RESUMEN
The levels and trends of four bioaccumulative synthetic musks (galaxolide - HHCB, tonalide - AHTN, musk xylene - MX and musk ketone - MK) were investigated in filter-feeding bivalves collected yearly since 2010 at sites of contrasted pressure along the French coasts. Quantification rates were high for all 4 compounds (85-99%), indicating their geographical and temporal extensive occurrence in the French coastal environment. The polycyclic musks HHCB and AHTN prevailed, with median concentrations of 2.27 ng g-1 dw and of 0.724 ng g-1 dw, whilst nitromusks were found 1 to 2 orders of magnitude lower. These levels were in the high range of those encountered for various other CEC families at the same sites and comparable to those from other locations on European coasts. Unlike for the other musks, the accumulation of HHCB was evidenced to be species-specific, with significantly lower levels found in oysters in comparison with mussels, possibly suggesting a higher metabolization in oysters. Geographical differences in musk distribution highlighted the sites under strong anthropogenic pressures and these differences were found to be consistent between years. The HHCB/AHTN ratio proved to be discriminant to explain the relative occurrence of polycyclic musks. The 8-year time series showed that only the now-banned compound MX displayed a significant decrease in most sites, whilst stable concentrations of the other musks suggested consistency in their usage over the last decade. These results provide reference data for future studies of the occurrence of personal care products on European coasts.
Asunto(s)
Bivalvos , Cosméticos , Contaminantes Químicos del Agua , Animales , Benzopiranos/análisis , Ácidos Grasos Monoinsaturados , Humanos , Proteínas Tirosina Quinasas Receptoras , Receptores Colinérgicos , Tetrahidronaftalenos/análisis , Contaminantes Químicos del Agua/análisisRESUMEN
In the present work, we address the issue of nontargeted screening of organohalogenated chemicals in complex matrixes. A global strategy aiming to seek halogenated signatures in full-scan high-resolution mass spectrometry (HRMS) fingerprints was developed. The resulting all-in-one user-friendly application, HaloSeeker 1.0, was developed to promote the accessibility of associated in-house bioinformatics tools to a large audience. The ergonomic web user interface avoids any interactions with the coding component while allowing interactions with the data, including peak detection (features), deconvolution, and comprehensive accompanying manual review for chemical formula assignment. HaloSeeker 1.0 was successfully applied to a marine sediment HRMS data set acquired on a liquid chromatography-heated electrospray ionization [LC-HESI(-)] Orbitrap instrument ( R = 140 000 at m/z 200). Among the 4532 detected features, 827 were paired and filtered in 165 polyhalogenated clusters. HaloSeeker was also compared to three similar tools and showed the best performances. HaloSeeker's ability to filter and investigate halogenated signals was demonstrated and illustrated by a potential homologue series with C12H xBr yCl zO2 as a putative general formula.
RESUMEN
We reviewed compliance monitoring requirements in the European Union, the United States, and the Oslo-Paris Convention for the protection of the marine environment of the North-East Atlantic, and evaluated if these are met by passive sampling methods for nonpolar compounds. The strengths and shortcomings of passive sampling are assessed for water, sediments, and biota. Passive water sampling is a suitable technique for measuring concentrations of freely dissolved compounds. This method yields results that are incompatible with the EU's quality standard definition in terms of total concentrations in water, but this definition has little scientific basis. Insufficient quality control is a present weakness of passive sampling in water. Laboratory performance studies and the development of standardized methods are needed to improve data quality and to encourage the use of passive sampling by commercial laboratories and monitoring agencies. Successful prediction of bioaccumulation based on passive sampling is well documented for organisms at the lower trophic levels, but requires more research for higher levels. Despite the existence of several knowledge gaps, passive sampling presently is the best available technology for chemical monitoring of nonpolar organic compounds. Key issues to be addressed by scientists and environmental managers are outlined.
