RESUMEN
For more than 15 years, integrative passive sampling has been successfully used for monitoring contaminants in water, but no passive sampling device exists for strongly polar organic compounds, such as glyphosate. We thus propose a polar organic chemical integrative sampler (POCIS)-like tool dedicated to glyphosate and its main degradation product aminomethylphosphonic acid (AMPA), and describe the laboratory calibration of such a tool for calculating the sampling rates of glyphosate and AMPA. This passive sampler consists of a POCIS with molecularly imprinted polymer as a receiving phase and a polyethersulfone diffusion membrane. The calibration experiment for the POCIS was conducted for 35 days in a continuous water-flow-through exposure system. The calibration results show that the sampling rates are 111 and 122 mL day-1 for glyphosate and AMPA respectively, highlighting the potential interest in and the applicability of this method for environmental monitoring. The influence of membrane porosity on the glyphosate sampling rate was also tested. Graphical Abstract á .
RESUMEN
Laboratory experimentation is essential for our understanding of the fate and behaviour of pollutants. Many analytical techniques exist, but they all have disadvantages either in terms of sensitivity or of selectivity. The number of samples that can be analysed, the low volume of samples available during the experiment and the need to identify different degradates are all obstacles that new techniques are able to overcome. The work presented here summarizes progress in the field of metrology as concerns online solid phase extraction technology coupled with liquid chromatography followed by tandem mass spectrometry detection. Recently developed analytical techniques were validated for both 18 pesticides and their degradates and 17 pharmaceuticals and their degradates. Limits of quantification from 20 to 70 ng L(-1) for pharmaceuticals and from 15 to 25 ng L(-1) for pesticides and metabolites have been obtained, with linearity range up to 1 µg L(-1). The limits of quantification of a few nanograms per litre, the possibility of working on less than 1 mL of sample and the simultaneous quantification of the target products and their transformation products are all advantages that are demonstrated by two environmental applications. The first application concerns the evaluation of ecotoxicological effects of pesticides on aquatic organisms exposed in mesocosms. The second application aims to determine the adsorption constants of pharmaceutical molecules on soils and river sediments. For both applications, the robustness, range of linearity and limit of quantification of the developed analytical methods satisfy the requirements for laboratory experiments conducted under controlled conditions. Specific constraints generated by this type of experiment (adding CaCl2 for the adsorption study and filtration of the water coming from the mesocosms) were not found to limit the use of online SPE. These two preliminary studies show that new experimental fields are possible thanks to online solid phase extraction coupled with liquid chromatography.
Asunto(s)
Cromatografía Líquida de Alta Presión/métodos , Plaguicidas/análisis , Preparaciones Farmacéuticas/análisis , Extracción en Fase Sólida/métodos , Espectrometría de Masas en Tándem/métodos , Contaminantes Químicos del Agua/análisis , Automatización , Monitoreo del Ambiente , Plaguicidas/aislamiento & purificación , Preparaciones Farmacéuticas/aislamiento & purificación , Ríos/química , Contaminantes Químicos del Agua/aislamiento & purificaciónRESUMEN
Emerging contaminants are a growing concern for scientists and public authorities. The group of per-polyfluoroalkyl substances (PFAS), known as 'forever chemicals', in complex environmental liquid and solid matrices was analysed in this study. The development of global analytical methods based on combustion ion chromatography (CIC) is expected to provide accurate picture of the overall PFAS contamination level via the determination of extractable organic fluorine (EOF) and adsorbable organic fluorine (AOF). The obtained results may be put into perspective with other methods such as targeted analyses (LC-MS/MS). The impact of pH, the presence of dissolved organic carbon and suspended particles on AOF measurements were explored. The effectiveness of the washing step to remove adsorbed inorganic fluorine (IF) has been proven for samples containing up to 8 mgF.L-1. CIC-based methods showed good repeatability and reproducibility for the complex matrices studied. Environmental applications of these methods have been tested. AOF and EOF analyses could explain between 1 % and 23 % and 0.1 % to 2 % of total organic fluorine (TOF), respectively. The sum of PFAS compounds expressed as fluorine could explain from 0.2 % to 11 % and from 0.003 % to 5 % for AOF and EOF, respectively. These results also suggest that some fluorinated compounds are not adsorbed or extractable and/or lost by volatilisation during the application of AOF and EOF analytical procedure. These findings highlight that AOF and EOF are not entirely efficient as proxy to assess "total PFAS" for assessing environmental contamination by PFAS. However, these methods could still be applied to gain a better understanding of the sources and fate of PFAS in the environment.
