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Bru M.,Jaume I University | Alfonso I.,Jordi Girona | Bolte M.,Goethe University Frankfurt | Burguete M.I.,Jaume I University | Luis S.V.,Jaume I University
Chemical Communications | Year: 2011

An anionic dicarboxylate is able to template the formation of geometrically disfavoured macrocycles from a dynamic covalent mixture of open chain oligoimines. © 2011 The Royal Society of Chemistry.


Campo J.,University of Valencia | Masia A.,University of Valencia | Pico Y.,University of Valencia | Farre M.,Jordi Girona | And 2 more authors.
Science of the Total Environment | Year: 2014

The concentrations of 21 perfluoroalkyl substances (PFASs: C4-C14, C16, C18 carboxylates, C4, C6-C8 and C10 sulfonates and C8 sulfonamide) were determined in influent, effluent and sludge from 16 different sewage treatment plants (STPs) located in the Ebro (6), Guadalquivir (5), Jucar (2) and Llobregat (3) Rivers, in two consecutive years (2010 and 2011). The analytes were extracted by solid phase extraction (SPE) and determined by Liquid Chromatography triple Quadrupole Mass Spectrometer (LC-QqQ-MS). All samples, except two sludges from Guadalquivir River STPs, were contaminated with at least one PFAS. Perfluorobutanoate (PFBA), perfluoropentanoate (PFPeA) and perfluorooctane sulfonate (L-PFOS) were the most frequently detected. The highest concentration in water was determined in 2010 in a Guadalquivir River STP (perfluorohexanoate, PFHxA: 5.60μgL-1) and, in 2011, in an Ebro River STP (perfluorobutane sulfonate, L-PFBS: 0.31μgL-1). In sludge samples, the maximum concentration in 2010 was 1.79μgg-1dry weight (dw) (L-PFOS, in a Llobregat River STP), and in 2011, 1.88μgg-1dw (PFBA, in one Guadalquivir River STP). High PFAS values in sludge could be related to positive removal efficiencies, and can be attributed to their adsorption. Distribution coefficients (Kd) were determined ranging between 0.32Lkg-1 (perfluorohexane sulfonate, L-PFHxS) and 36.6 103Lkg-1 (PFBA). The total PFAS loads discharged into the basins showed high values for the Ebro River STPs (66.9gday-1) while in the others, the loads were between 3.97gday-1, in the Jucar STPs, and 32.2gday-1, in the Guadalquivir STPs. © 2013 Elsevier B.V.


Bartrons M.,University of Wisconsin - Madison | Bartrons M.,CSIC - Center for Advanced Studies of Blanes | Grimalt J.O.,Jordi Girona | Catalan J.,CSIC - Center for Advanced Studies of Blanes
Limnetica | Year: 2012

Persistent organic pollutants (POPs) are toxic substances that are usually produced for use in agricultural, industrial, and domestic applications. Because of their long-range atmospheric transport capacity, POPs are distributed worldwide. The global distillation theory predicts that there will be a temperature-dependent partitioning of these low volatility compounds in the environment. Concentration patterns of POPs in agreement with the theory have been observed for different environmental compartments, such as lake sediments and mosses, and along altitudinal and latitudinal gradients. However, concentration patterns in lake fish do not exactly match the expected results, indicating that further investigation into the bioaccumulation processes in food webs is required. Here, we briefly review the state of the question of POPs bioaccumulation in high mountain lake food webs and present some hypotheses concerning processes worthy of investigation. © Asociacion Iberica de Limnologia, Madrid. Spain.


Anglada J.M.,Jordi Girona | Olivella S.,Jordi Girona | Sole A.,University of Barcelona
Physical Chemistry Chemical Physics | Year: 2013

The reaction of formaldehyde carbonyl oxide (H2COO) with the methyl peroxy radical (CH3OO), a prototype of the reactions of carbonyl oxides with alkyl peroxy radicals of potential interest in atmospheric chemistry, has been investigated by means of quantum-mechanical electronic structure methods (CASSCF, CASPT2, UQCISD, and UCCSD(T)) and DFT functionals (B3LYP, BH&HLYP, M05 and M06-2X). Two reaction paths have been found for the lowest-barrier reaction, namely the CH3OO radical addition to the carbon atom of H2COO leading to the formation of the CH 3OOCH2OO radical adduct. Both pathways begin with the formation of a pre-reactive complex with binding energies of 5.39 and 5.13 kcal mol-1. The corresponding transition states are predicted to lie 2.64 and 0.25 kcal mol-1, respectively, below the energy of the reactants and the rate constant of the global reaction is calculated to be 3.74 × 10-12 cm3 molecules-1 s-1 at 298 K. Since the CH3OOCH2OO radical adduct is formed with an internal energy excess of about 45 kcal mol-1, it can decompose unimolecularly into formaldehyde and the CH2(O)OOCH radical. This unimolecular decomposition involves an intramolecular H-atom transfer followed by the decomposition of the CH2OOCH2OOH radical intermediate. Kinetic calculations based on the collision-reaction master equation employing the MultiWell Program Suite reveal that the CH 3OOCH2OO radical adduct is stabilized in 86.9%, whereas 13.10% of the reaction corresponds to the formation of H2CO plus the CH2(O)OOH radical. It is concluded that the methyl peroxy radical addition to substituted carbonyl oxides might be the source of low volatility oligomers observed in secondary organic aerosols in chamber studies. © 2013 the Owner Societies.


