New biosourced chiral molecularly imprinted polymer: Synthesis, characterization, and evaluation of the recognition capacity of methyltestosterone.

New biosourced chiral cross-linkers were reported for the first time in the synthesis of methyltestosterone (MT) chiral molecularly imprinted polymers (cMIPs). Isosorbide and isomannide, known as 1,4:3,6-dianhydrohexitols, were selected as starting diols. The cMIPs were synthesized following a noncovalent approach via thermal radical polymerization and monitored by Raman spectroscopy. These cross-linkers were fully characterized by 1 H and 13 C nuclear magnetic resonance (NMR) spectroscopy and high-resolution mass spectrometry. The cross-polarization magic angle spinning 13 C NMR, Fourier transform infrared spectroscopy, scanning electron microscopy, and specific surface areas following the Brunauer-Emmett-Teller (BET) method were used to characterize the cMIPs. The effect of stereochemistry of cross-linkers on the reactivity of polymerization, morphology, and adsorption-recognition properties of the MIP was evaluated. The results showed that the cMIP exhibited an obvious improvement in terms of rebinding capacity for MT as compared with the nonimprinted polymer (NIP). The highest binding capacity was observed for cMIP-Is (27.298 mg g-1 ) for high concentrations (500 mg L-1 ). However, the isomannide homologue cMIP-Im showed higher recovery-up to 65% and capacity for low concentrations (15 mg L-1 ). The experimental data were properly fitted by the Freundlich adsorption isothermal model.

Monitoring the extraction of additives and additive degradation products from polymer packaging into solutions by multi-residue method including solid phase extraction and ultra-high performance liquid chromatography-tandem mass spectrometry analysis.

The use of polymer materials in industry for product packaging is increasing. The presence of additives in the polymer matrix enables the modification or improvement of the properties and performance of the polymer, but these industries are concerned regarding the extractability of these additives. The quantification of these additives is particularly challenging because of the presence of these substances as contaminants in all the analytical equipment and the diversity of their physicochemical properties. In this context, a multi-residue analytical method was developed for the trace analysis of the twenty main additives (and their degradation products) authorized in plastic products such as pharmaceutical packaging (e.g., antioxidants, release agents, and light absorbers). This analytical method consisted of a solid phase extraction (SPE) followed by an analysis using ultra-high performance liquid chromatography coupled to a tandem mass spectrometer (UHPLC-MS/MS). A comparison of two ionization interfaces and the optimization of the extraction procedure were discussed. The influence of the quality of the solvent type (distilled versus not distilled) and the nature of the SPE cartridges (Polypropylene versus Teflon(®)) were demonstrated. The optimized method exhibited a quantification limit lower than 20 ng mL(-1) and recoveries between 70 % and 120 % for all compounds. Finally, the method was validated according to the ICH directive and was subsequently applied to the extraction of polymers under different pH conditions and storage temperatures. To the best of our knowledge, this study presents the first methodology allowing the simultaneous quantification of 24 additives at low ng mL(-1).

Multi-residue analysis of emerging pollutants in sediment using QuEChERS-based extraction followed by LC-MS/MS analysis.

Emerging contaminants are suspected to cause adverse effects in humans and wildlife. Aquatic ecosystems are continuously contaminated by agricultural and industrial sources. To establish a causality relationship between the occurrence of contaminants in the environment and disease, experiments including all environmental matrices must be performed. Consequently, the current analytical tools must be improved. A new multi-residue method for analysing 15 emerging pollutants in sediments based on the Quick, Easy, Cheap, Effective, Rugged and Safe approach is reported. The development of such a multirisque, inter-family method for sediment including pharmaceuticals, pesticides, personal care products and plasticizers is reported for the first time. The procedure involves salting-out liquid-liquid extraction using acetonitrile and clean-up with dispersive solid phase extraction, followed by liquid chromatography coupled with tandem mass spectrometry. The validated analytical procedure exhibited recoveries between 40 and 98% for every target compound. This methodology facilitated the determination of pollutant contents at nanogram-per-gram concentrations.

Multiresidue method to quantify pesticides in fish muscle by QuEChERS-based extraction and LC-MS/MS.

