Anne Togola

Screening of French groundwater for regulated and emerging contaminants

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.

Simple methodology coupling microwave-assisted extraction to SPE/GC/MS for the analysis of natural steroids in biological tissues: application to the monitoring of endogenous steroids in marine mussels Mytilus sp.

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.

Coated capillaries with highly charged polyelectrolytes and carbon nanotubes co-aggregated with sodium dodecyl sulphate for the analysis of sulfonylureas by capillary electrophoresis.

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.

Environmental forensics in groundwater coupling passive sampling and high resolution mass spectrometry for screening.

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.

Laboratory calibration of a POCIS-like sampler based on molecularly imprinted polymers for glyphosate and AMPA sampling in water

AbstractFor 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 Abstractᅟ

Interactions of ciprofloxacin (CIP), titanium dioxide (TiO2) nanoparticles and natural organic matter (NOM) in aqueous suspensions

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.