Susana González

Presence and biological effects of emerging contaminants in Llobregat River basin: A review

Llobregat River (North-East Spain) is the most important drinking water source for Barcelona and its surrounding area. As one of the only water sources in the area the river water have been overexploited and effluents from more than 30 urban wastewater treatment plants, industries and agriculture runoffs have been discharged into the river. This article reviews the presence of emerging contaminants published during the last decades, emphasizing on the observed effects on ecosystems caused by the contamination. Pesticides, surfactants, estrogens, pharmaceuticals and personal care products and even abuse drugs are the main groups detected in different studies, reporting alterations in species composition, abundance or biomass and endocrine disruption measured by alterations in enzymatic activity or specific protein production. The information available provides an overview of the river status according to the Water Framework Directive.

Analysis of the occurrence and risk assessment of polar pesticides in the Llobregat River Basin (NE Spain)

Contamination of surface waters by pesticides continues to be the focus of concern for water authorities due to the growing evidence of their deleterious effects on aquatic life. In this context, the present work investigates the occurrence of 16 selected pesticides belonging to the classes of triazines, phenylureas, organophosphates, chloroacetanilides and thiocarbamates in surface waters from the Llobregat River (NE Spain) and some of its tributaries (Anoia and Rubí) and assesses their potential impact on the aquatic organisms by applying a recently developed index, the Short-term Pesticide Risk Index for the Surface Water System (PRISW-1), which takes into account the pesticides concentrations and their overall toxicity against three aquatic organisms (algae, Daphnia, and fish). Chemical analysis, performed by means of a fully automated method based on isotope dilution on-line solid phase extraction-liquid chromatography-electrospray-tandem mass spectrometry (on-line SPE-LC-ESI-MS/MS), revealed diuron and diazinon as the most ubiquitous and abundant compounds with levels up to 818 and 132 ng L(-1), respectively. Total pesticide concentrations, which in only 1 out of 66 samples surpassed 500 ng L(-1), were higher in the tributaries than in the river but their contribution in terms of mass-loads to the overall pesticide pollution of the Llobregat River was relatively small. Contamination increased downstream of the river and was clearly influenced by rainfall and hence river flow. Application of the PRISW-1 index indicated that, although pesticides levels fulfilled the European Union Environmental Quality Standards (EQS) for surface waters, the existing pesticide contamination poses a low to high ecotoxicological risk for aquatic organisms, that algae and macro-invertebrates are at higher risk than fish, and that the organophosphates diazinon and malathion and the phenylurea diuron are the major contributors to the overall toxicity and therefore the most problematic compounds.

Evaluation of an automated luminescent bacteria assay for in situ aquatic toxicity determination

A new system for monitoring toxicity TOXcontrol® (MicroLAN BV, The Netherlands) has been used to assess the toxicity of a selection of priority or emergent compounds in the laboratory. In this study, inhibition curves and EC50 - Effective Concentration causing 50% inhibition - of selected compounds (including pesticides, pharmaceuticals, surfactants and metals commonly detected in surface or drinking waters) were determined. This new technology is based on the measurement of Vibrio fischeri bioluminescence inhibition (ISO 11348). The main advantage of this equipment, compared to other laboratory assays, is the fully automation of the procedure. The instrument can be operated online in a simple, rapid and reproducible way. The variability of the results obtained with the TOXcontrol® biomonitoring system has been studied. A comparison with standardised technology based in V. fischeri (Microtox®) and additional test with Daphnia magna for selected organic compounds is presented. The results show that the methodology based on the TOXcontrol® system being validated is accurate and reproducible enough enabling this system to be used as an on-line automatic alert system to detect abnormal concentrations of toxic compounds.

Metabolic markers in blood can separate prostate cancer from benign prostatic hyperplasia.

