Aerosolomics based approach to discover source molecular markers: A case study for discriminating residential wood heating vs garden green waste burning emission sources.

Biomass burning is a significant source of particulate matter (PM) in ambient air and its accurate source apportionment is a major concern for air quality. The discrimination between residential wood heating (RWH) and garden green waste burning (GWB) particulate matter (PM) is rarely achieved. The objective of this work was to evaluate the potential of non-targeted screening (NTS) analyses using HRMS (high resolution mass spectrometry) data to reveal discriminating potential molecular markers of both sources. Two residential wood combustion appliances (wood log stove and fireplace) were tested under different output conditions and wood moisture content. GWB experiments were carried out using two burning materials (fallen leaves and hedge trimming). PM samples were characterized using NTS approaches with both LC- and GC-HRMS (liquid and gas chromatography-HRMS). The analytical procedures were optimized to detect as many species as possible. Chemical fingerprints obtained were compared combining several multivariate statistical analyses (PCA, HCA and PLS-DA). Results showed a strong impact of the fuel nature and the combustion quality on the chemical fingerprints. 31 and 4 possible markers were discovered as characteristic of GWB and RWH, respectively. Complementary work was attempted to identify potential molecular formulas of the different potential marker candidates. The combination of HRMS NTS chemical characterization with multivariate statistical analyses shows promise for uncovering organic aerosol fingerprinting and discovering potential PM source markers.

Per- and polyfluoroalkyl substances (PFAS) in surface sediments: Occurrence, patterns, spatial distribution and contribution of unattributed precursors in French aquatic environments.

While perfluoroalkyl sulfonic acids (PFSAs) and perfluoroalkyl carboxylic acids (PFCAs) are ubiquitous in aquatic environments, non-targeted methods have recently revealed the presence of numerous unidentified per- and polyfluoroalkyl substances (PFAS). Besides those methods, the total oxidizable precursor (TOP) assay has proved useful to estimate the contribution of unattributed perfluoroalkyl acids precursors (pre-PFAAs). In this study, an optimized extraction method was developed to examine the spatial distribution of 36 targeted PFAS in surface sediments collected at French nationwide scale (n = 43), including neutral, anionic and zwitterionic molecules. In addition, a TOP assay procedure was implemented to estimate the contribution of unattributed pre-PFAAs in these samples. Conversion yields of targeted pre-PFAAs were determined for the first time under realistic conditions and led to differences in oxidation profiles compared to the common spiked ultra-pure water method. PFAS were detected in 86 % of samples and ∑PFAStargeted was in the range < Limit of Detection - 23 ng g-1 dry weight (dw) (median: 1.3 ng g-1 dw), with ∑pre-PFAAstargeted representing on average 29 ± 26 % of ∑PFAS. Among pre-PFAAs, compounds of emerging interest such as the fluorotelomer sulfonamidoalkyl betaines 6:2 FTAB and 8:2 FTAB were respectively detected in 38 % and 24 % of samples, with levels similar to those of L-PFOS (<0.36-2.2, <0.50-6.8 and < 0.08-5.1 ng g-1 dw, respectively). A hierarchical cluster analysis coupled with a geographic information system-based approach revealed similarities between groups of sampling sites. For instance, elevated contribution of FTABs were associated with the proximity to airport activities where betaine-based aqueous film-forming foam (AFFFs) might have been used. In addition, unattributed pre-PFAAs were strongly correlated with ∑PFAStargeted and they accounted for 58 % of ∑PFAS (median value); they were generally found in larger quantity near industrial and urban areas where the highest ∑PFAStargeted were also observed.

Ultrasound-assisted sample preparation for simultaneous extraction of anionic, cationic and non-ionic surfactants in sediment.

Despite their very wide use in various fields, knowledge concerning surfactants in environmental solid matrices is generally poor. One of the difficulties encountered in the analysis of surfactants is their very diverse physicochemical properties which require different extraction techniques. The objective of this work was therefore to develop an extraction method in sediments that allows the simultaneous analysis of anionic, cationic and non-ionic surfactants. Different extraction techniques (salting-out, ultrasound), solvents and additives were compared. The optimized method, followed by analysis by coupling liquid chromatography with tandem mass spectrometry, was then validated and applied to real samples in which the analytes were quantified by matrix matched calibration. Optimization of the extraction parameters showed different trends depending on the surfactant family. However, ultrasound assisted extraction with a 90/10 acetonitrile/water mixture at 1% acetic acid and 0.1 M EDTA showed the best results overall. The quantification limits obtained, between 6.4 µg/kg for linear alkylbenzene sulfonate (LAS) C10 and 158 µg/kg for 1-laureth sulfate, allow the analysis of traces in sediments. Eighteen of the 27 targeted surfactants were thus detected. The highest concentrations were found for LAS and quaternary ammoniums. Strong correlations between concentrations of different homologues of the same families of surfactants were observed.