Damasio J.,Jordi Girona | Damasio J.,University of Aveiro | Fernandez-Sanjuan M.,Jordi Girona | Sanchez-Avila J.,Jordi Girona | And 5 more authors.
Water Research | Year: 2011

Biological indexes, based on benthic macroinvertebrate taxa, are currently used worldwide to measure river ecological quality. These indexes assign a global ecological status of the biotic community, but not necessarily may detect specific effects of water pollutants. Conversely a large set of biochemical markers measured in macroinvertebrate benthic species can detect sublethal effects and inform us about additional environmental factors that are impairing benthic communities. This is especially interesting in moderately polluted sites, where other stressors are already affecting communities but not too strongly to be detected by biotic indexes. Up to ten different markers belonging to distinct metabolic paths and 42 contaminants measured in sample collections of the caddis fly Hydropsyche exocellata were assessed across a polluted gradient in the industrialized Mediterranean River basins of Besós and Llobregat (NE, Spain). Twenty four sample collections were selected to include macroinvertebrate communities representing the five impairment degrees defined by the Spanish Environmental authorities using the biotic metrics. Results evidenced a clear deterioration of the ecological water quality parameters and benthic communities towards downstream reaches. Biochemical responses varied significantly across the studied samples and were able to differentiate samples within communities having a good and deteriorated ecological stage. Principal Component Analyses indicated that salinity was one of the major stresses affecting macroinvertebrate assemblages, whereas antioxidant and metabolizing enzymes responded differently and were closely related to high and presumably toxic levels of accumulated organic pollutants. Therefore these results indicate that the use of multiple -markers sensitive to water pollution may provide complementary information to diagnose environmental factors that are impairing macroinvertebrate communities. © 2011 Elsevier Ltd.


Cirpka O.A.,University of Tübingen | Rolle M.,University of Tübingen | Rolle M.,Stanford University | Chiogna G.,University of Trento | And 2 more authors.
Journal of Contaminant Hydrology | Year: 2012

We study plumes originating from continuous sources that require a dissolved reaction partner for their degradation. The length of such plumes is typically controlled by transverse mixing. While analytical expressions have been derived for homogeneous flow fields, incomplete characterization of the hydraulic conductivity field causes uncertainty in predicting plume lengths in heterogeneous domains. In this context, we analyze the effects of three sources of uncertainty: (i) The uncertainty of the effective mixing rate along the plume fringes due to spatially varying flow focusing, (ii) the uncertainty of the volumetric discharge through (and thus total mass flux leaving) the source area, and (iii) different parameterizations of the Darcy-scale transverse dispersion coefficient. The first two are directly related to heterogeneity of hydraulic conductivity. In this paper, we derive semi-analytical expressions for the probability distribution of plume lengths at different levels of complexity. The results are compared to numerical Monte Carlo simulations. Uncertainties in mixing and in the source strength result in a statistical distribution of possible plume lengths. For unconditional random hydraulic conductivity fields, plume lengths may vary by more than one order of magnitude even for moderate degrees of heterogeneity. Our results show that the uncertainty of volumetric flux through the source is the most relevant contribution to the variance of the plume length. The choice of different parameterizations for the local dispersion coefficient leads to differences in the mean estimated plume length. © 2012 Elsevier B.V.


Rodrigues A.C.M.,University of Aveiro | Gravato C.,University of Aveiro | Quintaneiro C.,University of Aveiro | Barata C.,Jordi Girona | And 2 more authors.
Environmental Pollution | Year: 2015

Integrative studies focused on sub-organismal responses to pyrethroid exposure are important to understand life history responses. In this study, the ecotoxicological effects of esfenvalerate (ESF) on Chironomus riparius were assessed using five biochemical biomarkers related to neurophysiological function (acetylcholinesterase) and oxidative stress (catalase; glutathione-S-transferase; total glutathione and lipid peroxidation). In addition, effects on cellular energy allocation were assessed and all results were compared with organismal level responses (larval growth, emergence and sex ratio). Exposure to sub-lethal concentrations of ESF caused the failure of C. riparius antioxidant defenses (inhibition of catalase activity and decreased levels of total glutathione), which was reflected as oxidative damage. C. riparius energy budget was decreased by exposure to ESF due to an increased energy consumption. Life cycle tests showed that exposure to ESF impaired C. riparius developmental rates and increased male:female ratios, thereby confirming its toxicity and potential population level effects at environmentally relevant concentrations. © 2015 Elsevier Ltd. All rights reserved.


