Removal of emerging micropollutants from wastewater discharges by powdered and micro-grain activated carbon - Progress of the CarboPlus® project

International audienceThe implementation of a tertiary treatment in conventional wastewater treatment plants is more and more considered by managers to reduce the emerging contaminant discharges into the aquatic environment. In this context, a collaboration between the public sanitation service of Paris conurbation and the Water Environment and Urban Systems laboratory has been initiated since 2013 to study at large scale a pilot (CarboPlus® - SAUR/STEREAU) based on a high concentration fluidized bed activated carbon reactor (>100 kg/m3) with continuous fresh activated carbon injection. The objectives of this project are to i) characterize the efficiency of the process for emerging pollutants for powdered (PAC) and micro-grain (µGAC) activated carbons, ii) characterize the parameters influencing the sorption mechanism (organic matter, operating parameters, activated carbon structure and properties, etc.) and iii) identify the eventual improvements of the conventional quality parameters.In addition to the 14 campaigns already performed in 2013 in PAC configuration, 14 campaigns have been planed in 2014 (8 already performed) to study the fate of 131 micropollutants, including 61 pharmaceuticals and hormones and 70 other emerging pollutants, in addition to conventional wastewater parameters. This presentation aims at displaying the pilot efficiency in µGAC configuration and comparing it to the PAC configuration. The use of µGAC instead of PAC has several operational and economical advantages, but this new type of carbon was never tested with wastewater. Based on the first 8 campaigns, the results tend to indicate that the pilot is as efficient with µGAC than with PAC. In particular, ketoprofen, paracetamol, ibuprofen, ofloxacin, ciprofloxacin, trimethoprim, roxithromycin, atenolol, propranolol, carbamazepine, oxazepam, lorazepam and estrone have removals higher than 80% in average. In addition, first results on the other emerging micropollutants show high or very high removals for pesticides (60-95%), bisphenol A (60-90%), alkylphenols (60-95%), PFOS (75-95%) and X-ray contrast agents (50-70%). Moreover, the high solid retention time (60-90 days) of the µGAC leads to a biological activity within the reactor, as displayed by NO2- (65-99%) and NH4+ (20-70%) removals. However, the results are still partial at this stage of the project, another µGAC dose is currently tested on the pilot and complementary lab-scale tests are still performed to better understand the sorption mechanism

Développement d'une méthode d'analyse multi-résidus permettant l'étude de la bioaccumulation de polluants émergents dans des micro-organismes aquatiques d'eau douce par extraction miniaturisée de type QuEChERS suivie d'une analyse par NanoLC-MS/MS

communication par afficheNational audienc

Development of an analytical method for the targeted screening and multi-residue quantification of environmental contaminants in urine by liquid chromatography coupled to high resolution mass spectrometry for evaluation of human exposures

International audienceThe aim of this study was to develop an analytical method and contribute to the assessment of the Exposome. Thus, a targeted analysis of a wide range of contaminants in contact with humans on daily routines in urine was developed. The method focused on a list of 38 contaminants, including 12 pesticides, one metabolite of pesticide, seven veterinary drugs, five parabens, one UV filter, one plastic additive, two surfactants and nine substances found in different products present in the everyday human environment. These contaminants were analyzed by high performance liquid chromatography coupled to high resolution mass spectrometry (HPLC-HRMS) with a quadrupole-time-of-flight (QqToF) instrument from a raw urinary matrix. A validation according to the FDA guidelines was employed to evaluate the specificity, linear or quadratic curve fitting, inter- and intra-day precision, accuracy and limits of detection and quantification (LOQ). The developed analysis allows for the quantification of 23 contaminants in the urine samples, with the LOQs ranging between 43 ng.mL(-1) and 113.2 ng.mL(-1). This method was applied to 17 urine samples. Among the targeted contaminants, four compounds were detected in samples. One of the contaminants (tributyl phosphate) was detected below the LOQ, The three others (4-hydroxybenzoic acid, sodium dodecylbenzenesulfonate and O,O-diethyl thiophosphate potassium) were detected but did not fulfill the validation criteria for quantification. Among these four compounds, two of them were found in all samples: tributyl phosphate and the surfactant sodium dodecylbenzenesulfonat

