Chemical occurrence of pesticides and transformation products in two small lentic waterbodies at the head of agricultural watersheds and biological responses in caged Gasterosteus aculeatus.

Recent monitoring campaigns have revealed the presence of mixtures of pesticides and their transformation products (TP) in headwater streams situated within agricultural catchments. These observations were attributed to the use of various agrochemicals in surrounding regions. The aim of this work was to compare the application of chemical and ecotoxicological tools for assessing environmental quality in relation to pesticide and TP contamination. It was achieved by deploying these methodologies in two small lentic water bodies located at the top of two agricultural catchments, each characterized by distinct agricultural practices (ALT: organic, CHA: conventional). Additionally, the results make it possible to assess the impact of contamination on fish caged in situ. Pesticides and TP were measured in water using active and passive samplers and suspended solid particles. Eighteen biomarkers (innate immune responses, oxidative stress, biotransformation, neurotoxicity, genotoxicity, and endocrine disruption) were measured in Gasterosteus aculeatus encaged in situ. More contaminants were detected in CHA, totaling 25 compared to 14 in ALT. Despite the absence of pesticide application in the ALT watershed for the past 14 years, 7 contaminants were quantified in 100 % of the water samples. Among these contaminants, 6 were TPs (notably atrazine-2-hydroxy, present at a concentration exceeding 300 ng·L-1), and 1 was a current pesticide, prosulfocarb, whose mobility should prompt more caution and new regulations to protect adjacent ecosystems and crops. Regarding the integrated biomarker response (IBRv2), caged fish was similarly impacted in ALT and CHA. Variations in biomarker responses were highlighted depending on the site, but the results did not reveal whether one site is of better quality than the other. This outcome was likely attributed to the occurrence of contaminant mixtures in both sites. The main conclusions revealed that chemical and biological tools complement each other to better assess the environmental quality of wetlands such as ponds.

Evidence of large-scale deposition of airborne emissions of per- and polyfluoroalkyl substances (PFASs) near a fluoropolymer production plant in an urban area.

Airborne emissions of per- and polyfluoroalkyl substances (PFASs) from fluoropolymer manufacturing facilities-especially those producing polyvinylidene (PVDF)-have rarely been investigated. Once PFASs are released into the air from the facility stacks, they settle in the surrounding environment, contaminating all surfaces. Human beings living in close proximity to these facilities can be exposed through air inhalation and ingestion of contaminated vegetables, drinking water or dust. In this study, we collected nine surface soil and five outdoor settled dust samples within 200 m of the fence line of a PVDF and fluoroelastomer production site near Lyon (France). Samples were collected in an urban area including a sports field. High concentrations of long-chain perfluoroalkyl carboxylic acids (PFCAs) (C ≥ 9) were found at sampling points downwind of the facility. Perfluoroundecanoic acid (PFUnDA) was the predominant PFAS in surface soil (12-245 ng/g dw), whereas perfluorotridecanoic acid (PFTrDA) was in outdoor dust (<0.5-59 ng/g dw). The PFAS profiles observed in soil and dust samples very likely originate from the processing aids used for PVDF and fluoroelastomer production. To our knowledge, long-chain PFCA concentrations as high as reported herein have never been found outside the perimeter fencing of a fluoropolymer plant. PFAS concentrations in other environmental compartments (such as air, vegetables or groundwater) should be monitored to assess all potential pathways to exposure of nearby residents before carrying out human biomonitoring.

Distribution of pesticides and some of their transformation products in a small lentic waterbody: Fish, water, and sediment contamination in an agricultural watershed.

More than 20 years after the Water Framework Directive was adopted, there are still major gaps in the sanitary status of small rivers and waterbodies at the head of basins. These small streams supply water to a large number of wetlands that support a rich biodiversity. Many of these waterbodies are fishponds whose production is destined for human consumption or for the restocking of other aquatic environments. However, these ecosystems are exposed to contaminants, including pesticides and their transformation products. This work aims to provide information on the distribution, diversity, and concentrations of agricultural contaminants in abiotic and biotic compartments from a fishpond located at the head of watersheds. A total of 20 pesticides and 20 transformation products were analyzed by HPLC-ESI-MS/MS in water and sediment sampled monthly throughout a fish production cycle, and in three fish species at the beginning and end of the cycle. The highest mean concentrations were found for metazachlor-OXA (519.48 ± 56.52 ng.L-1) in water and benzamide (4.23 ± 0.17 ng g-1 dry wt.) in sediment. Up to 20 contaminants were detected per water sample and 26 per sediment sample. The transformation products of atrazine (banned in Europe since 2003 but still widely used in other parts of the world), flufenacet, imidacloprid (banned in France since 2018), metazachlor, and metolachlor were more concentrated than their parent compounds. Fewer contaminants were detected in fish and principally prosulfocarb accumulated in organisms during the cycle. Our work brings innovative data on the contamination of small waterbodies located at the head of a basin. The transformation products with the highest frequency of occurrence and concentrations should be prioritized for further environmental monitoring studies, and specific toxicity thresholds should be defined. Few contaminants were found in fish, but the results challenge the widely use of prosulfocarb.

