Jean-François Munoz

Effect of temperature on the release of intentionally and non-intentionally added substances from polyethylene terephthalate (PET) bottles into water: Chemical analysis and potential toxicity

The purpose of this study was to investigate the impact of temperature on the release of PET-bottle constituents into water and to assess the potential health hazard using in vitro bioassays with bacteria and human cell lines. Aldehydes, trace metals and other compounds found in plastic packaging were analysed in PET-bottled water stored at different temperatures: 40, 50, and 60°C. In this study, temperature and the presence of CO2 increased the release of formaldehyde, acetaldehyde and antimony (Sb). In parallel, genotoxicity assays (Ames and micronucleus assays) and transcriptional-reporter gene assays for estrogenic and anti-androgenic activity were performed on bottled water extracts at relevant consumer exposure levels. As expected, and in accordance with the chemical formulations specified for PET bottles, neither phthalates nor UV stabilisers were present in the water extracts. However, 2,4-di-tert-butylphenol, a degradation compound of phenolic antioxidants, was detected. In addition, an intermediary monomer, bis(2-hydroxyethyl)terephthalate, was found but only in PET-bottled waters. None of the compounds are on the positive list of EU Regulation No. 10/2011. However, the PET-bottled water extracts did not induce any cytotoxic, genotoxic or endocrine-disruption activity in the bioassays after exposure.

Occurrence of eight household micropollutants in urban wastewater and their fate in a wastewater treatment plant. Statistical evaluation

The occurrence in urban wastewater of eight micropollutants (erythromycin, ibuprofen, 4-nonylphenol (4-NP), ofloxacin, sucralose, triclosan, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS)) originating from household activities and their fate in a biological wastewater treatment plant (WWTP) were investigated. Their concentrations were assessed in the liquid and solid phases (sewage particulate matter and wasted activated sludge (WAS)) by liquid chromatography-tandem mass spectrometry. The analysis of sewage from two different urban catchments connected to the WWTP showed a specific use of ofloxacin in the mixed catchment due to the presence of a hospital, and higher concentrations of sucralose in the residential area. The WWTP process removed over 90% of ibuprofen and triclosan from wastewater, while only 25% of ofloxacin was eliminated. Erythromycin, sucralose and PFOA were not removed from wastewater, the influent and effluent concentrations remaining at about 0.7 μg/L, 3 μg/L and 10 ng/L respectively. The behavior of PFOS and 4-nonylphenol was singular, as concentrations were higher at the WWTP outlet than at its inlet. This was probably related to the degradation of some of their precursors (such as alkylphenol ethoxylates and polyfluorinated compounds resulting in 4-NP and PFOS, respectively) during biological treatment. 4-NP, ofloxacin, triclosan and perfluorinated compounds were found adsorbed on WAS (from 5 ng/kg for PFOA to 1.0mg/kg for triclosan). The statistical methods (principal component analysis and multiple linear regressions) were applied to examine relationships among the concentrations of micropollutants and macropollutants (COD, ammonium, turbidity) entering and leaving the WWTP. A strong relationship with ammonium indicated that some micropollutants enter wastewater via human urine. A statistical analysis of WWTP operation gave a model for estimating micropollutant output from the WWTP based on a measurement of macropollution parameters.

Mass flows and fate of per- and polyfluoroalkyl substances (PFASs) in the wastewater treatment plant of a fluorochemical manufacturing facility