RESUMEN
The chemical burden on the environment and human population is increasing. Consequently, regulatory risk assessment must keep pace to manage, reduce, and prevent adverse impacts on human and environmental health associated with hazardous chemicals. Surveillance of chemicals of known, emerging, or potential future concern, entering the environment-food-human continuum is needed to document the reality of risks posed by chemicals on ecosystem and human health from a one health perspective, feed into early warning systems and support public policies for exposure mitigation provisions and safe and sustainable by design strategies. The use of less-conventional sampling strategies and integration of full-scan, high-resolution mass spectrometry and effect-directed analysis in environmental and human monitoring programmes have the potential to enhance the screening and identification of a wider range of chemicals of known, emerging or potential future concern. Here, we outline the key needs and recommendations identified within the European Partnership for Assessment of Risks from Chemicals (PARC) project for leveraging these innovative methodologies to support the development of next-generation chemical risk assessment.
Asunto(s)
Exposición a Riesgos Ambientales , Monitoreo del Ambiente , Humanos , Exposición a Riesgos Ambientales/análisis , Monitoreo del Ambiente/métodos , Monitoreo del Ambiente/normas , Contaminantes Ambientales/análisis , Sustancias Peligrosas/análisis , Espectrometría de Masas/métodos , Medición de Riesgo/métodosRESUMEN
Antimicrobial resistance (AMR) is a major global public health concern, shared by a large number of human and animal health actors. Within the framework of a One Health approach, actions should be implemented in the environmental realm, as well as the human and animal realms. The Government of France commissioned a report to provide policy and decision makers with an evidential basis for recommending or taking future actions to mitigate AMR in the environment. We first examined the mechanisms that underlie the emergence and persistence of antimicrobial resistance in the environment. This report drew up an inventory of the contamination of aquatic and terrestrial environments by AMR and antibiotics, anticipating that the findings will be representative of some other high-income countries. Effluents of wastewater treatment plants were identified as the major source of contamination on French territory, with spreading of organic waste products as a more diffuse and incidental contamination of aquatic environments. A limitation of this review is the heterogeneity of available data in space and time, as well as the lack of data for certain sources. Comparing the French Measured Environmental Concentrations (MECs) with predicted no effect concentrations (PNECs), fluoroquinolones and trimethoprim were identified as representing high and medium risk of favoring the selection of resistant bacteria in treated wastewater and in the most contaminated rivers. All other antibiotic molecules analyzed (erythromycin, clarithromycin, azithromycin, tetracycline) were at low risk of resistance selection in those environments. However, the heterogeneity of the data available impairs their full exploitation. Consequently, we listed indicators to survey AMR and antibiotics in the environment and recommended the harmonization of sampling strategies and endpoints for analyses. Finally, the objectives and methods used for the present work could comprise a useful example for how national authorities of countries sharing common socio-geographic characteristics with France could seek to better understand and define the environmental dimension of AMR in their particular settings.
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Antibacterianos , Farmacorresistencia Bacteriana , Animales , Antibacterianos/análisis , Antibacterianos/farmacología , Bacterias/genética , Farmacorresistencia Bacteriana/genética , Ríos , Aguas Residuales/análisisRESUMEN
The impacts of current and alternative wheat crop protection programs were compared in outdoor pond mesocosms in a 10-month long study. Realistic exposure scenarios were built based upon the results of modelling of drift, drainage and runoff of pesticides successively applied under two environmental situations characteristics of drained soils of northern France. Each situation was associated to two crop protection programs ("Conventional" and "Low-input") differing in the nature of pesticides used, number of treatments and application rate. Both programs induced significant direct negative effects on various invertebrate groups. Bifenthrin and cyprodynil were identified as the main responsible for these effects in conventional and low-input program, respectively. Indirect effects were also demonstrated especially following treatments with cyprodynil. Litter breakdown was significantly reduced in all treated mesocosms as the functional consequence of the decrease in the abundance of shredders (asellids, Gammarus pulex) illustrating the link between structural and functional effects of pesticides on macroinvertebrate communities. Recovery was observed for many taxa before the end of the study but not for the most sensitive non mobile taxa such as G. pulex. No influence of the agropedoclimatic situation on the effects was shown, suggesting than the main impacts were associated to inputs from drift. The results confirm that the proposed low-input program was less hazardous than the conventional program but the observed structural and functional impact of the low-input program suggest that further improvement of alternative crop protection programs is still needed.
