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Flores C.,Mass Spectrometry Laboratory Organic Pollutants | Ventura F.,IDAEA | Martin-Alonso J.,AGBAR Aigues de Barcelona | Caixach J.,Mass Spectrometry Laboratory Organic Pollutants
Science of the Total Environment | Year: 2013

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are two emerging contaminants that have been detected in all environmental compartments. However, while most of the studies in the literature deal with their presence or removal in wastewater treatment, few of them are devoted to their detection in treated drinking water and fate during drinking water treatment. In this study, analyses of PFOS and PFOA have been carried out in river water samples and in the different stages of a drinking water treatment plant (DWTP) which has recently improved its conventional treatment process by adding ultrafiltration and reverse osmosis in a parallel treatment line. Conventional and advanced treatments have been studied in several pilot plants and in the DWTP, which offers the opportunity to compare both treatments operating simultaneously. From the results obtained, neither preoxidation, sand filtration, nor ozonation, removed both perfluorinated compounds. As advanced treatments, reverse osmosis has proved more effective than reverse electrodialysis to remove PFOA and PFOS in the different configurations of pilot plants assayed. Granular activated carbon with an average elimination efficiency of 64. ±. 11% and 45. ±. 19% for PFOS and PFOA, respectively and especially reverse osmosis, which was able to remove ≥. 99% of both compounds, were the sole effective treatment steps. Trace levels of PFOS (3.0-21. ng/L) and PFOA (<. 4.2-5.5. ng/L) detected in treated drinking water were significantly lowered in comparison to those measured in precedent years. These concentrations represent overall removal efficiencies of 89. ±. 22% for PFOA and 86. ±. 7% for PFOS. © 2013 Elsevier B.V.

Calderon-Preciado D.,IDAEA | Matamoros V.,University of Girona | Bayona J.M.,IDAEA
Science of the Total Environment | Year: 2011

Emerging contaminants have received much attention in recent years due to their presence in surface waters, but little attention has been paid to their occurrence in agricultural irrigation waters. This study investigated the occurrence of these compounds in an agricultural irrigation network in northeastern Spain and, for the first time, using two plant uptake models, estimated the concentration of selected micropollutants in crops. The concentration of micropollutants in agricultural irrigation waters ranged from 10 to 5130ngL -1 and exhibited some attenuation over the course of the irrigation network. Bromoform, chloroform, diclofenac, caffeine, ibuprofen, naproxen, methyl dihydrojasmonate, galaxolide, butylated hydroxytoluene, and butylated hydroxyanisole were the most abundant contaminants (>200ngL -1, on average). The estimated concentration of micropollutants in crops ranged from <1 to 7677ngkg -1, with the neutral compounds being the most abundant. Moreover, the predicted data obtained by fate models generally agreed with experimental data. Finally, human exposure to micropollutants through fruit and vegetable consumption was estimated to be 9.8μg per person and week (σ 27 contaminants detected). Further studies are needed to determine the health implications that the presence of these compounds in fruit and vegetables may have for consumers. © 2011 Elsevier B.V.

Feo M.L.,IDAEA. | Eljarrat E.,IDAEA. | Barcelo D.,IDAEA. | Barcelo D.,Catalan Institute for Water Research
Journal of Chromatography A | Year: 2010

A simple, efficient and environmentally friendly analytical methodology is proposed for extracting and preconcentrating pyrethroids from water samples prior to gas chromatography-negative ion chemical ionization mass spectrometry (GC-NCI-MS) analysis. Fourteen pyrethroids were selected for this work: bifenthrin, cyfluthrin, λ-cyhalothrin, cypermethrin, deltamethrin, esfenvalerate, fenvalerate, fenpropathrin, τ-fluvalinate, permethrin, phenothrin, resmethrin, tetramethrin and tralomethrin. The method is based on ultrasound-assisted emulsification-extraction (UAEE) of a water-immiscible solvent in an aqueous medium. Chloroform was used as extraction solvent in the UAEE technique. Target analytes were quantitatively extracted achieving an enrichment factor of 200 when 20mL aliquot of pure water spiked with pyrethroid standards was extracted. The method was also evaluated with tap water and river water samples. Method detection limits (MDLs) ranged from 0.03 to 35.8ngL-1 with RSDs values ≤3-25% (n=5). The coefficients of estimation of the calibration curves obtained following the proposed methodology were ≥0.998. Recovery values were in the range of 45-106%, showing satisfactory robustness of the method for analyzing pyrethroids in water samples. The proposed methodology was applied for the analysis of river water samples. Cypermethrin was detected at concentration levels ranging from 4.94 to 30.5ngL-1. © 2010 Elsevier B.V.

