brokerage, and policy advocacy. GLOBAQUA studies six river basins (Ebro, Adige, Sava, Evrotas, Anglian and Souss Massa) affected by water scarcity, and aims to answer the following questions: how does water scarcity interact with other existing stressors in the study river basins? How will these interactions change according to the different scenarios of future global change? Which will be the foreseeable consequences for river ecosystems? How will these in turn affect the services the ecosystems provide? How should management and policies be adapted to minimise the ecological, economic and societal consequences? These questions will be approached by combining data-mining, field- and laboratory-based research, and modelling. Here, we outline the general structure of the project and the activities to be conducted within the fourteen work-packages of GLOBAQUA.

Pesticide monitoring in the basin of Llobregat River (Catalonia, Spain) and comparison with historical data.

Through an extensive sampling in the Llobregat River basin, the presence of 50 currently used pesticides in water, sediment, and biota was assessed. Pesticides were detected primarily in water (up to 56% of the analytes), whereas their presence in sediments was more intermittent, and in biota was scarce. Those at high concentrations in water were the benzimidazoles (carbendazim in 22% of the samples up to 697 ng L(-1)), the organophosphorus (malathion in 54% of the samples up to 320 ng L(-1)), and the ureas (diuron in 54% of the samples up to 159 ng L(-1)). However, this pattern differed in sediments and biota, which were contaminated primarily with organophosphorus (higher Kow) (chlorpyrifos 93% of sediments up to 131 ng g(-1)). According to the results of this study, pesticide residues in the Llobregat River basin do not seem to represent a high risk to biota, even though some algae and fish can be affected. Nevertheless, the monitoring program can be very useful to control the contamination of the river basin, as the availability of historical data on the basin confirmed background contamination in the last 20 years.

Accumulation of perfluoroalkyl substances in human tissues.

Perfluoroalkyl substances (PFASs) are environmental pollutants with an important bioaccumulation potential. However, their metabolism and distribution in humans are not well studied. In this study, the concentrations of 21 PFASs were analyzed in 99 samples of autopsy tissues (brain, liver, lung, bone, and kidney) from subjects who had been living in Tarragona (Catalonia, Spain). The samples were analyzed by solvent extraction and online purification by turbulent flow and liquid chromatography coupled to tandem mass spectrometry. The occurrence of PFASs was confirmed in all human tissues. Although PFASs accumulation followed particular trends depending on the specific tissue, some similarities were found. In kidney and lung, perfluorobutanoic acid was the most frequent compound, and at highest concentrations (median values: 263 and 807ng/g in kidney and lung, respectively). In liver and brain, perfluorohexanoic acid showed the maximum levels (median: 68.3 and 141ng/g, respectively), while perfluorooctanoic acid was the most contributively in bone (median: 20.9ng/g). Lung tissues accumulated the highest concentration of PFASs. However, perfluorooctane sulfonic acid and perfluorooctanoic acid were more prevalent in liver and bone, respectively. To the best of our knowledge, the accumulation of different PFASs in samples of various human tissues from the same subjects is here reported for the very first time. The current results may be of high importance for the validation of physiologically based pharmacokinetic models, which are being developed for humans. However, further studies on the distribution of the same compounds in the human body are still required.

Integration of research advances in modelling and monitoring in support of WFD river basin management planning in the context of climate change.

The integration of scientific knowledge about possible climate change impacts on water resources has a direct implication on the way water policies are being implemented and evolving. This is particularly true regarding various technical steps embedded into the EU Water Framework Directive river basin management planning, such as risk characterisation, monitoring, design and implementation of action programmes and evaluation of the "good status" objective achievements (in 2015). The need to incorporate climate change considerations into the implementation of EU water policy is currently discussed with a wide range of experts and stakeholders at EU level. Research trends are also on-going, striving to support policy developments and examining how scientific findings and recommendations could be best taken on board by policy-makers and water managers within the forthcoming years. This paper provides a snapshot of policy discussions about climate change in the context of the WFD river basin management planning and specific advancements of related EU-funded research projects. Perspectives for strengthening links among the scientific and policy-making communities in this area are also highlighted.

Assessing the effects of multiple stressors on the functioning of Mediterranean rivers using poplar wood breakdown.

Mediterranean rivers in the Iberian Peninsula are being increasingly affected by human activities, which threaten their ecological status. A clear picture of how do these multiple stressors affect river ecosystem functioning is still lacking. We addressed this question by measuring a key ecosystem process, namely breakdown of organic matter, at 66 sites distributed across Mediterranean Spain. We performed breakdown experiments by measuring the mass lost by wood sticks for 54 to 106 days. Additionally, we gathered data on physico-chemical, biological and geomorphological characteristics of study sites. Study sites spanned a broad range of environmental characteristics and breakdown rates varied fiftyfold across sites. No clear geographic patterns were found between or within basins. 90th quantile regressions performed to link breakdown rates with environmental characteristics included the following 7 variables in the model, in decreasing order of importance: altitude, water content in phosphorus, catchment area, toxicity, invertebrate-based biotic index, riparian buffer width, and diatom-based quality index. Breakdown rate was systematically low in high-altitude rivers with few human impacts, but showed a high variability in areas affected by human activity. This increase in variability is the result of the influence of multiple stressors acting simultaneously, as some of these can promote whereas others slow down the breakdown of organic matter. Therefore, stick breakdown gives information on the intensity of a key ecosystem process, which would otherwise be very difficult to predict based on environmental variables.

