Ongoing Laboratory Performance Study on Chemical Analysis of Hydrophobic and Hydrophilic Compounds in Three Aquatic Passive Samplers

The quality of chemical analysis is an important aspect of passive sampling-based environmental assessments. The present study reports on a proficiency testing program for the chemical analysis of hydrophobic organic compounds in silicone and low-density polyethylene (LDPE) passive samplers and hydrophilic compounds in polar organic chemical integrative samplers. The median between-laboratory coefficients of variation (CVs) of hydrophobic compound concentrations in the polymer phase were 33% (silicone) and 38% (LDPE), similar to the CVs obtained in four earlier rounds of this program. The median CV over all rounds was 32%. Much higher variabilities were observed for hydrophilic compound concentrations in the sorbent: 50% for the untransformed data and a factor of 1.6 after log transformation. Limiting the data to the best performing laboratories did not result in less variability. Data quality for hydrophilic compounds was only weakly related to the use of structurally identical internal standards and was unrelated to the choice of extraction solvent and extraction time. Standard deviations of the aqueous concentration estimates for hydrophobic compound sampling by the best performing laboratories were 0.21 log units for silicone and 0.27 log units for LDPE (factors of 1.6 to 1.9). The implications are that proficiency testing programs may give more realistic estimates of uncertainties in chemical analysis than within-laboratory quality control programs and that these high uncertainties should be taken into account in environmental assessments

Rapid SPE – LC MS/MS analysis for atrazine, its by-products, simazine and S metolachlor in groundwater samples

International audienceA rapid analysis of pesticides using on-line Solid phase extraction LC MS/MS (Agilent Technology) was performed using only 2-mL water samples. SPE cartridge PLRP-s was used for the pre-concentration sample with methanol elution in back flush. Sensitive transitions and mass spectrometry conditions were optimized by direct infusion of individual standard solutions in a positive electrospray mode. Water samples were spiked with internal standards to compensate the matrix effect. The limit of quantification was calculated to be 20 ng L −1 using the standard deviation of blank analysis injected ten times and uncertainties were estimated at less than 20% on concentrations. This method was validated to study leaching water samples for which only small quantities of water were available. • Only 2 mL water sample was used. • Samples were filtered at 0.2 μm and spiked with individual standard. • Compounds were separated in an 18.5-min elution time using the dynamic MRM program

Determination of glyphosate and AMPA in fish bile from the Marne River, France

International audienceGlyphosate is a widely used herbicide. In France, it is used during intercultural operations and to control weeds in non-agricultural areas. Glyphosate and AMPA (its main degradation product) can reach high concentrations in rivers, especially in the Seine basin including the Paris suburb (France). Although it is not bioaccumulative, the associated use of surfactants in pesticide formulations allows better assimilation in biological tissues. The aim of our study was first to develop a method to assess glyphosate and AMPA levels in biological tissues and then to determine the contamination of an freshwater fish, the European chub (Squalius cephalus) by glyphosate and AMPA. Fish were fished in the Marne River (a tributary of the Seine River situated in the East part of Paris) at 4 sites characteristic of agricultural and urban areas. Water was also sampled for analysis to compare sites contamination. Bile is an ideal material to identify metabolites of pollutants. This biological fluid was taken directly from the gallbladder with a syringe on freshly euthanized chub and frozen for further analysis. Then, 100μL of bile was taken and 500μL of internal standard (13C-Glyphosate and 13C-AMPA) were added before extraction with milliQ water (5mL) and ultrasonic method for 30 minutes. The extract was then derivatizated (FMOC-Cl) and concentrated on SPE OASIS HLB cartridge (60cc) before LC MS MS analysis. Preliminary tests were performed to establish and validate the protocol and to find the lowest limit of quantification and the best reproducibility. Results showed that glyphosate is detected in a fish sample coming from the most contaminated site by AMPA. This suggests that glyphosate is assimilated in fish and is still detectable after glyphosate has been degraded to AMPA in the water river. Glyphosate content in fish could be an indicator of environmental contamination. Further developments are needed to validate the protocol and complete the study with other organs than bile

Fish from urban rivers and with high pollutant levels have shorter telomeres

International audienceEnvironmental pressures, such as urbanization and exposure to pollutants may jeopardize survival of free-living animals. Yet, much remains to be known about physiological and ecological responses to currently-released pollutants, especially in wild vertebrate ectotherms. We tested the effect of urbanization and pollution (phthalates, organochlorine and pyrethroid pesticides, polychlorobiphenyls, polybromodiphenylethers, polycyclic aromatic hydrocarbons, and some of their metabolites) on telomere length, a suggested biomarker of life expectancy, in the European chub, Squalius cephalus, from urban and agricultural rivers of the Marne hydrographic network, France. We showed that telomere length was reduced in chub from urban rivers. Moreover, among the wide range of anthropogenic contaminants investigated, high levels of phthalate metabolites in liver were associated with shorter telomeres. This study suggests that urbanization and chemical pollution may compromise survival of wild fish, by accelerating telomere attrition