Asunto(s)
Monitoreo del Ambiente/métodos , Compuestos Orgánicos/análisis , Contaminantes Químicos del Agua/análisis , Biota , Sedimentos Geológicos/química , Compuestos Orgánicos/químicaRESUMEN
PCB levels in plankton were investigated in the Bay of Marseille, Western Mediterranean Sea, between September 2010 and October 2011. Concentrations of PCB congeners (CB 18, CB 52, CB 101, CB 118, CB 138, CB 153, CB 180) were determined in three plankton size-classes (60-200, 200-500 and 500-1000µm) together with different parameters: chlorophyll content, plankton dry-weight biomass, carbon and nitrogen stable isotope ratios and plankton-community structure. The ∑PCB7 concentrations ranged between 14.2 and 88.1ngg(-1)d.w., for all size classes and all sampling periods. The results do not show the biomass dilution effect and indicate moderate but significant biomagnification with plankton trophic position estimated by δ(15)N signatures. Equilibrium with water phase may notably contribute in controlling the PCB levels in the plankton. More generally, presented results imply that PCB accumulation in the plankton is an effect of abiotic and trophic complex interactions in the Bay of Marseille.
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Cadena Alimentaria , Plancton/química , Bifenilos Policlorados/análisis , Contaminantes Químicos del Agua/análisis , Bahías , Biomasa , Isótopos de Carbono/análisis , Clorofila/análisis , Monitoreo del Ambiente , Mar Mediterráneo , Isótopos de Nitrógeno/análisis , Estaciones del AñoRESUMEN
Marine biotoxins are algal metabolites that can accumulate in fish or shellfish and render these foodstuffs unfit for human consumption. These toxins, released into seawater during algal occurrences, can be monitored through passive sampling. Acetone, methanol and isopropanol were evaluated for their efficiency in extracting toxins from algal biomass. Isopropanol was chosen for further experiments thanks to a slightly higher recovery and no artifact formation. Comparison of Oasis HLB, Strata-X, BondElut C18 and HP-20 sorbent materials in SPE-mode led to the choice of Oasis HLB, HP-20 and Strata-X. These three sorbents were separately exposed as passive samplers for 24 h to seawater spiked with algal extracts containing known amounts of okadaic acid (OA), azaspiracids (AZAs), pinnatoxin-G (PnTX-G), 13-desmethyl spirolide-C (SPX1) and palytoxins (PlTXs). Low density polyethylene (LDPE) and silicone rubber (PDMS) strips were tested in parallel on similar mixtures of spiked natural seawater for 24 h. These strips gave significantly lower recoveries than the polymeric sorbents. Irrespective of the toxin group, the adsorption rate of toxins on HP-20 was slower than on Oasis HLB and Strata-X. However, HP-20 and Strata-X gave somewhat higher recoveries after 24 h exposure. Irrespective of the sorbent tested, recoveries were generally highest for cyclic imines and OA group toxins, slightly lower for AZAs, and the lowest for palytoxins. Trials in re-circulated closed tanks with mussels exposed to Vulcanodinium rugosum or Prorocentrum lima allowed for further evaluation of passive samplers. In these experiments with different sorbent materials competing for toxins in the same container, Strata-X accumulated toxins faster than Oasis HLB, and HP-20, and to higher levels. The deployment of these three sorbents at Ingril French Mediterranean lagoon to detect PnTX-G in the water column showed accumulation of higher levels on HP-20 and Oasis HLB compared to Strata-X. This study has significantly extended the range of sorbents for passive sampling of marine toxins. In particular, sorbents were included that had previously been evaluated for polyhalogenated contaminants, pharmaceuticals, phytochemicals or veterinary residues. Moreover, this study has for the first time demonstrated the usefulness of the polymeric Oasis HLB and Strata-X sorbents in laboratory and field studies for various microalgal toxins.
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Lípidos/química , Toxinas Marinas/análisis , Polímeros/química , Toxinas Marinas/químicaRESUMEN
Pore concentration and partition coefficients of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were determined in sediments from five distinct contaminated sites in France (marine harbour, rivers canals and highway sedimentation tank). The assessment of the risk caused by such micropollutants requires, in most cases, the measurement of their availability. To assess this availability, low density polyethylene (LDPE) membrane samplers were exposed to these sediments under constant and low-level agitation over a period of 46 days. Freely dissolved pore water contaminant concentrations were estimated from the concentration at equilibrium in the LDPE membrane. The depletion of contaminants in the sediments was monitored by the use of performance reference compounds (PRCs). Marked differences in freely dissolved PAH and PCB concentrations and resulting sediment-pore water partition coefficients between these five sediments were observed. Data set was tested onto different empirical and mechanistic models. As final findings, triple domain sorption (a total organic carbon, black carbon and oil phase model) could model PCB data successfully whereas the best fitting for PAH partitioning was obtained by Raoult's Law model.