Although industrial sites producing perfluoroalkyl and polyfluoroalkyl substances (PFASs) may introduce these chemicals into the aquatic environment, they are rarely investigated. This study entailed measuring concentrations, mass flows and the fate of 51 PFASs in an industrial wastewater treatment plant receiving raw effluents from a fluorochemical manufacturing facility. Grab and 24-h composite samples were collected at various stages of wastewater treatment over four sampling campaigns. One perfluoroalkyl carboxylic acid (PFCA) and nine fluorotelomers (FTs) were systematically detected in the facilitys raw effluent. The overall PFCA mass flow ranged from 0.6 to 8.6g/day and was negligible compared to the overall mass flow of FTs (from 647 to 2,892g/day). PFCA mass flows increased drastically after secondary treatment (degradation of precursors) and decreased notably after the floatation tank (adsorption onto floatation sludge), but remained at relatively high levels in the final effluent (from 21 to 247g/day). Similar patterns in mass flow were observed for the FTs, with mass loadings discharged into the river ranging from 1,623 to 6,963g/day. Despite analyzing dozens of PFASs, adsorbable organic fluorine determination and oxidative conversion of PFCA precursors showed that a significant part of PFASs remained unidentified. Nevertheless, two overwhelmingly predominant PFASs-6:2 Fluorotelomer sulfonamide alkylbetaine (6:2 FTAB) and 6:2 Fluorotelomer sulfonamide propyl N,N dimethylamine (M4)-were detected and quantified for the first time in water samples, accounting for >75% of the total PFAS mass flow in the final effluent. This study also provided evidence of soil contamination by the aerosol produced over the aeration basin and inadvertent spillage of pieces of sludge cake.

Effect of sunlight exposure on the release of intentionally and/or non-intentionally added substances from polyethylene terephthalate (PET) bottles into water: Chemical analysis and in vitro toxicity

The effect of sunlight exposure on chemical migration into PET-bottled waters was investigated. Bottled waters were exposed to natural sunlight for 2, 6 and 10 days. Migration was dependent on the type of water. Formaldehyde, acetaldehyde and Sb migration increased with sunlight exposure in ultrapure water. In carbonated waters, carbon dioxide promoted migration and only formaldehyde increased slightly due to sunlight. Since no aldehydes were detected in non-carbonated waters, we conclude that sunlight exposure has no effect. Concerning Sb, its migration levels were higher in carbonated waters. No unpredictable NIAS were identified in PET-bottled water extracts. Cyto-genotoxicity (Ames and micronucleus assays) and potential endocrine disruption effects (transcriptional-reporter gene assays) were checked in bottled water extracts using bacteria (Salmonella typhimurium) and human cell lines (HepG2 and MDA-MB453-kb2). PET-bottled water extracts did not induce any toxic effects (cyto-genotoxicity, estrogenic or anti-androgenic activity) in vitro at relevant consumer-exposure levels.

Analysis of 29 per- and polyfluorinated compounds in water, sediment, soil and sludge by liquid chromatography–tandem mass spectrometry

ABSTRACT Several analytical methods were optimised for the analysis of 29 per- and polyfluoroalkyl substances (PFASs), including perfluorocarboxylic acids, perfluoroalkyl sulphonic acids and fluorotelomers (FTs), such as sulphonate, saturated carboxylic acid, unsaturated carboxylic acid, sulphonamide and sulphonamide betaine (FTAB), in environmental samples in order to assess pollution by PFASs around heavily contaminated sites. Non-filtered water samples were extracted, purified and pre-concentrated by a solid-phase extraction (SPE) procedure. Solid samples (sediments, soils and sludges) were extracted through solvent extraction under acidic conditions and thereafter purified and pre-concentrated using the same SPE procedure as for the water samples. An ultra-high performance liquid chromatography coupled to tandem mass spectrometry in negative electrospray ionisation mode was employed to separate and detect targeted compounds. Twelve labelled internal standards were used to provide an adequate correction compensating for matrix effects. The limits of quantification (LOQs) were between 4 and 10 ng/L in water depending on the analytes. For solid samples, the LOQs were 2 ng/g dry weight (dw) in sediments and soils, and 20 ng/g dw in sludges for all analytes. A surrogate parameter method based on the carboxylation of perfluoroalkyl acid precursors under basic pH conditions was furthermore implemented to estimate the occurrence of non-targeted PFAS compounds. In order to evaluate the reliability of these analytical methods, environmental samples collected around a training area in France, where aqueous fire-fighting foam is used, were analysed. Of all the compounds detected in these environmental samples, 6:2 FTAB was found in the highest concentrations.