Background:An individualised risk-stratified screening for prostate cancer (PCa) would select the patients who will benefit from further investigations as well as therapy. Current detection methods suffer from low sensitivity and specificity, especially for separating PCa from benign prostatic conditions. We have investigated the use of metabolomics analyses of blood samples for separating PCa patients and controls with benign prostatic hyperplasia (BPH).Methods:Blood plasma and serum samples from 29 PCa patient and 21 controls with BPH were analysed by metabolomics analysis using magnetic resonance spectroscopy, mass spectrometry and gas chromatography. Differences in blood metabolic patterns were examined by multivariate and univariate statistics.Results:By combining results from different methodological platforms, PCa patients and controls were separated with a sensitivity and specificity of 81.5% and 75.2%, respectively.Conclusions:The combined analysis of serum and plasma samples by different metabolomics measurement techniques gave successful discrimination of PCa and controls, and provided metabolic markers and insight into the processes characteristic of PCa. Our results suggest changes in fatty acid (acylcarnitines), choline (glycerophospholipids) and amino acid metabolism (arginine) as markers for PCa compared with BPH.

Presence of metals in drinking water distribution networks due to pipe material leaching: a review

Drinking water quality should remain constant from the drinking water treatment plant to the consumers tap. However, water quality characteristics might be affected by interactions with pipe materials. This review describes the iron, copper, lead, zinc, aluminum, chromium, and cadmium in drinking water leached from the pipe material present in drinking water, as well as the factors and mechanisms that affect leaching processes. Data analysis suggests that monitoring the water quality in distribution systems is important for their proper management; however, the low measured concentrations highlight the need for sensitive sensors. In addition, further research is necessary to anticipate possible future effects before the installation of new materials/infrastructure or changes in water source/treatment.

Assessment of the water chemical quality improvement based on human health risk indexes: Application to a drinking water treatment plant incorporating membrane technologies.

A methodology has been developed in order to evaluate the potential risk of drinking water for the health of the consumers. The methodology used for the assessment considered systemic and carcinogenic effects caused by oral ingestion of water based on the reference data developed by the World Health Organisation (WHO) and the Risk Assessment Information System (RAIS) for chemical contaminants. The exposure includes a hypothetical dose received by drinking this water according to the analysed contaminants. An assessment of the chemical quality improvement of produced water in the Drinking Water Treatment Plant (DWTP) after integration of membrane technologies was performed. Series of concentration values covering up to 261 chemical parameters over 5 years (2008-2012) of raw and treated water in the Sant Joan Despí DWTP, at the lower part of the Llobregat River basin (NE Spain), were used. After the application of the methodology, the resulting global indexes were located below the thresholds except for carcinogenic risk in the output of DWTP, where the index was slightly above the threshold during 2008 and 2009 before the upgrade of the treatment works including membrane technologies was executed. The annual evolution of global indexes showed a reduction in the global values for all situations: HQ systemic index based on RAIS dropped from 0.64 to 0.42 for surface water and from 0.61 to 0.31 for drinking water; the R carcinogenic index based on RAIS was negligible for input water and varied between 4.2×10(-05) and 7.4×10(-06) for drinking water; the W systemic index based on the WHO data varied between 0.41 and 0.16 for surface water and between 0.61 and 0.31 for drinking water. A specific analysis for the indexes associated with trihalomethanes (THMs) showed the same pattern.

Fate of Surfactants in Membrane Bioreactors and Conventional Activated Sludge Plants

Two membrane bioreactors (MBRs) were operated at high sludge retention time (SRT) (between 30 and 75 d) in parallel to a conventional activated sludge plant (CASP) conducted at SRT = 10 d. The fate of linear alkylbenzene sulfonate (LAS), nonylphenol ethoxylates (NP(n)EO, n = 1-15), nonylphenoxy carboxylates (NP(n)EC, n = 1-2), and nonylphenol (NP) in these systems was investigated. All systems were very efficient in the removal of LAS (around 99%). The analysis of variance showed that the difference in the removal efficiency of LAS in the CASP and the MBR operated at SRT = 65-75 d (respectively 99.0 ± 0.43 and 99.8 ± 0.11) were significant (p < 0.05), confirming the importance of SRT in the removal of LAS. Comparison between the CASP and the MBRs in the removal efficiency of nonylphenolic compounds were conducted considering NP(3-15)EO, the sum of NP(1-15)EO, NP(1-2)EC, and nonylphenol (NP). In all cases MBRs were more efficient than the CASP. In the case of NP the removal was about 76 ± 7.5% for the CASP and 90% ± 12.1 and 82 ± 8.7% for the MBRs. Better performance of MBRs in the removal of nonylphenolic compounds can be attributed to a better degradation. For example, if the sum of NP(1-15)EO and NP(1-2)EC is considered, estimated biodegradation was about 48% for the CASP and 72% for MBRs.