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Monitoreo del Ambiente/métodos , Sedimentos Geológicos/química , Bifenilos Policlorados/análisis , Hidrocarburos Policíclicos Aromáticos/análisis , Navíos , Contaminantes Químicos del Agua/análisis , Monitoreo del Ambiente/instrumentación , Francia , Polietileno , RíosRESUMEN
This study aimed at evaluating and comparing five integrative samplers for the monitoring of indicator and dioxin-like polychlorinated biphenyls (PCBs) in water: semi-permeable membrane device (SPMD), silicone rubber, low-density polyethylene (LDPE) strip, Chemcatcher and a continuous-flow integrative sampler (CFIS). These samplers were spiked with performance reference compounds (PRCs) and then simultaneously exposed under constant agitation and temperature in a 200 L stainless steel tank for periods ranging from one day to three months. A constant PCB concentration of about 1 ng·L(-1) was achieved by immersing a large amount of silicone rubber sheets ("dosing sheets") spiked with the target PCBs. The uptake of PCBs in the five samplers showed overall good repeatability and their accumulation was linear with time. The samplers SPMD, silicone rubber and LDPE strip were the most promising in terms of achieving low limits of quantification. Time-weighted average (TWA) concentrations of PCBs in water were estimated from uptake of PCBs using the sampling rates calculated from the release of PRCs. Except for Chemcatcher, a good agreement was found between the different samplers and TWA concentrations ranged between 0.4 and 2.8 times the nominal water concentration. Finally, the influence of calculation methods (sampler-water partition coefficients, selected PRCs, models) on final TWA concentrations was studied.
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Dioxinas/análisis , Monitoreo del Ambiente/instrumentación , Bifenilos Policlorados/análisis , Contaminantes Químicos del Agua/análisis , Monitoreo del Ambiente/métodos , Dibenzodioxinas Policloradas , Temperatura , Agua/químicaRESUMEN
Chemical contamination of the coastal marine environment by polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) was assessed along with emerging contaminants such as polybrominated diphenyl ethers (PBDEs) in an industrially well-developed country (France) and a fast-developing country (Korea). Other chemicals, i.e. nonylphenol (NP) and 5 beta(H)-cholestan-3beta-ol (coprostanol) were determined to trace industrial waste and/or domestic inputs. These compounds were analyzed in coastal sediments and mussels in two enclosed coastal water bodies: Masan Bay (South Korea) and Thau lagoon (France). The overall levels of target organic contaminants were higher in Masan Bay than in Thau lagoon. The mean concentrations of 17 PCDD/Fs, 13 PBDEs, NP and coprostanol in Masan Bay sediments were, respectively, 1.3, 11, 248 and 291 ng g(-1) dry weight (d.w.); in Thau lagoon sediments they were, respectively, 0.39, not detectable (nd), 23 and 395 ng g(-1)d.w. Mean concentrations in mussels (coprostanol and cholestanol were not measured) were 0.0093, 13, 140 ng g(-1)d.w. in Masan Bay and 0.016, 0.94, 38 ng g(-1)d.w. in Thau lagoon. Principal component analysis of the contaminants and chemical tracers indicates possible point sources of pollution for Masan Bay and Thau lagoon. This study highlights a growing pollution problem in Asia and in particular a tremendous uptrend in Korea, in comparison to more controlled discharges and releases in Western Europe.