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Biota , Exposición a Riesgos Ambientales , Invertebrados/efectos de los fármacos , Plaguicidas/toxicidad , Contaminantes Químicos del Agua/toxicidad , Animales , Productos Agrícolas , Ecosistema , Francia , Plaguicidas/análisis , Hojas de la Planta/metabolismo , Estanques , Piretrinas/toxicidad , Pirimidinas/toxicidadRESUMEN
Pharmaceutical compounds are nowadays an emerging group of organic pollutants in aquatic systems. Several methodologies have already been published to measure these pollutants in the environment, showing the difficulties to take into account the various compounds belonging to numerous therapeutical and chemical groups. In order to develop environmental monitoring, there is a need for a less costly and time-consuming multi-component procedure. The work presented here deals with the development of an extraction procedure which enables the measurement of a wide spectrum of pharmaceuticals at trace levels (ng 1(-1)) with quite simple equipment (i.e. GC-MS with single quadruple as analyzer). The analyzed compounds comprise anti-inflammatories, antidepressants and hypolipidic drugs. The reliability and sensitivity have been tested on 18 different compounds (7 basic compounds and 11 acidic drugs) extracted simultaneously and analyzed by GC-MS. The optimized procedure has been successfully applied to the analysis of wastewaters, surface waters and drinking waters from the following areas: first the Cortiou rocky inlet, in the Mediterranean Sea (South coast of France), highly impacted by the Marseilles wastewater treatment plant effluent and secondly the Hérault watershed by studying drinking water, surface water and wastewater. In both cases, the level of pharmaceuticals was totally unknown. Results obtained have demonstrated the suitability of the method for multi-residue analysis of different types of water matrices.
Asunto(s)
Residuos de Medicamentos/análisis , Contaminantes Químicos del Agua/análisis , Cromatografía de Gases y Espectrometría de Masas , Estándares de ReferenciaRESUMEN
An analytical procedure involving solid-phase extraction (SPE) and gas chromatography-mass spectrometry (GC-MS) has been developed for determination of pharmaceutical compounds (aspirin, caffeine, carbamazepine, diclofenac, ketoprofen, naproxen, ibuprofen, clofibrate, clofibric acid, and gemfibrozil) in a variety of aqueous samples (wastewater and surface water). After filtration, samples were extracted and concentrated using C(18) or HLB cartridges, depending on the type of compound. Sample storage conditions were checked and optimized to ensure preservation of the pharmaceutical substance, taking into consideration environmental sampling conditions. For most of the pharmaceuticals monitored, recovery was in the range 53 to 99% and the variability was below 15% for the complete procedure, with limits of detection ranging from 0.4 to 2.5 ng L(-1), depending on the compound. The methods were successfully applied to monitoring of pharmaceutical contamination of the Seine estuary. Concentrations varied from several dozens of nanograms per liter for surface waters to several hundreds of nanograms per liter for wastewaters.