Spatio-temporal assessment of pregnant women exposure to chlorpyrifos at a regional scale.

BACKGROUND: The aim of this study was to use an integrated exposure assessment approach, combining spatiotemporal modeling of environmental exposure and fate of the chemical to assess the exposure of vulnerable populations. In this study, chlorpyrifos exposure of pregnant women in Picardy was evaluated at a regional scale during 1 year. This approach provided a mapping of exposure indicators of pregnant women to chlorpyrifos over fine spatial and temporal resolutions using a GIS environment. METHODS: Fate and transport models (emission, atmospheric dispersion, multimedia exposure, PBPK) were combined with environmental databases in a GIS environment. Quantities spread over agricultural fields were simulated and integrated into a modeling chain coupling models. The fate and transport of chlorpyrifos was characterized by an atmospheric dispersion statistical metamodel and the dynamiCROP model. Then, the multimedia model Modul'ERS was used to predict chlorpyrifos daily exposure doses which were integrated in a PBPK model to compute biomarker of exposure (TCPy urinary concentrations). For the concentration predictions, two scenarios (lower bound and upper bound) were built. RESULTS: At fine spatio-temporal resolutions, the cartography of biomarkers in the lower bound scenario clearly highlights agricultural areas. In these maps, some specific areas and hotspots appear as potentially more exposed specifically during application period. Overall, predictions were close to biomonitoring data and ingestion route was the main contributor to chlorpyrifos exposure. CONCLUSIONS: This study demonstrated the feasibility of an integrated approach for the evaluation of chlorpyrifos exposure which allows the comparison between modeled predictions and biomonitoring data.

Emission factors and chemical characterization of particulate emissions from garden green waste burning.

This work provides an evaluation of the emission factors (EFs) of typical garden waste burning (fallen leaves and hedge trimming) in terms of particulate matter (PM), elemental and organic carbon (EC-OC) together with a detailed chemical characterization of 88 particle-bound organic species including polycyclic aromatic hydrocarbons (PAHs), levoglucosan and its isomers, lignin breakdown products (methoxyphenols), cholesterol, alkanes, polyols and sugars. Furthermore, wood-log based burning experiments have been performed to highlight key indicators or chemical patterns of both, green waste and wood burning (residential heating) sources, that may be used for PM source apportionment purposes. Two residential log wood combustion appliances, wood stove (RWS) and fireplace, under different output conditions (nominal and reduced) and wood log moisture content (mix of beech, oak and hornbeam), have been tested. Open wood burning experiments using wood logs were also performed. Green waste burning EFs obtained were comparable to the available literature data for open-air biomass burning. For PM and for most of the organic species studied, they were about 2 to 30 times higher than those observed for wood log combustion experiments. Though, poor performance wood combustions (open-air wood log burning, fireplace and RWS in reduced output) showed comparable EFs for levoglucosan and its isomers, methoxyphenols, polyols, PAHs and sugars. Toxic PAH equivalent benzo[a]pyrene EFs were even 3-10 times higher for the fireplace and open-air wood log burning. These results highlighted the impact of the nature of the fuel burnt and the combustion performances on the emissions. Different chemical fingerprints between both biomass burning sources were highlighted with notably a predominance of odd high-molecular weight n-alkanes (higher carbon preference index, CPI), lower levoglucosan/mannosan ratio and lower sinapylaldehyde abundance for green waste burning. However, the use of such indicators seems limited, especially if applied alone, for a clear discrimination of both sources in ambient air.

A multi-family offline SPE LC-MS/MS analytical method for anionic, cationic and non-ionic surfactants quantification in surface water.