Dentz M.,IDAEA | Tartakovsky D.M.,University of California at San Diego
Geophysical Research Letters | Year: 2010

Spatial and temporal heterogeneity of ambient natural environments play a significant role in large scale transport phenomena. Uncertainty about spatio-temporal fluctuations in system parameters (e.g., flow velocity) make deterministic predictions of macroscopic system states (e.g., solute concentration) elusive. Distributions of system states generally exhibit highly non-Gaussian behavior, which cannot be captured solely by the corresponding mean and variance. Instead, these features of transport are described by the probability density function (PDF) of a system state, e.g., the PDF of concentration at a certain point in space and time. We study the PDF of a passive scalar that disperses in a random velocity field. We derive an explicit map between the velocity distribution and the scalar PDF, and obtain approximate solutions for the PDF of the normalized scalar. These solutions enable one to quantify explicitly the impact of dispersion on the evolution of the passive scalar PDF without recurrence to classical closure approximations used in mixing models. Copyright 2010 by the American Geophysical Union.

Lana A.,CSIC - Institute of Marine Sciences | Simo R.,CSIC - Institute of Marine Sciences | Vallina S.M.,Massachusetts Institute of Technology | Dachs J.,IDAEA
Atmospheric Chemistry and Physics | Year: 2012

Aerosols have a large potential to influence climate through their effects on the microphysics and optical properties of clouds and, hence, on the Earth's radiation budget. Aerosol-cloud interactions have been intensively studied in polluted air, but the possibility that the marine biosphere plays an important role in regulating cloud brightness in the pristine oceanic atmosphere remains largely unexplored. We used 9 yr of global satellite data and ocean climatologies to derive parameterizations of the temporal variability of (a) production fluxes of sulfur aerosols formed by the oxidation of the biogenic gas dimethylsulfide emitted from the sea surface; (b) production fluxes of secondary organic aerosols from biogenic organic volatiles; (c) emission fluxes of biogenic primary organic aerosols ejected by wind action on sea surface; and (d) emission fluxes of sea salt also lifted by the wind upon bubble bursting. Series of global monthly estimates of these fluxes were correlated to series of potential cloud condensation nuclei (CCN) numbers derived from satellite (MODIS). More detailed comparisons among weekly series of estimated fluxes and satellite-derived cloud droplet effective radius (r e) data were conducted at locations spread among polluted and clean regions of the oceanic atmosphere. The outcome of the statistical analysis was that positive correlation to CCN numbers and negative correlation to r e were common at mid and high latitude for sulfur and organic secondary aerosols, indicating both might be important in seeding cloud droplet activation. Conversely, primary aerosols (organic and sea salt) showed widespread positive correlations to CCN only at low latitudes. Correlations to r e were more variable, non-significant or positive, suggesting that, despite contributing to large shares of the marine aerosol mass, primary aerosols are not widespread major drivers of the variability of cloud microphysics. Validation against ground measurements pointed out that the parameterizations used captured fairly well the variability of aerosol production fluxes in most cases, yet some caution is warranted because there is room for further improvement, particularly for primary organic aerosol. Uncertainties and synergies are discussed, and recommendations of research needs are given. © 2012 Author(s).

Lopez-Serna R.,IDAEA | Petrovic M.,Catalan Institute for Water Research | Petrovic M.,Catalan Institution for Research and Advanced Studies | Barcelo D.,IDAEA | Barcelo D.,Catalan Institute for Water Research
Journal of Chromatography A | Year: 2012

The work describes the development and validation of an analytical method for simultaneous determination of 58 pharmaceuticals and 19 metabolites and transformation products in environmental waters. The method is fully automated and consists of a direct injection of a small volume (several mL) of water sample to an on-line system composed of TurboFlow™ chromatography for the extraction and clean-up followed by liquid chromatography-electrospray-tandem mass spectrometry (TFC-LC-ESI-MS/MS). The feasibility and limitations of the technique in the analysis of environmental and wastewaters is discussed. The main advantages include high throughput, minimum sample manipulation, low error introduction, high selectivity, sensibility and reliability. The method provided a tool for the determination of a high number of active metabolites and transformation products and was successfully applied in the analysis of samples from the river Ebro basin. © 2012 Elsevier B.V.

Benzothiazoles (BTHs) and benzotriazoles (BTRs) belong to a high production volume chemicals widely used in both industrial and household applications. Since they are recalcitrant to biodegradation, they are widespread in the environment. However, the BTHs and BTRs determination in environmental matrices is hindered by the coelution with coextracted organic matter and the poor selectivity in mass spectrometry due to the low mass of their diagnostic ions. Accordingly, this study examines the selectivity and suitability of new commercially available ionic liquid (IL) stationary phases for GC-MS and their application to the determination of BTHs and BTRs in wastewater samples. Five different IL columns were tested and the best results in terms of resolution, peak symmetry and analysis time were obtained with the SLB-IL59. © 2012 Elsevier B.V.