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Agua Dulce/análisis , Cromatografía de Gases y Espectrometría de Masas/métodos , Preparaciones Farmacéuticas/análisis , Extracción en Fase Sólida , Contaminantes Químicos del Agua/análisis , Calibración , Monitoreo del Ambiente , Francia , Concentración de Iones de Hidrógeno , Estructura Molecular , Preparaciones Farmacéuticas/química , Estándares de Referencia , Reproducibilidad de los Resultados , Estaciones del Año , Sensibilidad y Especificidad , Contaminantes Químicos del Agua/química , Purificación del Agua/métodosRESUMEN
One of the difficulties encountered when monitoring groundwater quality is low and fluctuating concentration levels and complex mixtures of micropollutants, including emerging substances or transformation products. Combining passive sampling techniques with analysis by high resolution mass spectrometry (HRMS) should improve environmental metrology. Passive samplers accumulate compounds during exposure, which improves the detection of organic compounds and integrates pollution fluctuations. The Polar Organic Chemical Integrative Sampler (POCIS) were used in this study to sequester polar to semi-polar compounds. The methodology described here improves our knowledge of environmental pollution by highlighting and identifying pertinent compounds to be monitored in groundwater. The advantage of combining these two approaches is demonstrated on two different sites impacted by agricultural and/or urban pollution sources where groundwater was sampled for several months. Grab and passive sampling were done and analyzed by liquid chromatography coupled to a hybrid quadrupole time-of-flight mass spectrometer (LC-QTOF). Various data processing approaches were used (target, suspect and non-target screening). Target screening was based on research from compounds listed in a homemade database and suspect screening used a database compiled using literature data. The non-target screening was done using statistical tools such as principal components analysis (PCA) with direct connections between original chromatograms and ion intensity. Trend plots were used to highlight relevant compounds for their identification. The advantage of using POCIS to improve screening of polar organic compounds was demonstrated. Compounds undetected in water samples were detected with these tools. The subsequent data processing identified sentinel molecules, molecular clusters as compounds never revealed in these sampling sites, and molecular fingerprints. Samples were compared and multidimensional visualization of chemical patterns such as molecular fingerprints and recurrent or specific markers of each site were given.
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Cromatografía Líquida de Alta Presión/métodos , Monitoreo del Ambiente/métodos , Agua Subterránea/análisis , Espectrometría de Masas/métodos , Contaminantes Químicos del Agua/análisisRESUMEN
The aim of the present study was to investigate interactions of the antibiotic ciprofloxacin (CIP), titanium dioxide nanoparticles (TiO2 NP) and natural organic matter (NOM) in aqueous suspensions. The mean hydrodynamic diameter of particles of TiO2 NP and NOM in the suspensions ranged from 113 to 255nm. During batch experiments the radioactivity resulting from (14)CIP was determined in the filtrate (filter pore size 100nm) by scintillation measurements. Up to 72h, no significant sorption of NOM to TiO2 NP was observed at a TiO2 NP concentration of 5mg/L. When the concentration of TiO2 NP was increased to 500mg/L, a small amount of NOM of 9.5%±0.6% was sorbed at 72h. The low sorption affinity of NOM on TiO2 NP surfaces could be explained by the negative charge of both components in alkaline media or by the low hydrophobicity of the NOM contents. At a TiO2 NP concentration of 5mgL(-1), the sorption of CIP on TiO2 NP was insignificant (TiO2 NP/CIP ratio: 10). When the TiO2 NP/CIP ratio was increased to 1000, a significant amount of 53.6%±7.2% of CIP was sorbed on TiO2 NP under equilibrium conditions at 64h. In alkaline media, CIP is present mainly as zwitterions which have an affinity to sorb on negatively charged TiO2 NP surfaces. The sorption of CIP on TiO2 NP in the range of TiO2 NP concentrations currently estimated for municipal wastewater treatment plants is estimated to be rather low. The Freundlich sorption coefficients (KF) in the presence of NOM of 2167L(n)mgmg(-n)kg(-1) was about 10 times lower than in the absence of NOM. This is an indication that the particle fraction of NOM<100nm could play a role as a carrier for ionic organic micro-pollutants as CIP.