Of the large number of emerging pollutants discharged from wastewaters into surface waters, surfactants are among those with the highest concentrations. However, few monitoring in river waters of these substances have already been performed and only on a few families, mostly anionic. This work aimed to develop a multi-family analytical strategy suitable for the quantification of low concentrations of surfactant in surface waters. Twelve families of surfactants, anionic, cationic and non-ionic were selected. Their quantification by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) and their extraction by SPE were optimized by comparing different retention mechanisms. The best performances were obtained with a C18 grafted silica LC column and a hydrophilic-lipophilic balanced (HLB) polymeric SPE cartridge. The final analytical method was validated and applied for the quantification of surfactants in 36 river water samples. Method limits of quantification (LQ), intra and inter days precision and trueness were evaluated. With LQ between 15 and 485 ng/L, and trueness over 80%, this method was suitable for monitoring surfactants in surface water. Application on French river water samples revealed the presence of anionic, cationic and non-ionic surfactants with median concentrations from 24 ng/L for octylphenol ethoxylates (OPEO), up to 4.6 µg/L regarding linear alkylbenzene sulfonates (LAS).

Characterizing environmental geographic inequalities using an integrated exposure assessment.

BACKGROUND: At a regional or continental scale, the characterization of environmental health inequities (EHI) expresses the idea that populations are not equal in the face of pollution. It implies an analysis be conducted in order to identify and manage the areas at risk of overexposure where an increasing risk to human health is suspected. The development of methods is a prerequisite for implementing public health activities aimed at protecting populations. METHODS: This paper presents the methodological framework developed by INERIS (French National Institute for Industrial Environment and Risks) to identify a common framework for a structured and operationalized assessment of human exposure. An integrated exposure assessment approach has been developed to integrate the multiplicity of exposure pathways from various sources, through a series of models enabling the final exposure of a population to be defined. RESULTS: Measured data from environmental networks reflecting the actual contamination of the environment are used to gauge the population's exposure. Sophisticated methods of spatial analysis are applied to include additional information and take benefit of spatial and inter-variable correlation to improve data representativeness and characterize the associated uncertainty. Integrated approaches bring together all the information available for assessing the source-to-human-dose continuum using a Geographic Information System, multimedia exposure and toxicokinetic model. DISCUSSION: One of the objectives of the integrated approach was to demonstrate the feasibility of building complex realistic exposure scenarios satisfying the needs of stakeholders and the accuracy of the modelling predictions at a fine spatial-temporal resolution. A case study is presented to provide a specific application of the proposed framework and how the results could be used to identify an overexposed population. CONCLUSION: This framework could be used for many purposes, such as mapping EHI, identifying vulnerable populations and providing determinants of exposure to manage and plan remedial actions and to assess the spatial relationships between health and the environment to identify factors that influence the variability of disease patterns.

Analytical methods for the determination of oil carryover from CNG/biomethane refueling stations recovered in a solvent.

Vehicle gas is often compressed to about 200 bar at the refueling station prior to charging to the vehicle's tank. If a high amount of oil is carried over to the gas, it may cause damage to the vehicles; it is therefore necessary to accurately measure oil carryover. In this paper, three analytical methods for accurate quantification of the oil content are presented whereby two methods are based on gas chromatography and one on FTIR. To better evaluate the level of complexity of the matrix, 10 different compressor oils in use at different refueling stations were initially collected and analysed with GC and FTIR to identify their analytical traces. The GC traces could be divided into three different profiles: oils exhibiting some well resolved peaks, oils exhibiting globally unresolved peaks with some dominant peaks on top of the hump and oils exhibiting globally unresolved peaks. After selection of three oils; one oil from each type, the three methods were evaluated with regards to the detection and quantification limits, the working range, precision, trueness and robustness. The evaluation of the three measurement methods demonstrated that any of these three methods presented were suitable for the quantification of compressor oil for samples. The FTIR method and the GC/MS method both resulted in measurement uncertainties close to 20% rel. while the GC/FID method resulted in a higher measurement uncertainty (U = 30% rel.).

The strength in numbers: comprehensive characterization of house dust using complementary mass spectrometric techniques.