Pesticide residues in fish muscle are an environmental and a health safety concern which requires analytical methods presenting high sensitivity and low limits of quantification. In this study, adapted QuEChERS method, coupled to liquid chromatography tandem mass spectrometry (Scheduled MRM-5500 QTRAP), was developed to quantify 13 pesticides (azoxystrobin, clomazone, diflufenican, dimethachlor, carbendazim, iprodion, isoproturon, mesosulfuron-methyl, metazachlor, napropamid, quizalofop and thifensulfuron-methyl) in muscle of fish. Quantification limits were below 1 ng g(-1) except for clomazone (1.8 ng g(-1)) and quizalofop (7.4 ng g(-1)). Best recoveries were observed for perch (>80%) and roach (>68%), except for thifensulfuron-methyl. Lower recoveries had been observed for carp (6% to 86%). Relative standard deviation was lower than 28% for intra-day and 29% for inter-day analysis, respectively. This method was successfully tested on three fish species, naturally or orally exposed: roach (Rutilus rutilus), perch (Perca fluviatilis) and carp (Cyprinus carpio). Few levels were observed in fish naturally exposed, but carp and perch orally contaminated showed measurable levels in their muscles.

Multi-residue analysis of steroids at sub-ng/L levels in surface and ground-waters using liquid chromatography coupled to tandem mass spectrometry.

Most analytical methodologies currently available for the determination of steroids in water only identify a few representative compounds (mainly estrogens). In this context, a multi-residue methodology based on liquid chromatography-tandem mass spectrometry was developed for the determination of 26 steroids including natural and synthetic estrogens, progestagens and androgens. The method described involves limited sample preparation as it includes a filtration followed by a single solid-phase extraction step using a C18 cartridge. The analytical procedure allows the determination of the target analytes in the lower ng/L range, with recoveries above 80%. The methodology was successfully applied to the analysis of steroids in several surface and ground-waters. In all the waters, estrogens, androgens and/or progestagens were determined.

Occurrence of multi-class surfactants in urban wastewater: contribution of a healthcare facility to the pollution transported into the sewerage system.

Healthcare facility discharges, by their nature, are often considered as non-domestic effluent, which can provide significant pollution comparatively to other domestic sources. In this context, a total of 12 monthly sampling campaigns were collected from a healthcare facility as well as the output of a sewerage system of Site Pilote de Bellecombe (SIPIBEL) observatory. This study focuses more specifically on 12 surfactants and biocides: four anionics, four cationic, two non-ionic, one zwitterionic, and one dispersive agent, among the most commonly used commercial surfactants. Particular attention was also provided to routine wastewater quality parameters. Both effluents were heavily contaminated by most anionic surfactants; they displayed median concentrations up to 1 to 2 mg/L for linear alkylbenzene sulfonates and between 10 and 100 µg/L for other sodium sulfate congeners (lauryl and laureth). Overall, for the majority of surfactants, the healthcare facility contribution to the total flux reaching the wastewater treatment plant ranges between 5 and 9%.

Two-year survey of specific hospital wastewater treatment and its impact on pharmaceutical discharges.

It is well known that pharmaceuticals are not completely removed by conventional activated sludge wastewater treatment plants. Hospital effluents are of major concern, as they present high concentrations of pharmaceutically active compounds. Despite this, these specific effluents are usually co-treated with domestic wastewaters. Separate treatment has been recommended. However, there is a lack of information concerning the efficiency of separate hospital wastewater treatment by activated sludge, especially on the removal of pharmaceuticals. In this context, this article presents the results of a 2-year monitoring of conventional parameters, surfactants, gadolinium, and 13 pharmaceuticals on the specific study site SIPIBEL. This site allows the characterization of urban and hospital wastewaters and their separate treatment using the same process. Flow proportional sampling, solid-phase extraction, and liquid chromatography coupled with tandem mass spectrometry were used in order to obtain accurate data and limits of quantification consistent with ultra-trace detection. Thanks to these consolidated data, an in-depth characterization of urban and hospital wastewaters was realized, as well as a comparison of treatment efficiency between both effluents. Higher concentrations of organic carbon, AOX, phosphates, gadolinium, paracetamol, ketoprofen, and antibiotics were observed in hospital wastewaters compared to urban wastewaters. Globally higher removals were observed in the hospital wastewater treatment plant, and some parameters were shown to be of high importance regarding removal efficiencies: hydraulic retention time, redox conditions, and ambient temperature. Eleven pharmaceuticals were still quantified at relevant concentrations in hospital and urban wastewaters after treatment (e.g., up to 1 µg/L for sulfamethoxazole). However, as the urban flow was about 37 times higher than the hospital flow, the hospital contribution appeared relatively low compared to domestic discharges. Thanks to the SIPIBEL site, data obtained from this 2-year program are useful to evaluate the relevance of separate hospital wastewater treatment.