Parabens in water and sediment: occurrence in river and lakes in different rural and urban environments

Parabens are a group of alkyl esters of the p-hydroxybenzoic acid that are widely used as preservatives in pharmaceutical and personal care products. In order to gain knowledge about presence (or not) of parabens in different water categories, a screening study was performed in France and in 5 overseas territories in 2012. More than 1700 occurrence data were obtained in water and sediment samples for 3 parabens (methylparaben, ethylparaben and propylparaben). Samples were collected on more than 160 sites during 3 sampling campaigns (spring/summer/fall). Sampling sites representing different types of landcover were chosen. This screening study has been conducted on a larger datasets compared to previous reported literature data. For methylparaben and propylparaben, concentrations are similar in all samples, and no obvious effect could be identified associated to the type of anthropogenic sources. The occurrence of parabens as ubiquitous contaminats in almost 100% of the analysed samples can represent a risk. At the measured levels, acute and chronic toxicity is not expected with any of these compounds tested individually. However, currently available PNEC values do not take into account non-standard endpoints, such as endocrine disrupting effects which need to be considered in assessing the potential risksassociated to occurrence of parabens in the aquatic environment. Parabens are common hygiene product ingredients and special care must be considered for sampling

Characterization of the endocrine disruptors pollutant load according to the size of air particles

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Assessment of Adult Human Exposure to Phthalate Esters in the Urban Centre of Paris (France)

International audienceHuman exposure to phthalates was assessed through digestive and respiratory intakes. Six phthalates (DMP, DEP, DnBP, BBP, DEHP, DnOP) were investigated in drinking water, in current foodstuff and in ambient air. Digestive intake was prevailing (92 %) with a major contribution of food (95.5 %). Phthalate intake from water was mainly due to bottled water (60 %) in spite of the minor volume absorbed daily. From the respiratory tract, it was dominated by DEP: 30.3 ng kg(-1) bw day(-1) and the part played by indoor air prevailed. Total intake were as ng kg(-1) bw day(-1), for DEHP: 1458, DnBP: 191.8, BBP: 164.3, DEP: 107.7, DMP: 79.1

Record of trace organic contaminants in a river sediment core: from historical wastewater management to historical use

International audienceSome trace organic contaminants (TrOCs) can be considered as ubiquitous contaminants since the 1950s, and the study of their historical distribution within river sediments allows us to better understand the temporal variation of the chemical quality of sediments, and make assumptions about the most insightful forcings impacting these distributions. In this study, the occurrence of 41 TrOCs of various classes (i.e. pharmaceutical products and pesticides) was studied in a sedimentary core sampled in a disused dock along the Seine River, France. This core covers a 60 year-long period between 1944 and 2003, and 23 TrOCs were detected at least once. Their concentrations mainly ranged between 1 and 10 ng g-1 within the core, except for tetracycline that exhibited higher concentrations (~hundreds of ng.g-1). The dating of the core, based on previous studies, enabled the characterization of the changes since 1945, potentially impacted by (i) the sewer connectivity, (ii) the upgrading of wastewater treatment technologies, (iii) historical modifications in the use of each TrOC, and (iv) the sedimentary composition. In every case the deepest occurrence of each TrOC in the core matched its market authorization date, indicating the potential of TrOC to be used as chronomarkers. This study also reveals that the recent upgrading of wastewater treatment technologies within the 2 watershed decreased the concentrations of each TrOC, despite an increase in TrOC diversity in the most recent years

Influence of Hydrological Parameters on Organohalogenated Micropollutant (Polybrominated Diphenyl Ethers and Polychlorinated Biphenyls) Behaviour in the Seine (France)

International audienceThe temporal dynamics of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) were investigated in a heavily urbanized river (Seine River, Paris, France) from November 2009 to May 2010. Pollutant concentrations were in the range of 0.2 to 3.8 ng l(-1) (median 1.1) and 0.4 to 3.6 ng l(-1) (median 1.1) for a tri-deca BDEs and a 7PCBs, respectively. In addition, for both PBDEs and PCBs, the partitioning between the particulate and dissolved phases was investigated. Due to their low water solubility, PBDEs were mainly (> 70%) bound to particles. In contrast, only 54% of a 7PCBs occurred in the particulate phase, and their partitioning was influenced by the degree of chlorination. During the sampling period, PBDE/PCB fluxes were quite similar and ranged from 3 to 128 and from 6 to 125 g day(-1), respectively. The annual mass flow of PBDEs and PCBs was estimated to 10 kg for both. Contrary to PCBs and BDE-209, the temporal evolution of a tri-hepta BDEs was related to particulate organic matter content, which is controlled by river flow variations. This suggests that they exhibit different sources or behavior in the Seine River