Untargeted analysis of a composite house dust sample has been performed as part of a collaborative effort to evaluate the progress in the field of suspect and nontarget screening and build an extensive database of organic indoor environment contaminants. Twenty-one participants reported results that were curated by the organizers of the collaborative trial. In total, nearly 2350 compounds were identified (18%) or tentatively identified (25% at confidence level 2 and 58% at confidence level 3), making the collaborative trial a success. However, a relatively small share (37%) of all compounds were reported by more than one participant, which shows that there is plenty of room for improvement in the field of suspect and nontarget screening. An even a smaller share (5%) of the total number of compounds were detected using both liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS). Thus, the two MS techniques are highly complementary. Most of the compounds were detected using LC with electrospray ionization (ESI) MS and comprehensive 2D GC (GC×GC) with atmospheric pressure chemical ionization (APCI) and electron ionization (EI), respectively. Collectively, the three techniques accounted for more than 75% of the reported compounds. Glycols, pharmaceuticals, pesticides, and various biogenic compounds dominated among the compounds reported by LC-MS participants, while hydrocarbons, hydrocarbon derivatives, and chlorinated paraffins and chlorinated biphenyls were primarily reported by GC-MS participants. Plastics additives, flavor and fragrances, and personal care products were reported by both LC-MS and GC-MS participants. It was concluded that the use of multiple analytical techniques was required for a comprehensive characterization of house dust contaminants. Further, several recommendations are given for improved suspect and nontarget screening of house dust and other indoor environment samples, including the use of open-source data processing tools. One of the tools allowed provisional identification of almost 500 compounds that had not been reported by participants.

Occurrence survey and spatial distribution of perfluoroalkyl and polyfluoroalkyl surfactants in groundwater, surface water, and sediments from tropical environments.

The occurrence and spatial distribution of 22 selected perfluoroalkyl and polyfluoroalkyl substances (PFASs) in surface water (n=75), groundwater (n=80) and surficial sediment (n=15) were investigated for the first time in the tropical areas constituted by the French Overseas Territories (French Guiana, Guadeloupe, Martinique, Mayotte and Reunion). Descriptive statistics and correlations between PFASs were evaluated through the use of specific statistical treatments to handle left-censored data ("non-detects"). PFASs were ubiquitous in these samples and detection frequencies as high as 79% for perfluorooctane sulfonate (PFOS) and 65% for perfluorooctanoate (PFOA) were reported in surface waters. ∑PFASs was in the range

Analysis of zwitterionic, cationic, and anionic poly- and perfluoroalkyl surfactants in sediments by liquid chromatography polarity-switching electrospray ionization coupled to high resolution mass spectrometry.

A new analytical method is proposed for the determination of a wide span of fluoroalkylated surfactants (PFASs) of various chain lengths and polarities in sediments, including newly-identified compounds such as zwitterionic and cationic PFASs. Extraction conditions were optimized so as to maintain a common preparation procedure for all analytes (recovery range: 60-110%). Instrumental analysis was performed with ultra-high performance liquid chromatography coupled to Orbitrap mass spectrometry through polarity-switching electrospray ionization. Calibration curves with excellent coefficients of determination (R(2)>0.994) were generally obtained over 0.002-10ngg(-1) dry weight (dw) and limits of detection were in the range 0.0006-0.46 ng g(-1) dw. Intra-day precision remained<9% and inter-day precision<23%. While perfluorooctane sulfonate (PFOS) generally prevailed over other perfluoroalkyl acids (PFAAs) in sediments from mainland France, fluorotelomer sulfonamide amines and fluorotelomer sulfonamide betaines were also ubiquitous in these samples, especially in the vicinity of airports wherein firefighting training activities may occur on a regular basis.

Assessment of background concentrations of organometallic compounds (methylmercury, ethyllead and butyl- and phenyltin) in French aquatic environments.