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Antibacterianos/química , Ciprofloxacina/química , Sustancias Húmicas , Nanopartículas del Metal/química , Titanio/química , Contaminantes Químicos del Agua/química , Adsorción , Monitoreo del Ambiente , SuspensionesRESUMEN
Discharge of antimicrobial residues and resistant bacteria in hospital effluents is supposed to have strong impacts on the spread of antibiotic resistant bacteria in the environment. This study aimed to characterize the effluents of the Gabriel Montpied teaching hospital, Clermont-Ferrand, France, by simultaneously measuring the concentration of ciprofloxacin and of biological indicators resistant to this molecule in biofilms formed in the hospital effluent and by comparing these data to ciprofloxacin consumption and resistant bacterial isolates of the hospital. Determination of the measured environmental concentration of ciprofloxacin by spot sampling and polar organic chemical integrative (POCIS) sampling over 2 weeks, and comparison with predicted environmental concentrations produced a hazard quotient >1, indicating a potential ecotoxicological risk. A negative impact was also observed with whole hospital effluent samples using the Tetrahymena pyriformis biological model. During the same period, biofilms were formed within the hospital effluent, and analysis of ciprofloxacin-resistant isolates indicated that Gamma-Proteobacteria were numerous, predominantly Aeromonadaceae (69.56%) and Enterobacteriaceae (22.61%). Among the 115 isolates collected, plasmid-mediated fluoroquinolone-resistant genes were detected, with mostly aac(6')-lb-cr and qnrS. In addition, 60% of the isolates were resistant to up to six antibiotics, including molecules mostly used in the hospital (aminosides and third-generation cephalosporins). In parallel, 1247 bacteria isolated from hospitalized patients and resistant to at least one of the fluoroquinolones were collected. Only 5 of the 14 species identified in the effluent biofilm were also found in the clinical isolates, but PFGE typing of the Gram-negative isolates found in both compartments showed there was no clonality among the strains. Altogether, these data confirm the role of hospital loads as sources of pollution for wastewater and question the role of environmental biofilms communities as efficient shelters for hospital-released resistance genes.
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Antibacterianos/análisis , Bacterias/crecimiento & desarrollo , Biopelículas , Ciprofloxacina/análisis , Farmacorresistencia Bacteriana , Hospitales , Aguas Residuales , Antibacterianos/farmacología , Bacterias/efectos de los fármacos , Bacterias/genética , Ciprofloxacina/farmacología , Farmacorresistencia Bacteriana/genética , Francia , Genes Bacterianos , Humanos , Plásmidos , Aguas Residuales/química , Aguas Residuales/microbiologíaRESUMEN
The presence of acrylamide in natural systems is of concern from both environmental and health points of view. We developed an accurate and robust analytical procedure (offline solid phase extraction combined with UPLC/MS/MS) with a limit of quantification (20 ng L(-1)) compatible with toxicity threshold values. The optimized (considering the nature of extraction phases, sampling volumes, and solvent of elution) solid phase extraction (SPE) was validated according to ISO Standard ISO/IEC 17025 on groundwater, surface water, and industrial process water samples. Acrylamide is highly polar, which induces a high variability during the SPE step, therefore requiring the use of C(13)-labeled acrylamide as an internal standard to guarantee the accuracy and robustness of the method (uncertainty about 25 % (k = 2) at limit of quantification level). The specificity of the method and the stability of acrylamide were studied for these environmental media, and it was shown that the method is suitable for measuring acrylamide in environmental studies.
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Acrilamida/análisis , Agua Dulce/análisis , Agua Subterránea/análisis , Contaminantes Químicos del Agua/análisis , Cromatografía Líquida de Alta Presión/métodos , Ambiente , Extracción en Fase Sólida/métodos , Espectrometría de Masas en Tándem/métodos , Agua , Calidad del AguaRESUMEN
Nationwide screening of 411 emerging contaminants and other regulated compounds, including parent molecules and transformation products (TPs) having various uses and origins, was done at 494 groundwater sites throughout France during two sampling campaigns in the Spring and the Fall of 2011. One hundred and eighty substances (44% of the targeted compounds) were quantified in at least one sampling point. These included pharmaceuticals, industrial products, pesticides, their transformation products and other emerging compounds. Fifty-five compounds were quantified in more than 1% of the samples. Both regulated and emerging compounds were found. Among the unregulated compounds, acetaminophen, carbamazepine, perfluorinated compounds, dioxins/furans, tolyltriazole, bisphenol A, triazine transformation products, and caffeine were quantified in more than 10% of the samples analyzed. Concentrations exceeding the threshold of toxicological concern of 0.1 µg/L were found for tolyltriazole, bisphenol A and some of the triazine transformation products (DEDIA). These new results should help the water resource managers and environmental regulators develop sound policies regarding the occurrence and distribution of regulated and emerging contaminants in groundwater.