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Benzofuranos/análisis , Contaminantes Ambientales/análisis , Éteres Difenilos Halogenados/análisis , Fenoles/análisis , Dibenzodioxinas Policloradas/análogos & derivados , Animales , Benzofuranos/química , Bivalvos/química , Dibenzofuranos Policlorados , Monitoreo del Ambiente , Contaminantes Ambientales/química , Francia , Sedimentos Geológicos/química , Éteres Difenilos Halogenados/química , Residuos Industriales , Fenoles/química , Dibenzodioxinas Policloradas/análisis , Dibenzodioxinas Policloradas/química , Análisis de Componente Principal , República de Corea , Contaminantes del Suelo/análisis , Contaminantes del Suelo/químicaRESUMEN
Although various single-concentration measurements of pharmaceuticals are available in the literature, detailed information on the variation over time of the concentration and the load in wastewater effluents and rivers and on the fate of these compounds in the aquatic environment are lacking. We measured the concentrations of six pharmaceuticals, carbamazepine, clofibric acid, diclofenac, ibuprofen, ketoprofen, and naproxen, in the effluents of three wastewater treatment plants (WWTPs), in two rivers and in the water column of Lake Greifensee (Switzerland) over a time period of three months. In WWTP effluents, the concentrations reached 0.95 microg/L for carbamazepine, 0.06 microg/L for clofibric acid, 0.99 microg/L for diclofenac, 1.3 microg/L for ibuprofen, 0.18 microg/L for ketoprofen, and 2.6 microg/L for naproxen. The relative importance in terms of loads was carbamazepine, followed by diclofenac, naproxen, ibuprofen, clofibric acid, and ketoprofen. An overall removal rate of all these pharmaceuticals was estimated in surface waters, under real-world conditions (in a lake), using field measurements and modeling. Carbamazepine and clofibric acid were fairly persistent. Phototransformation was identified as the main elimination process of diclofenac in the lake water during the study period. With a relatively high sorption coefficient to particles, ibuprofen might be eliminated by sedimentation. For ketoprofen and naproxen, biodegradation and phototransformation might be elimination processes. For the first time, quantitative data regarding removal rates were determined in surface waters under real-world conditions. All these findings are important data for a risk assessment of these compounds in surface waters.
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Preparaciones Farmacéuticas/análisis , Contaminantes Químicos del Agua/análisis , Monitoreo del Ambiente , Medición de Riesgo , Eliminación de Residuos LíquidosRESUMEN
Since its design 25 years ago (Olton & Samuelson, 1976), the eight-arm radial maze has become very popular and is now widely used to assess spatial memory in rodents. Two versions of the full-baited maze protocol are present in the literature: with or without confinement between the visit of each arm. The confinement was introduced by Olton himself as early as 1977 (Olton, Collison, & Werz, 1977) to eliminate stereotypic behaviors that he had previously observed. It is widely regarded that the confinement prevents rodents from developing these response patterns, and as such it is considered an improved procedure to test spatial memory. Surprisingly, to the best of our knowledge, no study has been especially designed to demonstrate the efficacy of the confinement in blocking the stereotypic behaviors of the animals. The present study compares the strategies of rats trained with or without a confinement procedure. The results show that, after nine days of training, rats submitted to a 5- or a 10-s confinement reach the same level of performance as rats without confinement. The confinement totally prevents stereotypic behaviors like clockwise serial searching strategies which are often observed without confinement. Even a 0-s confinement is sufficient to prevent clockwise strategies, but rats seem to develop other stratagems which do not imply spatial memory. Furthermore, rats previously trained without confinement are unable to perform the task when confinement is introduced on a test day. In contrast, rats previously trained with confinement perform the task correctly when the confinement is no longer present. Thus, without confinement, good levels of performance can be achieved without precise spatial representations.
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Aprendizaje por Laberinto/fisiología , Memoria/fisiología , Conducta Espacial/fisiología , Animales , Masculino , Ratas , Ratas Sprague-Dawley , Factores de TiempoRESUMEN
The phototransformation of the widely used biocide triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol) was quantified for surface waters using artificial UV light and sunlight irradiation. The pH of surface waters, commonly ranging from 7 to 9, determines the speciation of triclosan (pKa = 8.1) and therefore its absorption of sunlight. Direct phototransformation of the anionic form with a quantum yield of 0.31 (laboratory conditions at 313 nm) was identified as the dominant photochemical degradation pathway of triclosan. Combining the photochemical parameters with actual meteorological data and field measurements allowed us to validate a model describing the behavior of triclosan in the water column of a Swiss lake (Lake Greifensee). From August to October 1999, direct phototransformation accounted for 80% of the observed total elimination of triclosan from the lake. The remaining major sink for triclosan was the loss in the outflow. Thus, during the summer season, direct phototransformation appears to be a major elimination pathway of triclosan in this lake. Based on absorption spectra and quantum yield data, the phototransformation half-lives of triclosan were calculated under various environmental conditions typical for surface waters. Daily averaged half-lives were found to vary from about 2 to 2000 days, depending on latitude and time of year.