Calderon-Preciado D.,IDAEA | Jimenez-Cartagena C.,IDAEA | Jimenez-Cartagena C.,University of Antioquia | Matamoros V.,University of Girona | Bayona J.M.,IDAEA
Water Research | Year: 2011

Reclaimed water usage for crop irrigation is viewed both as an excellent sustainable water source and as a potential entrance for emerging organics into the food chain. This concern is backed by the already documented pollutant crop uptake potential. In the present study, irrigation waters used in agricultural fields (Torroella de Montgri, NE Spain) were screened for 47 analytes in a two year study (2007-2008). A total of 26 contaminants belonging to different chemical classes namely, pesticides, pharmaceuticals, personal care products, phenolic estrogens, antioxidants and disinfection by-products, were detected. Marked differences in concentration trends for the different chemical classes were evidenced from 2007 to 2008, and attributed to a persistent drought endured by the region in 2008. Also, loading mass rates of chemical classes were estimated based on crop irrigation regimes and they ranged from 0.8 to 121.3 g ha -1 per crop cycle. These values were contrasted with those obtained for other water sources from countries where crop irrigation is commonly practiced. Finally, crops grown under these irrigation regimes, namely alfalfa and apple, were analyzed and 5 anthropogenic compounds were identified and quantitated, whose concentrations ranged from 13.9 to 532 ng g -1 (fresh weight). © 2010 Elsevier Ltd.

Garcia-Galan M.J.,IDAEA | Diaz-Cruz S.,IDAEA | Barcelo D.,IDAEA | Barcelo D.,Catalan Institute for Water Research
Journal of Chromatography A | Year: 2013

The present study describes the development, validation and a practical application of a fully automated analytical method based on pressurized liquid extraction (PLE) followed by solid-phase extraction-liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) for the simultaneous determination of 22 sulfonamides, including five acetylated metabolites, in sewage sludge and soil samples. Both matrix matched calibration curves and standard calibration curves were built in order to evaluate the potential matrix effects during analysis, and different internal standards were used to compensate these effects during quantification. The recovery efficiencies were found to be 60-130% for the majority of the sulfonamides in both matrices and at two spike levels. The intra-day and inter-day precisions, expressed by the relative standard deviation (RSD), were below 23%. The method limits of detection (MLODs) achieved were in the range 0.03-2.23ngg-1 for sewage sludge and 0.01-4.19ngg-1 for soil samples. The methodology was applied to evaluate the occurrence of the target sulfonamides in several sewage sludge and soil samples taken in different wastewater treatment plants (WWTPs) and agricultural areas. Results confirmed the wide presence of sulfonamides in both matrices, being sulfathiazole and sulfamethazine the sulfonamides most frequently detected in sewage sludge and soil samples, respectively. Maximum concentrations corresponded to sulfamethazine in both cases (139.2ngg-1 and 8.53ngg-1 for sewage sludge and soils respectively). Levels were generally lower in soils. Three of the five acetylated metabolites were detected in sewage sludge and two of them in soils, at concentrations not higher than 9.81ngg-1. © 2012 Elsevier B.V.

Sanchez-Trujillo M.A.,CSIC - Institute of Natural Resources and Agriculture Biology of Seville | Morillo E.,CSIC - Institute of Natural Resources and Agriculture Biology of Seville | Villaverde J.,CSIC - Institute of Natural Resources and Agriculture Biology of Seville | Lacorte S.,IDAEA
Environmental Pollution | Year: 2013

The objective of the present study was to characterise the polycyclic aromatic hydrocarbons (PAHs) content of an aged contaminated soil and to propose remediation techniques using cyclodextrins (CDs). Four CDs solutions were tested as soil decontamination tool and proved more efficient in extracting PAHs than when an aqueous solution was used; especially two chemically modified CDs resulted in higher extraction percentages than natural β-CD. The highest extraction percentages were obtained for 3-ring PAHs, because of the appropriate size and shape of these compounds relative to those of the hydrophobic cavities of the CDs studied. A detailed mechanistic interpretation of the chemical modification of CDs on the extraction of the different PAHs has been performed, and connected with the role that the different hydrophobicities of the PAHs play in the extraction behaviour observed for the 16 PAHs, limiting their accessibility and the remaining risk of those PAHs not extractable by CDs. © 2013 Elsevier Ltd. All rights reserved.

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