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Monitoreo del Ambiente , Agua Subterránea/química , Contaminantes Químicos del Agua/análisis , Contaminación Química del Agua/legislación & jurisprudencia , Compuestos de Bencidrilo/análisis , Dioxinas/análisis , Francia , Plaguicidas/análisis , Fenoles/análisisRESUMEN
Aggregate quarries play a major role in land settlement. However, like all industrial operations, they can have impacts on the environment, notably due to the use of polyacrylamide (PAM)-based flocculants, which contain residual acrylamide (AMD), a carcinogenic, mutagenic, and reprotoxic monomer. In this study, the dissemination of AMD throughout the environment has been investigated in a French quarry. The presence of AMD has been determined in the process water and in the sludge, as well as in the surrounding surface water and groundwater. From the results of several sampling campaigns carried out on this case study, we can (a) confirm that the AMD contained in the commercial product is found in the quarry's water circuit (0.41 to 5.66 µg/l); (b) show that AMD is transported to the surrounding environment, as confirmed by the contamination of a pond near the installation (0.07 to 0.08 µg/l) and the presence of AMD in groundwater (0.01 to 0.02 µg/l); and (c) show that the sludge in both the current and former settling basins contains AMD (between 4 and 26 µg/kg of dry sludge). Therefore, we demonstrated in this case study that using PAM-based flocculants leads to the release of AMD to the environment beyond the treatment plant and creates a reserve of AMD in sludge basins.
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Acrilamida/análisis , Resinas Acrílicas/análisis , Contaminantes Químicos del Agua/análisis , Acrilamida/química , Resinas Acrílicas/química , Ambiente , Floculación , Agua Subterránea/análisis , Minería , Dióxido de Silicio/análisis , Agua , Contaminantes Químicos del Agua/químicaRESUMEN
Sulfonylureas (SUs) are one of the most widely used herbicides to control weeds in crops. Herein, capillary electrophoresis (CE) was used to determine four sulfonylureas in natural waters, namely chlorsulfuron (CS), iodosulfuron methyl (IM), metsulfuron methyl (MSM) and mesosulfuron methyl (MSS). First of all, a bare silica capillary was chosen with 10mM of 1-butyl-3-methylimidazolium tetrafluoroborate (bminBF4) as electrophoretic buffer (pH 9.6) containing 2 mg L(-1) of surfactant-coated single-wall carbon nanotubes (SC-SWCNTs). A dramatic deviation in migration times was observed. Therefore, a poly(diallyldimethylammonium) chloride (PDADMAC) statically coated cationic capillary was used to improve repeatability and to alter the selectivity of the separation. The electroosmotic flow (EOF) measurement revealed that the SC-SWCNTs were strongly adsorbed at the surface of the PDADMAC coating even in the absence of the surfactant-coated nanotubes in the electrolyte buffer. Consequently, a stable strong cathodic EOF and excellent repeatabilities were obtained with relative standard deviations (RSDs) on migration times and on corrected peak areas below 0.9 and 1.5%, respectively. The separation of the SUs was conducted in only 6 min. No regeneration of the coating between analyses was necessary, and high peak efficiencies up to 173,000 theoretical plates were obtained. The bi-layer coating was subsequently used to analyze sulfonylureas in tap water, in several mineral waters as well as in underground waters spiked with SUs and directly injected into the CE capillary.
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Electroforesis Capilar/métodos , Nanotubos de Carbono/química , Dodecil Sulfato de Sodio/química , Urea/análisis , Compuestos Alílicos/química , Electrólitos/química , Electroósmosis , Imidazoles/química , Polietilenos/química , Compuestos de Amonio Cuaternario/química , Tensoactivos/químicaRESUMEN
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
Over the past years, passive sampling devices have been successfully used for the monitoring of various pollutants in water. The present work studied the uptake kinetics in surface water of ten polar pesticides and metabolites, using pharmaceutical POCIS samplers. The aim was to determine sampling rates from in-situ calibration and to compare results with those obtained earlier under laboratory conditions, with the final objective of assessing the impact of environmental conditions on POCIS field performance. Field results showed a low efficiency of POCIS uptake capacity for moderately polar compounds, such as propiconazole (log Kow=3.72) and tebuconazole (log Kow=3.7), that were present in the aqueous phase at very low levels. The in-situ sampling rates obtained in this study ranged from 169 to 479 mL g(-1)day(-1) and differ by a factor of 3-7.5 from Rs determined under laboratory conditions.