The aim of this work is to estimate background concentrations of organometallic compounds, such as tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT), triphenyltin (TPhT), diphenyltin (DPhT), monophenyltin (MPhT), methylmercury (MeHg), inorganic mercury (iHg) and diethyllead (Et2Pb) in the aquatic environment at the French national scale. Both water and sediment samples were collected all over the country, resulting in 152 water samples and 123 sediment samples collected at 181 sampling points. Three types of surface water bodies were investigated: rivers (140 sites), lakes (19 sites) and coastal water (42 sites), spread along the 11 French river basins. The choice of sites was made on the basis of previous investigation results and the following target criteria: reference, urban sites, agricultural and industrial areas. The analytical method was properly validated for both matrices prior to analysis, resulting in low limits of quantification (LOQ), good precision and linearity in agreement with the Water Framework Directive demands. The results were first evaluated as a function of their river basins, type of surrounding pressure and water bodies. Later, background concentrations at the French national scale were established for both water and sediment matrices, as well as their threshold, i.e., the concentration that distinguishes background from anomalies or contaminations. Background concentrations in water are ranging between <0.04-0.14 ng Hg. L(-1) for MeHg, <0.14-2.10 ng Hg. L(-1) for iHg, <1.0-8.43 ng Pb. L(-1) for Et2Pb and 0.49-151 ng Sn. L(-1), <0.08-3.04 ng Sn. L(-1) and <0.08-0.25 ng Sn. L(-1) for MBT, DBT and TBT, respectively. For sediments, background concentrations were set as <0.09-1.11 ng Hg. g(-1) for MeHg, <0.06-24.3 ng Pb. g(-1) for Et2Pb and <1.4-13.4 ng Sn. g(-1), <0.82-8.54 ng Sn. g(-1), <0.25-1.16 ng Sn. g(-1) and <0.08-0.61 ng Sn. g(-1) for MBT, DBT, TBT and DPhT, respectively. TBT occurs in higher concentrations than the available environmental protection values in 24 and 38 sampling sites for both water and sediment samples, respectively. Other phenyltins (MPhT and TPhT) did not occur above their LOQ and therefore no background was possible to establish. Throughout this work, which is the first assessment of background concentrations for organometallic compounds at the French national level ever being published, it was possible to conclude that over the last 10-20 years organotin concentrations in French river basins have decreased while MeHg concentration remained stable.

PBPK modeling of the cis- and trans-permethrin isomers and their major urinary metabolites in rats.

Permethrin, a pyrethroid insecticide, is suspected to induce neuronal and hormonal disturbances in humans. The widespread exposure of the populations has been confirmed by the detection of the urinary metabolites of permethrin in biomonitoring studies. Permethrin is a chiral molecule presenting two forms, the cis and the trans isomers. Because in vitro studies indicated a metabolic interaction between the trans and cis isomers of permethrin, we adapted and calibrated a PBPK model for trans- and cis-permethrin separately in rats. The model also describes the toxicokinetics of three urinary metabolites, cis- and trans-3-(2,2 dichlorovinyl)-2,2-dimethyl-(1-cyclopropane) carboxylic acid (cis- and trans-DCCA), 3-phenoxybenzoic acid (3-PBA) and 4'OH-phenoxybenzoic acid (4'-OH-PBA). In vivo experiments performed in Sprague-Dawley rats were used to calibrate the PBPK model in a Bayesian framework. The model captured well the toxicokinetics of permethrin isomers and their metabolites including the rapid absorption, the accumulation in fat, the extensive metabolism of the parent compounds, and the rapid elimination of metabolites in urine. Average hepatic clearances in rats were estimated to be 2.4 and 5.7 L/h/kg for cis- and trans-permethrin, respectively. High concentrations of the metabolite 4'-OH-PBA were measured in urine compared to cis- and trans-DCCA and 3-PBA. The confidence in the extended PBPK model was then confirmed by good predictions of published experimental data obtained using the isomers mixture. The extended PBPK model could be extrapolated to humans to predict the internal dose of exposure to permethrin from biomonitoring data in urine.

Development of liquid chromatography methods coupled to mass spectrometry for the analysis of substances with a wide variety of polarity in meconium.

Meconium is the first fecal excretion of newborns. This complex accumulative matrix allows assessing the exposure of the fetus to xenobiotics during the last 6 months of pregnancy. To determine the eventual effect of fetal exposure to micropollutants in this matrix, robust and sensitive analytical methods must be developed. This article describes the method development of liquid chromatography methods coupled to triple quadrupole mass spectrometry for relevant pollutants. The 28 selected target compounds had different physico-chemical properties from very polar (glyphosate) to non-polar molecules (pyrethroids). Tests were performed with three different types of columns: reversed phase, ion exchange and HILIC. As a unique method could not be determined for the simultaneous analysis of all compounds, three columns were selected and suitable chromatographic methods were optimized. Similar results were noticed for the separation of the target compounds dissolved in either meconium extract or solvent for reversed phase and ion exchange columns. However, for HILIC, the matrix had a significant influence on the peak shape and robustness of the method. Finally, the analytical methods were applied to "real" meconium samples.

Spatial distribution and partitioning behavior of selected poly- and perfluoroalkyl substances in freshwater ecosystems: a French nationwide survey.