Priority substances in accumulated sediments in a stormwater detention basin from an industrial area.

One of the most adopted solutions in developed countries to manage stormwater is detention/retention basins which generate large quantities of sediments that have to be removed regularly. In order to manage them properly, accurate data are needed about their physical and chemical characteristics, particularly on micropollutant concentrations and their associated risk. This work consisted in a two-year sampling of dry sediments from a detention-settling basin. Priority substances, including pesticides, polybrominated diphenyl ethers (PBDE), alkylphenols and bisphenol A (BPA), were monitored. Different sites in the basin bottom were sampled in order to investigate spatial distribution of the contamination. Results show that the increase of the sediment thickness in the basin was heterogeneous with a maximum of 15 cm after two years. Pesticides and PBDE were, if detected, mainly found in low concentrations from 2 ng/g to 286 ng/g. Conversely, alkylphenols and bisphenol A were always quantified at concentrations varying from 6 ng/g to 3400 ng/g. These high levels suggest that these sediments should be managed with precautions. Spatial heterogeneity of alkylphenol ethoxylates and BPA concentrations was observed, with higher contamination of alkylphenol ethoxylates in anaerobic zones and BPA levels correlated with total organic carbon and in a lesser extent to fine particles.

MicroQuEChERS-nanoliquid chromatography-nanospray-tandem mass spectrometry for the detection and quantification of trace pharmaceuticals in benthic invertebrates.

Due to industrialization and the use of chemical products in everyday life, various types of drugs and pesticides are present in our environment, which threaten and cause negative impacts on aquatic ecosystems. The consequences of these pollutants are gradually becoming visible. Recent evidence confirms that long term exposure to environmental pharmaceutical concentrations can induce adverse effects in aquatic vertebrates and invertebrates such as reproductive impairments and collapse wild populations. Consequently, one of the challenges of environmental science is to evaluate the associated risks. In this context, a new methodology has been developed using nano-LC-nano-ESI MS/MS to quantify traces of two pharmaceuticals (a neuropharmaceutical drug, fluoxetine, and an anticonvulsant drug, carbamazepine) in two molluscs, Potamopyrgus antipodarum and Valvata piscinalis, which are both prosobranch gastropods. A simple and quick extraction method was developed based on a modified and miniaturized version of the QuEChERS method. The procedure involves the extraction of approximately 10 mg of wet mollusc tissue by 500 µL of a mixture of acetonitrile/water/hexane (50/20/30) and 100 mg of buffer salt. Thus, the extraction step was carried out on an individual scale. The sensitivity of this method allowed for the detection of levels as low as 18 ng/g and 128 ng/g for carbamazepine and fluoxetine, respectively, with recoveries of greater than 85% for the two targeted compounds. This method was then applied to both gastropod species exposed to fluoxetine under laboratory conditions. The results provide evidence of bioaccumulation in both P. antipodarum and V. piscinalis and reveal the inter-species differences.

A national reconnaissance for selected organic micropollutants in sediments on French territory.