Assessing and forecasting the impacts of global change on Mediterranean rivers. The SCARCE Consolider project on Iberian basins.

INTRODUCTION: The Consolider-Ingenio 2010 project SCARCE, with the full title "Assessing and predicting effects on water quantity and quality in Iberian Rivers caused by global change" aims to examine and predict the relevance of global change on water availability, water quality, and ecosystem services in Mediterranean river basins of the Iberian Peninsula, as well as their socio-economic impacts. Starting in December 2009, it brought together a multidisciplinary team of 11 partner Spanish institutions, as well as the active involvement of water authorities, river basin managers, and other relevant agents as stakeholders. METHODS: The study areas are the Llobregat, Ebro, Jucar, and Guadalquivir river basins. These basins have been included in previous studies and projects, the majority of whom considered some of the aspects included in SCARCE but individually. Historical data will be used as a starting point of the project but also to obtain longer time series. The main added value of SCARCE project is the inclusion of scientific disciplines ranging from hydrology, geomorphology, ecology, chemistry, and ecotoxicology, to engineering, modeling, and economy, in an unprecedented effort in the Mediterranean area. The project performs data mining, field, and lab research as well as modeling and upscaling of the findings to apply them to the entire river basin. RESULTS: Scales ranging from the laboratory to river basins are addressed with the potential to help improve river basin management. The project emphasizes, thus, linking basic research and management practices in a single framework. In fact, one of the main objectives of SCARCE is to act as a bridge between the scientific and the management and to transform research results on management keys and tools for improving the River Basin Management Plans. Here, we outline the general structure of the project and the activities conducted within the ten Work Packages of SCARCE.

Environmental distribution of PAHs in pine needles, soils, and sediments.

INTRODUCTION: The content of 16 polycyclic aromatic hydrocarbons (PAHs) was determined in 60 samples from three environmental matrices (soils, sediments, and pine needles) in an effort to assess their distribution on a river basin scale. METHODS: A sampling campaign was carried out in 2006, selecting urban, industrial, and agricultural sampling sites along the northeast of Spain. Techniques used included pressurized liquid extraction and solid-liquid ultrasonic extraction followed by gas chromatography-electron impact ionization mass spectrometry. RESULTS: The mean total PAHs concentrations were 290 < 613 < 1,628 ng/g (dry weight) in pine needles, soil, and sediments, respectively. There is a good correspondence between the total concentration of soils and pine needles, as opposed to the levels between sediments and pine needles. The high concentrations found in some Pinus halepensis samples may reflect a superior uptake potential of this species in comparison to the others studied. The three matrices present a very different PAH distribution pattern, with pine needles showing a predominance of the lighter (2-, 3-, and 4-ring) PAHs, whereas 5- and 6-ring PAHs are the most abundant in soils. Sediments display a more heterogeneous pattern, with contributions of all the PAHs but different distribution depending on the site, suggesting a wider range of input sources. Established PAH molecular ratios and principal component analysis were used to identify the origins and profiles of PAHs. While sediments showed a wide range attributed to historical inputs, soils and pine needles confirmed the compartmentalization of the PAHs, with lighter airborne PAHs accumulated in pine needles and heavier ones in soils. CONCLUSIONS: It can be suggested that the monitoring of several matrices is a strong tool to elucidate the contamination sources and accumulation patterns of PAHs. However, given the influence of the matrix type on this assessment, the information should be considered complementary, yet allowing a more comprehensive depiction of the area in question.

Identifying major pesticides affecting bivalve species exposed to agricultural pollution using multi-biomarker and multivariate methods.

The aim of this investigation was to identify major pesticides that may cause detrimental effects in bivalve species affected by agricultural pollution. Investigations were carried out using freshwater clams (Corbicula fluminea) transplanted in the main drainage channels that collect the effluents coming from agriculture fields in the Ebro Delta (NE Spain) during the main growing season of rice (from May to August). Environmental hazards were assessed by measuring simultaneous up 46 contaminant levels and 9 biomarker responses. Measured biological responses showed marked differences across sites and months. Antioxidant and esterase enzyme responses were in most cases inhibited. Lipid peroxidation levels increased steadily from May in upstream stations to August in drainage channels. Principal Component (PCA) and Partial Least Squares to Latent Structure regression (PLS) analyses allowed the identification of endosulfan, propanil, and phenylureas as being the chemical contaminants causing the most adverse effects in the studied species.