The spatial distribution and partitioning of 22 poly- and perfluoroalkyl substances (PFASs) in 133 selected rivers and lakes were investigated at a nationwide scale in mainland France. ΣPFASs was in the range99% of ΣPFASs in the sediment, likely as a consequence of industrial point source discharge). Several treatments for data below detection limits (non-detects) were used to compute descriptive statistics, differences among groups, and correlations between congeners, as well as log Kd and log Koc partition coefficients; in that respect, the Regression on Order Statistics (robust ROS) method was preferred for descriptive statistics computation while the Akritas-Theil-Sen estimator was used for regression and correlation analyses. Multiple regression results suggest that PFAS levels in the dissolved phase and sediment characteristics (organic carbon fraction and grain size) may be significant controlling factors of PFAS levels in the sediment.

Towards a generic variable column length method development strategy for samples with a large variety in polarity.

The development of a novel set-up for the sequential analysis of compounds with a large variety in polarity on HILIC and reversed-phase columns, coupled in series, is discussed. For this purpose, a commercially available ultra-high performance LC system, equipped with two switching valves is employed. The switching valves allow connecting the HILIC and reversed-phase columns either in series or in parallel to the system. An interface to couple the HILIC and reversed-phase columns is developed and optimized. The sample is first injected onto a HILIC column. Apolar compounds in the sample are not retained and will elute close to or within the void volume of the HILIC column. Accurate switching of the valves allows redirecting these compounds towards a trap loop while more polar compounds are retained and separated on the HILIC column. After separation and detection of the polar compounds, the configuration of the valves is switched again to direct the apolar compounds from the trap loop towards a reversed-phase column for separation. To deal with the incompatibility of the mobile phases of HILIC and reversed-phase column separations, commercially available Jet weaver mixers are included in the set-up to allow for an intermediate solvent exchange. The proof-of-concept is demonstrated for the analysis of pharmaceuticals that can be found in waste water and surface water. It is demonstrated that the set-up provides robust analyses with peak capacities that are intermediate to one-dimensional and two-dimensional separations.

Development of a multi-residue method in a fetal matrix: analysis of meconium.

Meconium is the earliest stool of newborns. It is a complex matrix that reflects the degree of fetal exposure to environmental pollutants. To investigate exposure to xenobiotics, an analytical method was developed to identify and quantify some pesticides and their metabolites and BTEX metabolites in meconium. Samples were prepared by two liquid-solid extractions and purified twice using SPE cartridges, followed by analysis with liquid chromatography coupled with tandem mass spectrometry. SPE cartridges (polymeric phase with hydrophilic and hydrophobic interactions, ion exchange, mixed mode) were tested and matrix effects were evaluated to determine purification performance. The quantification limits in meconium of this multi-residue method were in the range of 30 ng g(-1). The analytical method was applied to "real" meconium samples. Some target analytes were determined in most samples.

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.

Development of an analytical strategy based on LC-MS/MS for the measurement of different classes of pesticides and theirs metabolites in meconium: application and characterisation of foetal exposure in France.

It is important to evaluate the impact of pesticides on human health because exposure to these compounds has been linked to harmful effects in many research studies. This exposure may be particularly harmful during the early stages of development (e.g. the prenatal period). The aim of the present study was to develop an analytical strategy for quantifying a number of pesticides and their metabolites in meconium (the neonate's first faeces), in order to characterize the extent of foetal exposure. The meconium sample was dried and grinded in order to homogenize the sample, prior to solid-liquid extraction and a purification by solid-phase extraction using a weak anion mixed-mode polymeric sorbent. Analyte separation and quantification was performed by liquid chromatography coupled to electrospray-triple quadrupole mass spectrometry. Five pesticide families (carbamates, organophosphates, pyrethroids, phenylureas and phenoxy herbicides) and their metabolites could be quantified in meconium with limits of quantification ranging between 0.2 ng/g and 200 ng/g. This method was applied to a set of 171 meconium samples collected in the Picardie region of northern France. The highest prevalence was observed for metabolites of organophosphates and carbamates (57.9% and 22.8%, respectively). The parent pesticides were rarely present and were only found at very low concentrations, except for the pyrethroids cyfluthrin and cypermethrin, which were found in 7.6% of meconium samples at concentrations of between 43.8 and 480 ng/g. The most frequently detected contaminant was the organophosphate metabolite dimethyl thiophosphate detected in 49.1% of the samples and quantified with a median concentration of 344 ng/g. These data evidence significant foetal exposure to organophosphate pesticides, pyrethroids and carbamates.