Simultaneous determination of perfluoroalkyl iodides, perfluoroalkane sulfonamides, fluorotelomer alcohols, fluorotelomer iodides and fluorotelomer acrylates and methacrylates in water and sediments using solid-phase microextraction-gas chromatography/mass spectrometry

Here, we developed and validated a headspace-solid-phase microextraction-gas chromatography/mass spectrometry (HS-SPME-GC/MS) method for the determination of 14 volatile perfluorinated alkylated substances (PFASs) in water and sediment samples according to SANTE 11945/2015 guidelines. Three fluorotelomer alcohols (FTOHs), two perfluoroalkyl iodides (PFIs), three fluorotelomer iodides (FTIs), four fluorotelomer acrylates and methacrylates (FTACs and FTMACs) and two perfluoroalkyl sulfonamides (FASAs) were analysed simultaneously to assess the occurrence of these compounds from their emission sources to the outlets in water treatment plants. Several SPME parameters were optimised for both water and sediment to maximise responses and keep analysis time to a minimum. In tap water, the limits of quantification (LOQs) were found to be between 20ng/L and 100ng/L depending on the analyte, with mean recoveries ranging from 76 to 126%. For sediments, LOQs ranged from 1 to 3ng/g dry weight depending on the target compound, with mean recoveries ranging from 74 to 125%. SPME considerably reduced sample preparation time and its use provided a sensitive, fast and simple technique. We then used this HS-SPME-GC/MS method to investigate the presence of volatile PFASs in the vicinity of an industrial facility. Only 8:2 FTOH and 10:2 FTOH were detected in a few water and sediment samples at sub-ppb concentration levels. Moreover, several non-target fluorotelomers (12:2 FTOH, 14:2 FTOH and 10:2 FTI) were identified in raw effluent samples. These long-chain fluorotelomers have high bioaccumulative potential in the aquatic environment compared with short-chain fluorotelomers such as 6:2 FTOH and 6:2 FTI.

Impact of certain household micropollutants on bacterial behavior. Toxicity tests/study of extracellular polymeric substances in sludge

The impact of eight household micropollutants (erythromycin, ofloxacin, ibuprofen, 4-nonylphenol, triclosan, sucralose, PFOA and PFOS (PFAAs)) on the laboratory bacterial strain Escherichia coli MG1655 and on activated sludge from an urban wastewater treatment plant was studied. Growth-based toxicity tests on E. coli were performed for each micropollutants. The effect of micropollutants on activated sludge (at concentrations usually measured in wastewater up to concentrations disturbing the bacterial growth of E. coli) was examined in batch reactors and by comparison to a control reactor (without micropollutants). The bound extracellular polymeric substances (EPS) secreted by the sludge were measured by size exclusion chromatography and their overexpression was considered as an indicator of bacteria sensitivity to environmental changes. The chemical oxygen demand (COD) and the ammonium concentration were monitored to evaluate the biomass ability to remove the macropollution. Some micropollutants induced an increase of bound EPS in activated sludge flocs at concentrations depending on the micropollutant: erythromycin from 100 μg/L, ofloxacin from 10 μg/L, triclosan from 0.5 μg/L, 4-nonylphenol from 5000 μg/L and PFAAs from 0.1 μg/L. This suggests that the biomass had to cope with new conditions. Moreover, at high concentrations of erythromycin (10 mg/L) and ibuprofen (5 mg/L) bacterial populations were no longer able to carry out the removal of macropollution. Ibuprofen induced a decrease of bound EPS at all the studied concentrations, probably reflecting a decrease of general bacterial activity. The biomass was not sensitive to sucralose in terms of EPS production, however at very high concentration (1 g/L) it inhibited the COD decrease. Micropollution removal was also assessed. Ibuprofen, erythromycin, ofloxacin, 4-nonylphenol and triclosan were removed from wastewater, mainly by biodegradation. Sucralose and PFOA were not removed from wastewater at all, and PFOS was slightly eliminated by adsorption on sludge.