To collect a large data set regarding the occurrence of organic substances in sediment, this study presents the examination of 20 micropollutants, as a national survey. The list of target compounds contains two alkylphenols, three polycyclic aromatic hydrocarbons (PAHs) not commonly included in monitoring programmes, six pesticides or metabolites, five pharmaceutical compounds, two hormones, one UV filter and bisphenol A. The selective and sensitive analytical methods, based on quick, easy, cheap, effective, rugged, and safe (QuEChERS) sample preparation followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) or gas chromatography-time-of-flight mass spectrometry (GC-ToF-MS), allow the quantification at limits comprised between 0.5 and 23 ng/g, depending on the compound. The paper summarizes the analytical results from 154 sampling points. Of the 20 target compounds, 9 were determined at least once, and the sediments contained a maximum of 7 substances. The most frequently detected were PAHs (frequency, 77 %; max., 1,400 ng/g). The pharmaceutical compounds, hormones and pesticides were rarely detected in the samples; the most frequently detected was carbamazepine (frequency, 6 %; max., 31 ng/g). In some cases, the levels of PAHs and bisphenol A exceed the predicted no-effect concentration (PNEC) values.

Survey regarding the occurrence of selected organic micropollutants in the groundwaters of overseas departments.

To collect a complete dataset regarding the occurrence of organic substances in groundwater, this study presents the examination of 66 organic contaminants in the groundwater of overseas departments, including pesticides, pharmaceutical compounds, hormones and some industrial substances. The selective and sensitive analytical methods are described. These techniques begin with solid-phase extraction (SPE) followed by analysis using liquid chromatography-tandem mass spectrometry (LC-MS/MS) and gas chromatography-mass spectrometry (GC-ToF-MS). The paper summarises the analytical results from 40 sampling points collected during two campaigns in Guadeloupe, Martinique, Reunion, Mayotte and Guiana, representing 80 samples. Of the 66 target substances, 36 were determined at least once. Among the most frequently detected are bisphenol A (frequency, 96%; max., 7,400 ng/L), caffeine (frequency, 91%; max., 1,240 ng/L), pentachlorophenol (frequency, 55%; max., 418 ng/L), and carbamazepine (frequency, 56%; max., 22 ng/L). The results do not put in evidence that the origin of the sample or climatic characteristics of these regions influence the dilution and release of micropollutants.

Development of a multi-residue method using acetonitrile-based extraction followed by liquid chromatography-tandem mass spectrometry for the analysis of steroids and veterinary and human drugs at trace levels in soil.

The aim of this study was to develop an analytical method for the analysis of traces of hormonal steroids and veterinary and human drugs in soil. Thus, 31 substances were selected, including 14 veterinary products, 11 hormonal steroids and 6 other well-known human contaminant compounds. The procedure inspired by the quick, easy, cheap, effective, rugged and safe (QuEChERS) extraction method was developed. First the acetonitrile-based extraction was optimized. This step was followed by a solid-phase extraction (SPE) clean-up using both a strong anion-exchange cartridge and a polymeric cartridge. The analysis was then performed using liquid chromatography coupled to a triple quadrupole analyser operated with tandem mass spectrometry. This analytical procedure was validated using the ICH/2005 standard by evaluating the linearity (from 0.01 ng/g to 1000 ng/g--R²>0.99), the intra-day precision (relative standard deviation (RSD)<20%), the inter-day precision (RSD<30%), recoveries (40-110% for most of the compounds) and limits of detection and quantification. This method allowed for the determination of the target analytes in the lower ng/g concentration range. The methodology was then applied to real soil samples collected in several areas of France that received different manure or sludge treatments. Some target compounds were detected at very low level (inferior to the ng/g). Veterinary antibiotics, mainly from the sulfonamide family, were found in soils treated by manure (0.02-0.12 ng/g). On the other hand, pharmaceuticals usually used by humans (carbamazepine, ibuprofen) were detected in soils treated by domestic sludge.

Optimisation of pressurised liquid extraction for the ultra-trace quantification of 20 priority substances from the European Water Framework Directive in atmospheric particles by GC-MS and LC-FLD-MS/MS.