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Antiinfecciosos Locales/química , Triclosán/química , Contaminantes Químicos del Agua/análisis , Monitoreo del Ambiente , Fotoquímica , Estaciones del Año , Rayos UltravioletaRESUMEN
In order to assess the influence of the aromatic substitution on the ability of a soil bacterial strain, Arthrobacter sp. N2, to degrade phenylurea herbicides, biotransformation assays were performed in mineral medium with resting cells of this soil bacterial strain on three phenylurea herbicides (diuron, chlorotoluron and isoproturon). Each herbicide considered, led to the formation of only one metabolite detected by HPLC analysis. After isolation, the metabolites were identified by NMR and MS, as the corresponding substituted anilines. According to the Microtox test (realized on the bacterium Vibrio fischeri), these metabolites presented non-target toxicity far more important (up to 600 times higher for 4-isopropylaniline) than the parent molecule. For isoproturon and chlorotoluron, the amount of substituted anilines obtained at the end of the biotransformation was very low, whereas the biotransformation of diuron into 3,4-dichloroaniline was almost quantitative. In this last case, the degradation product accumulated in the medium. In soil, other microorganisms are present that might degrade it. So the biotransformation of 3,4-dichloroaniline was then tested with four fungal strains: Aspergillus niger, Beauveria bassiana, Cunninghamella echinulata var. elegans and Mortierella isabellina. The aniline was further transformed with all the microorganisms tested. Only one metabolite was detected by HPLC analysis and after isolation, it was identified to be 3,4-dichloroacetanilide. This acetylated compound led to biological effects less important on V. fischeri than 3,4-dichloroaniline. These results stress the importance of identifying the degradation products to assess the impact of a polluting agent. Indeed, the pollutant may undergo transformation yielding compounds more toxic than the parent molecule.
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Arthrobacter/fisiología , Diurona/metabolismo , Herbicidas/metabolismo , Compuestos de Metilurea/metabolismo , Compuestos de Fenilurea/metabolismo , Contaminantes del Suelo/metabolismo , Biotransformación , Diurona/química , Diurona/toxicidad , Hongos/efectos de los fármacos , Herbicidas/química , Herbicidas/toxicidad , Compuestos de Metilurea/química , Compuestos de Metilurea/toxicidad , Compuestos de Fenilurea/química , Compuestos de Fenilurea/toxicidad , Relación Estructura-ActividadRESUMEN
A bacterial strain able to transform diuron was isolated from a soil by enrichment procedures. Strain isolation was realized by plating on minimal-agarose medium spread with this herbicide and selecting the colonies surrounded by a clear thin halo. One strain was characterized and identified as an Arthrobacter sp. It metabolized diuron and the final transformation product, 3,4-dichloroaniline, was produced in stoichiometric amounts. The transformation of diuron at different concentrations was more efficient in the presence of alternative sources of carbon and nitrogen. The bacterial activity was also evaluated in soil microcosms with a consequent disappearance of diuron and concomitant appearance of 3,4-dichloroaniline, of which the concentration decreased thereafter. Bacterial cells inoculated in the microcosms survived as viable but eventually nonculturable cells.
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Arthrobacter/fisiología , Diurona/metabolismo , Herbicidas/metabolismo , Contaminantes del Suelo/metabolismo , Biodegradación Ambiental , Biotransformación , Diurona/química , Herbicidas/química , Estructura MolecularRESUMEN
Triclosan is used as an antimicrobial agent in a wide range of medical and consumer care products. To investigate the occurrence and fate of triclosan in the aquatic environment, analytical methods for the quantification of triclosan in surface water and wastewater, sludge, and sediment were developed. Furthermore, the fate of triclosan in a wastewater treatment plant (biological degradation, 79%; sorption to sludge, 15%; input into the receiving surface water, 6%) was measured during a field study. Despite the high overall removal rate, the concentration in the wastewater effluents were in the range of 42-213 ng/L leading to concentrations of 11-98 ng/L in the receiving rivers. Moreover, a high removal rate of 0.03 d(-1) for triclosan in the epilimnion of the lake Greifensee was observed. This is due to photochemical degradation. The measured vertical concentration profile of triclosan in a lake sediment core of lake Greifensee reflects its increased use over 30 years. As the measured concentrations in surface waters are in the range of the predicted no effect concentration of 50 ng/L, more measurements and a detailed investigation of the degradation processes are needed.