Ecological screening indicators of stress and risk for the Llobregat river water.

The objective of this article is to develop and apply several simple and rough indicators for river aquatic ecosystems assessment in order to screen potential chemical stressors. Several indicators, based on toxicity (PNEC) and on legislation levels (EQS) have been developed. All these indicators are ratios that were calculated by using public and private data of concentrations of a large list of compounds during a period of five years, including metals and organic compounds in the lower part of the Llobregat river basin at the intake of the drinking water treatment plant. Additionally, new campaigns were executed for increasing the information available on the presence of compounds not routinely analyzed, such as some other pesticides and pharmaceuticals. In the case of inorganic pollutants, the indicators obtained in this river section showed significant risk especially for zinc, but also for copper, nickel and barium. For organic pollutants, the pesticides terbuthylazine, diazinon, 2-methyl-4-chlorophenoxyacetic (MCPA), and in a few cases, chlorpyrifos and lindane, also showed indexes above the threshold. Among the pharmaceuticals, the antibiotics clarithromycin and ciprofloxacin were the only ones with risk indicators adverse to ecosystems. The specific values of the indexes obtained rely on the quantity and quality of the data available, so their interpretation should take into account that some values can be high due to the use of too conservative toxicological information.

Predicting consumer preferences for mineral composition of bottled and tap water

The overall liking for taste of water was correlated with the mineral composition of selected bottled and tap waters. Sixty-nine untrained volunteers assessed and rated twenty-five different commercial bottled and tap waters from. Water samples were physicochemical characterised by analysing conductivity, pH, total dissolved solids (TDS) and major anions and cations: HCO3-, SO42-, Cl-, NO3-, Ca2+, Mg2+, Na+, and K+. Residual chlorine levels were also analysed in the tap water samples. Globally, volunteers preferred waters rich in calcium bicarbonate and sulfate, rather than in sodium chloride. This study also demonstrated that it was possible to accurately predict the overall liking by a Partial Least Squares regression using either all measured physicochemical parameters or a reduced number of them. These results were in agreement with previously published results using trained panellists.

A novel compound isolated from Sclerochloa dura has anti-inflammatory effects

The activation of PLA 2 by means of pro-inflammatory cytokines results in the subsequent release of arachidonic acid (AA) and generates eicosanoids, which further propagate inflammation. By 6the cyclooxygenases (COX1/2) responsible for the enzymatic conversion of AA to eicosanoids, the non-steroidal anti-inflammatory drugs are effective in relieving the pain and discomfort of inflammation. By using AA release assay as a guide for biological and anti-inflammatory activity, novel compound 1- O -(3- O -linolenoyl-6-deoxy-6-sulfo- α -D-glucopyranosyl)-glycerol (1) together with five known compounds isovitexin, byzantionoside B, tricin 4 ’ - O -(erythro- β -guaiacylglyceryl) ether 7- O - β -glucopyranoside, 1- O -feruloyl glycerol and tricin 7-glucoside were isolated from the methanol extract of the aerial parts of Sclerochloa dura using LC techniques (Sephadex LH-20 column chromatography, preparative HPLC and semi-preparative HPLC). All isolated compounds were identified using spectroscopic NMR spectroscopy and MS spectrometry. Novel compound (1) was found to be an effective inhibitor of AA release with an IC 50 value of 0.09 ± 0.03 mg mL -1 .