Simultaneous determination of polycyclic aromatic hydrocarbons and their chlorination by-products in drinking water and the coatings of water pipes by automated solid-phase microextraction followed by gas chromatography-mass spectrometry.

In this study, an automated method for the simultaneous determination of polycyclic aromatic hydrocarbons (PAHs) and their chlorination by-products in drinking water was developed based on online solid-phase microextraction-gas chromatography-mass spectrometry. The main focus was the optimisation of the solid-phase microextraction step. The influence of the agitation rate, type of fibre, desorption time, extraction time, extraction temperature, desorption temperature, and solvent addition was examined. The method was developed and validated using a mixture of 17 PAHs, 11 potential chlorination by-products (chlorinated and oxidised PAHs) and 6 deuterated standards. The limit of quantification was 10 ng/L for all target compounds. The validated method was used to analyse drinking water samples from three different drinking water distribution networks and the presumably coal tar-based pipe coatings of two pipe sections. A number of PAHs were detected in all three networks although individual compositions varied. Several PAH chlorination by-products (anthraquinone, fluorenone, cyclopenta[d,e,f]phenanthrenone, 3-chlorofluoranthene, and 1-chloropyrene) were also found, their presence correlating closely with that of their respective parent compounds. Their concentrations were always below 100 ng/L. In the coatings, all PAHs targeted were detected although concentrations varied between the two coatings (76-12,635 mg/kg and 12-6295 mg/kg, respectively). A number of chlorination by-products (anthraquinone, fluorenone, cyclopenta[d,e,f]phenanthrenone, 3-chlorofluoranthene, and 1-chloropyrene) were also detected (from 40 to 985 mg/kg), suggesting that the reaction of PAHs with disinfectant agents takes place in the coatings and not in the water phase after migration.

Assessment of the fate of some household micropollutants in urban wastewater treatment plant

Everyday domestic activity is a significant source of water pollution. The presence of six household micropollutants in an urban wastewater treatment plant (WWTP) was assessed in wastewater and sludge. A multi-target analytical method was developed for the quantification of ibuprofen, erythromycin, ofloxacin, 4-nonylphenol, 5-chloro-2-(2,4-dichlorophenoxy)phenol (triclosan), and sucralose. The micropollutants were extracted from the liquid and solid phases and their concentrations were determined by LC-MS/MS. The efficiency of micropollutants’ removal within a conventional activated sludge process was assessed. From 50 % to 90 % of ibuprofen and erythromycin was removed from the wastewater liquid phase. Their removal can be attributed to biological degradation as they were not found adsorbed on the outlet sludge. Ofloxacin and triclosan were removed from the liquid phase with similar efficiencies; however, they were adsorbed on the sludge, so it was not possible to determine their removal mechanism (whether biodegradation or displacement to solid phase/sequestration). Sucralose was not removed from wastewater (3 μg L−1 in inlet and outlet liquid phase) and not adsorbed on the sludge. 4-Nonylphenol concentrations were sometimes higher in the WWTP outlet water; this may relate to the degradation of alkylphenol ethoxylates in the wastewater treatment process. 4-Nonylphenol was always present in the outlet sludge.

Ethoxyresorufin-O-deethylase induction in fish from a watershed exposed to a non-point source pollution of agricultural origin

Abstract The activity of a P -450-dependent enzyme, ethoxyresorufin- O -deethylase (EROD), was measured in liver of fish from a watershed exposed to pesticide runoff from nearby vineyards. A correlation was observed between pesticide runoff and enzyme activity. This is the first field trial on the use of the cytochrome P -450 system as a biochemical indicator for assessing potential exposure to trace levels of complex mixtures of pesticides in the aquatic environment. The results might be useful for agencies designing monitoring assessment programs for ecotoxicological risk.