Miniaturization of an extraction protocol for the monitoring of pesticides and polar transformation products in biotic matrices.

Monitoring pesticides in the environment requires the use of sensitive analytical methods. However, existing methods are generally not suitable for analyzing small organisms, as they require large matrix masses. This study explores the development of a miniaturized extraction protocol for the monitoring of small organisms, based on only 30 mg of matrix. The miniaturized sample preparation was developed using fish and macroinvertebrate matrices. It allowed the characterization of 41 pesticides and transformation products (log P from -1.9 to 4.8) in small samples with LC-MS/MS, based on European guidelines (European Commission DG-SANTE, 2019). Quantification limits ranged from 3 to 460 ng g-1 dry weight (dw) for fish and from 0.1 to 356 ng g-1 dw for invertebrates, with most below 60 ng g-1 dw. Extraction rates ranged from 70% to 120% for 35 molecules in fish. Recoveries ranged from 70% to 120% for 37 molecules in macroinvertebrates. Inter-day precision was below 30% for 32 molecules at quantification limits. The method was successfully applied to 17 fish and 19 macroinvertebrates collected from two ponds of the French region of Dombes in November and May 2018, respectively. Both sample matrices were nearly always contaminated with benzamide, imidacloprid-desnitro, and prosulfocarb at respective concentrations of 42-237, 3, and 30-165 ng g-1 dw in fish, and 62-438, 2-6, and 15-29 ng g-1 dw in macroinvertebrates. Results show that this method is an effective tool for characterizing polar pesticides in small biotic samples.

Occurrence of pesticides and their transformation products in headwater streams: Contamination status and effect of ponds on contaminant concentrations.

In France, more than 90% of monitored watercourses are contaminated with pesticides. This high contamination level increases at the head of agricultural watersheds, where dilution capacities are low and transport from treated lands is direct. Ponds, numerous around headwater streams, could provide additional protection against pesticide pollution. Because of their long hydraulic residence time and large water volumes, they mitigate pesticide concentrations between upstream and downstream rivers. However, pesticide transformation products may also be responsible for the degradation of environments, owing to their presence at high concentrations and their persistence, but related data are scarce, particularly because of their high level of molecular diversity. We first reported on the state of water contamination in agricultural headwater streams, based on high frequency water sampling. Analysis of 67 molecules (HPLC-ESI-MS/MS) showed pesticides and pesticide transformation product mixtures of up to 29 different compounds in one sample. Regardless of the sampling location, transformation products represented at least 50% of the detected compounds. Then, we demonstrated the capacity of a pond to reduce contaminant concentrations in downstream rivers for 90% of the detected compounds. Upstream from this pond, environmental quality or ecotoxicological standards were exceeded during sampling, with pesticide and transformation product sum concentrations of up to 27 µg/L. Downstream from the study pond, few exceedances were observed, with a maximum total concentration of 2.2 µg/L, reflecting significant water quality improvement.

Determination of nitroaromatic explosive residues in water by stir bar sorptive extraction-gas chromatography-tandem mass spectrometry.