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Agua Dulce/química , Plaguicidas/aislamiento & purificación , Triazoles/aislamiento & purificación , Contaminantes Químicos del Agua/aislamiento & purificación , Calibración , Cromatografía Líquida de Alta Presión , Monitoreo del Ambiente , Cinética , Extracción en Fase Sólida , Manejo de Especímenes/instrumentación , Electricidad Estática , Espectrometría de Masas en TándemRESUMEN
Polar organic chemical integrative samplers (POCIS) are useful for monitoring a wide range of chemicals, including polar pesticides, in water bodies. However, few calibration data are available, which limits the use of these samplers for time-weighted average concentration measurements in an aquatic medium. This work deals with the laboratory calibration of the pharmaceutical configuration of a polar organic chemical integrative sampler (pharm-POCIS) for calculating the sampling rates of 17 polar pesticides (1.15 ≤ logK(ow) ≤ 3.71) commonly found in water. The experiment, conducted for 21 days in a continuous water flow-through exposure system, showed an integrative accumulation of all studied pesticides for 15 days. Three compounds (metalaxyl, azoxystrobine, and terbuthylazine) remained integrative for the 21-day experiment. The sampling rates measured ranged from 67.9 to 279 mL day(-1) and increased with the hydrophobicity of the pesticides until reaching a plateau where no significant variation in sampling rate is observed when increasing the hydrophobicity.
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Compuestos Orgánicos/análisis , Plaguicidas/análisis , Contaminantes Químicos del Agua/análisis , Calibración , Fenómenos Químicos , Monitoreo del Ambiente/métodos , Estudios de Evaluación como Asunto , Concentración de Iones de Hidrógeno , Interacciones Hidrofóbicas e Hidrofílicas , Cinética , Compuestos Orgánicos/química , Plaguicidas/química , Tamaño de la Muestra , Agua/química , Contaminantes Químicos del Agua/químicaRESUMEN
Polar organic chemical integrative samplers (POCISs) for the monitoring of polar pesticides in groundwater were tested on two sites in order to evaluate their applicability by comparison with the spot-sampling approach. This preliminary study shows that, as in surface water, POCIS is a useful tool, especially for the screening of substances at low concentration levels that are not detected by laboratory analysis of spot samples. For quantitative results, a rough estimation is obtained. The challenge is now to define the required water-flow conditions for a relevant quantification of pesticides in groundwater and to establish more representative sampling rates for groundwater.
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Monitoreo del Ambiente/instrumentación , Agua Subterránea/química , Plaguicidas/análisis , Contaminantes Químicos del Agua/análisis , Monitoreo del Ambiente/métodos , FranciaRESUMEN
A simple analytical procedure for the simultaneous determination of eight endogenous steroids (testosterone, androstenedione, 17beta-estradiol, estrone, pregnenolone, progesterone, dihydroandrostenedione, and dihydrotestosterone) in aquatic molluscs by solid-phase extraction (SPE) and gas chromatography/mass spectrometry (GC-MS) has been developed. After a microwave-assisted extraction, samples were further extracted and purified using two successive SPE (EnviChrom-P and NH2) cartridges. Steroids were derivatized with a mixture of N-methyl-N(trimethylsilyl)trifluoroacetamide (MSTFA)/mercaptoethanol/ammonium iodide (NH4I) and determined by GC-MS in selective ion monitoring mode. Recoveries were in the range 85-114%, although slightly lower for dihydrotestosterone, and the repeatability of the procedure, expressed as the coefficient of variation, was lower than 16%. The limits of detection determined in digestive glands of mussels were in the range 0.1-0.4 ng g(-1) wet weight for all the steroids. The developed procedure was then applied to the monitoring of steroid profiles in the digestive glands of mussels from the Arcachon Bay (France) during two reproductive cycles. In parallel, two physiological parameters (lipid content and the condition index of mussels) were also monitored, as well as the seawater temperature and salinity. Only progesterone and pregnenolone were detected in the digestive glands of mussels, and the seasonal variations of progesterone levels seemed to be related to the spawning periods of Mytilus sp. in the Bay. The current challenge for the determination of natural steroids in aquatic invertebrates is also briefly discussed.