PubMed | University of South Bohemia, Jordi Girona and University of Aveiro
Type: | Journal: Aquatic toxicology (Amsterdam, Netherlands) | Year: 2016

Recent advances in video tracking technologies provide the tools for a sensitive and reproducible analysis of invertebrate activity under stressful conditions nurturing the field of behavioural ecotoxicology. This study aimed to evaluate behavioural responses of the freshwater planarian Dugesia subtentaculata exposed to a model compound, chlorantraniliprole (CAP). This compound is an anthranilic diamide insecticide and due to its neurotoxic action can, at low concentrations, impair behaviour of exposed organisms. Behavioural endpoints measured included feeding and locomotor activities. Feeding responses were based on planarian predatory behaviour using Chironomus riparius larvae as prey. Locomotion was measured by the traditional planarian locomotor velocity (pLMV) assay and additionally using an automated video tracking system using a Zebrabox() (Viewpoint, France) device. While feeding and pLMV were significantly impaired at 131.7g/L CAP, the video tracking system showed that total distance covered by planarians was significantly reduced at concentrations as low as 26.2g/L CAP. Our results show that more advanced automated video recording systems can be used in the development of sensitive bioassays allowing a reliable, time- and cost-effective quantification of behaviour in aquatic invertebrates. Due to their ecological relevance, behavioural responses should not be disregarded in risk assessment strategies and we advocate the suitability of planarians as suitable organisms for behavioural ecotoxicological studies.


Bayona J.M.,Jordi Girona | Dominguez C.,Jordi Girona | Albaiges J.,Jordi Girona
Trends in Environmental Analytical Chemistry | Year: 2015

Oil fingerprinting is widely used to defensibly determine the source of an oil spill by matching compositional parameters of both the spilled oil and candidate sources. The unambiguous identification of oil sources and their characteristics are of paramount importance for assessing the fate and environmental damage of the spill, provide an appropriate spill response and also for assigning responsibilities and liabilities. The most widely used methodologies in Europe and USA are, respectively, the CEN TR15522-2 and the ASTM5739-00 standard norms. Oil fingerprinting is currently based on profiling specific source biomarkers by GC-MS. However, new developments in gas chromatography and mass spectrometry (GC-MS/MS, GC. ×. GC-FID-TOF, GC-IRMS) have allowed an enhanced sensitivity, selectivity, resolution and isotopic determination of oil biomarkers, providing additional tools for oil fingerprinting. Spectroscopic (fluorescence, FT-IR) and ultra-high resolution mass spectrometry methods (FT-ICRMS) have also shown a great potential in oil characterization. In this review, analytical, chemometric and remote sensing developments that have been used for fingerprinting and environmental fate studies of oil spills will be presented. © 2015 Elsevier B.V.


Gomez-Canela C.,Jordi Girona | Lacorte S.,Jordi Girona
Environmental Science and Pollution Research | Year: 2016

The occurrence of 10 commonly used anticoagulant rodenticides in centrifuged sludge of 27 wastewater treatment plants was evaluated using solid-liquid extraction (SLE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS). Activated carbon, alumina, and Florisil cartridges with methanol/dichloromethane as eluting solvents were tested in combination with primary-secondary amine (PSA) to optimize an efficient sample cleanup. PSA in combination with Florisil was the best methodology to extract anticoagulant rodenticides in sludge providing recoveries between 42 ± 0.5 and 100 ± 2 %. Warfarin, bromadiolone, ferulenol, and coumachlor were the most ubiquitous compounds in sludge at concentrations up to 84.2 ng g−1 for the latter. Coumatetralyl, dicoumarol, and brodifacoum were detected sporadically at levels between 6.1 and 17.4 ng g−1. On the contrary, acenocoumarol, difenacoum, and flocoumafen were not detected in any sample. Finally, we estimated the amount of anticoagulant rodenticides discharged via sludge in order to determine the potential impact to agricultural soil according to different sludge usage practices in the region investigated. This study demonstrates that anticoagulant rodenticides are accumulated in sludge during activated sludge treatment and that the application of sludge as fertilizers may pose a future environmental risk, if not controlled. © 2016 Springer-Verlag Berlin Heidelberg

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