Atmospheric deposition plays an important role in environmental pollution and human health. However, very few information is available on the presence, in atmospheric particles, of organic priority substances in contrast to inorganic fraction. A method for the extraction and quantification of 20 priority organic substances listed in the European Water Framework Directive in atmospheric particles was developed. This method consists in a combination of gas chromatography coupled with mass spectrometry and ultra-high-pressure liquid chromatography coupled with tandem mass spectrometry and fluorescence. Optimized pressurized liquid extraction using a hexane/dichloromethane/isopropanol mixture was used as extraction procedure from atmospheric particulate matter. The influence of several extraction experimental factors related to the PLE was investigated. The optimized extraction method (80°C, 40 bar, 10 min, 1 cycle) exhibited average recoveries of target analytes higher than 62%. The method detection limits (MDL) were between 0.3 ng g(-1) and 83 ng g(-1). This extraction method, combined with sensitive analytical techniques, leads to satisfactory reliability, sensitivity, and accuracy. The method was applied to real samples, collected from two urban sites by an atmospheric sampling prototype developed in this study. The first results reveal a systematic presence of PAHs at high levels (ranging from 500 ng g(-1) to 10 µg g(-1)) and a variable and lower presence of pesticides at concentrations below 50 ng g(-1) in the samples.

Multiresidue method for the determination of 13 pesticides in three environmental matrices: water, sediments and fish muscle.

Pesticides residues in aquatic ecosystems are an environmental concern which requires efficient analytical methods. In this study, we proposed a generic method for the quantification of 13 pesticides (azoxystrobin, clomazone, diflufenican, dimethachlor, carbendazim, iprodion, isoproturon, mesosulfuron-methyl, metazachlor, napropamid, quizalofop and thifensulfuron-methyl) in three environmental matrices. Pesticides from water were extracted using a solid phase extraction system and a single solid-liquid extraction method was optimized for sediment and fish muscle, followed by a unique analysis by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Limits of quantification were below 5 ng L(-1) for water (except for fluroxypyr and iprodion) and ranged between 0.1 ng g(-1) and 57.7 ng g(-1) for sediments and regarding fish, were below 1 ng g(-1) for 8 molecules and were determined between 5 and 49 ng g(-1) for the 5 other compounds. This method was finally used as a new routine practice for environmental research.

Multi-residue analysis and ultra-trace quantification of 36 priority substances from the European Water Framework Directive by GC-MS and LC-FLD-MS/MS in surface waters.

A multi residue analysis was developed for screening, quantification and confirmation of 36 priority organic compounds included in the 2000/60/EC European Water Framework Directive. The compounds analyzed included 19 pesticides, 8 PAH, 5 endocrine-disruptors and 4 organochlorine compounds. The method was developed in three steps. First, automated off-line solid-phase extraction using Strata X cartridges was optimized to trap simultaneously the 36 studied compounds. Second, the more volatile compounds were analysed by gas chromatography coupled to mass spectrometry with electron impact ionisation in selected ion monitoring mode (SIM). Third, the last 20 compounds were detected and quantified, in one run, by liquid chromatography coupled to fluorescence detector and tandem mass spectrometry. The excellent selectivity and sensitivity allowed us satisfactory quantification and confirmation at levels as low as 0.2-67 ng L(-1) with recoveries between 59 and 105%. Such methodology was then applied to French surface waters: all the waters present organic contaminants, and their concentration varied according to the origin and nature of substances.

Development of HPLC/ESI-MS and HPLC/1H NMR methods for the identification of photocatalytic degradation products of iodosulfuron.

In the present study, HPLC/ESI-MS and stopped-flow HPLC/1H NMR methods were developed and applied to separate and characterize the byproducts arising from TiO2-catalyzed photodegradation of the herbicide iodosulfuron methyl ester (IOME) in aqueous solution under UV irradiation. Prior to identification, irradiated solutions of IOME (200 and 1000 mg.L(-1)) were concentrated by solid-phase extraction using two cartridges: Isolute C18 and Isolute ENV+. Analytical separation was achieved on a C18 reversed-phase column with ACN/H2O (HPLC/MS) or ACN/D2O (HPLC/NMR) as mobile phase and a linear gradient with a chromatographic run time of 35 min. The combination of UV and MS data allowed the structural elucidation of more than 20 degradation products, whereas 1H NMR data permitted an unequivocal confirmation of the identities of major products and the differentiation of several positional isomers, in particular, the hydroxylation isomers. The obtained results permitted us to propose a possible degradation scheme and to put in evidence the presence of privileged sites for the attack of OH radicals. This work shows, for the first time, the application of combined HPLC with UV, MS, and NMR detection for complete structural elucidation of photocatalytic degradation products, and it will be of particular value in studies on the elimination of pollutants in aqueous solutions by photocatalysis.