High-Resolution Mass Spectrometry as a Tool To Evaluate the Sample Preparation of Sludge

International audienc

Mise au point d'une analyse multi-résidus de produits phytosanitaires dans les miels, les abeilles et le pollen par LC-MS/MS et GC-ToF

communication par afficheNational audienc

Multi-residue analysis of emerging pollutants in benthic invertebrates by modified micro-QuEChERS extraction and nanoLC-MS/MS analysis: a new strategy to evaluate bioaccumulation.

International audienc

Trace level determination of pyrethroid and neonicotinoid insecticides in beebread using acetonitrile-based extraction followed by analysis with ultra-high-performance liquid chromatography-tandem mass spectrometry

International audienceBeebread is among the matrices suspected of contaminating honeybee. To better understand this contamination, the study aimed to develop an efficient, sensitive and reliable analytical method for the trace analysis of pesticides in beebread. This study focuses specifically on the insecticides pyrethroids and neonicotinoids and some of their metabolites. It describes the development and validation of an original analytical approach that consists of one simple extraction method based on modified QuEChERS followed by a selective and sensitive analysis by UHPLC-MS/MS to determine the target compounds in beebread. The method was validated using a quadratic fit. RSD values below 20% were obtained, except for 5-hydroxy-imidacloprid and imidacloprid at 0.5 ng/g, which exhibited RSDs of 25% and 21%, respectively. The intra-day precision was less than 10% for many of the investigated compounds. The inter-day precision varied between 2% and 36%, depending on the compound and the concentration. The recoveries varied from 53% to 119%, with averages of 83, 81 and 77% for the extraction of beebread samples spiked at 0.5, 5 and 10 ng/g, respectively. The LOD values for all the substances were below ng/g, with the exception of 6-chloronicotinic acid (LOD = 1.7 ng/g). The method was then applied to the analysis of 32 beebread samples and revealed the presence of 7 of the target substances. The most frequently detected pesticides belonged to the neonicotinoid family and were generally present at low concentrations, but in some cases exceeded 170 ng/g (acetamiprid and thiacloprid). Some pyrethroids were also detected (lambda-cyhalothrine and bifenthrine), but at very low levels Highlights * A single method for the analysis of pyrethroids and neonicotinoids in beebread. * An innovative and efficient sample extraction based on modified QuEChERS-UPLC-MS/MS. * Detection of the 13 target pesticides and metabolites at sub-ng/g levels. * 7 Target substances detected in beebread samples collected in hives

Développement et Validation d'une méthode de dosage d'insecticides et de leurs métabolites dans le pain d'abeille par UHPLC-MS/MS.

communication par affich

Distribution of neonicotinoids and pyrethrinoids in apiarian products: beebread and beeswax

International audienc

Development and optimisation of home-made stir bar sorptive extraction for analysis of plastic additives: application in human urine

International audienceThe overall objective of this study was to develop an analytical method to contribute to the assessment of the exposure of humans to plastic additives based on the use of a new polydimethylsiloxane-based stir bar extraction method. The method focuses on a list of 21 contaminants, including 18 plastic additives and 3 degradation products. They are analysed by ultra-high performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS) after a stir bar sorptive extraction from urine using a home-made stir bar. Thus, the paper focuses on the optimisation of the extraction method. The limits of quantification are variable from one substance to another, but they fall between 0.1 and 305 ng mL−1. The sample preparations lead to recoveries of up to 90% in water and 80% in urine. The method was successfully applied to 15 human urine samples. Among the targeted plastic additives and their degradation products, 7 compounds were quantified in samples at concentrations ranging from 0.3 ng mL−1 to 42.7 ng mL−1