Nitroaromatic compounds were massively used in the formulation of explosives during both world wars. Even several decades after the end of these wars, their residues are suspected to be widely present in the environment. Their occurrence and effect on ecosystems and human health are still not fully determined. This paper describes the development of a method for the determination of 28 nitroaromatic compounds in water, including isomers of nitrotoluene (NT), dinitrotoluene (DNT), trinitrotoluene (TNT), nitrobenzene (NB), dinitrobenzene (DNB), chloronitrobenzene (ClNB), chlorodinitrobenzene (DNCB), nitronaphthalene (NN), dinitronaphthalene (DNN), nitroaniline (NA), dinitroanisole (DNAN), diphenylamine (DPA), and nitrodiphenylamine (nitro-DPA). In order to separate and individually quantify all the analytes with the best possible sensitivity, stir bar sorptive extraction (SBSE) was chosen as the extraction and pre-concentration step prior to gas chromatography (GC) separation and tandem mass spectrometry detection (MS/MS). Our SBSE optimization efforts focused on parameters such as the type of stir bar, ionic strength, addition of organic solvent, and extraction and desorption times. After these optimizations, the analytical method enabled us to reach limits of quantification (LOQs) between 1 and 50 ng/L in tap water, groundwater, and surface water. The method was applied to the determination of targeted nitroaromatic explosive residues in spring and groundwater samples collected in an area where mine warfare had raged during World War I. Up to 16 different nitroaromatic compounds were detected in the same sample. The highest concentrations were recorded for 2,4-DNT and 1,3-DNB (1700 and 2690 ng/L respectively).

Development of a simple multiresidue extraction method for the quantification of a wide polarity range list of pesticides and transformation products in eggs by liquid chromatography and tandem mass spectrometry.

Waterfowl populations have been decreasing in Europe for the last years and pollution appears to be one of the main factors. This study was conducted to develop a single sensitive and robust analytical method for the monitoring of 2 fungicides, 15 herbicides, 3 insecticides and 24 transformation products in wild bird eggs. One of the major challenges addressed was the characterization of chemicals with large logP range (from -1.9 to 4.8). A total of 11 different extraction parameters were tested in triplicate to optimize the extraction protocol, on generic parameters, buffer addition and use of clean-up steps. Quantification was based on matrix-match approach with hen eggs as reference matrix (34 analytes with r²>0.99). Particular attention was payed to matrix effects (-28% on average), quantification limits (0.5 to 25 ng.g-1 dry mass / 0.2 to 7.5 ng.g-1 fresh mass) and extraction yields (46 to 87% with 25 analytes up to 70%) to ensure the relevance of the method and its compatibility with ultra-trace analysis. It led to a simple solid/liquid low temperature partitioning extraction method followed by LC-MS/MS. Analysis of 29 field samples from 3 waterfowl species revealed that eggs were slightly contaminated with pesticides as only one egg presented a contamination (terbutryn, herbicide, 0.7 ng.g-1) and confirmed the relevance of the method.

How to select relevant metabolites based on available data for parent molecules: Case of neonicotinoids, carbamates, phenylpyrazoles and organophosphorus compounds in French water resources.

The presence of pesticide in water resources is a topical issue in France as in many other countries. Resources can be contaminated by current-used pesticides and their metabolites but also by molecules banned 50 years ago. The number of reported studies on the impact of these substances on human health and environment increases every day. Currently, pesticides and their relevant degradation products are subjected to the European regulation for water intended for human consumption. It sets an individual quality limit of 0.1 µg/L, and another of 0.5 µg/L for the sum of their concentrations. The constant improvement of analytical methods allows laboratories to detect pesticides, at lower and lower concentrations but also more and more metabolites. However, regulation does not provide a national indicative metabolites list to be monitored. Each regional health agency offers their own list based on local agricultural practices and quantities of pesticides sold. This article reports a prioritization method allowing to identify new metabolites to be monitored in water resources, along drinking water treatment plants and in treated water; it describes its application in France in order to anticipate possible non-compliance with raw water and treated water and to provide solutions upstream of changes in sanitary control. This methodology has been developed to rank pesticides and to select the corresponding metabolites by combining three main criteria: use (sale and type of use), toxicity, and environmental fate (based on physical and chemical properties). Prioritization method was applied to four families of pesticides: carbamates, organophosphorus compounds, phenylpyrazoles and neonicotinoids, for which there is a real lack of knowledge as regards the occurrence of their metabolites in metropolitan France. 146 pesticides have been prioritized. The first 50 molecules were considered allowing the identification of 72 metabolites to be monitored in water resources and along drinking water treatment plants.

National screening study investigating nine phthalates and one adipate in raw and treated tap water in France.

The goal of this study was to determine the potential exposure of much of the French population to nine phthalates and bis (2-ethylhexyl) adipate (DEHA) due to water consumption. The occurrence of these compounds was investigated in raw and treated water from public water systems. Water samples were collected in one sampling campaign equally distributed across 101 French départements (a French administrative unit) from November 2015 to July 2016. In all, 271 raw water samples and 283 treated water samples were collected. A specific sampling protocol was conducted in order to assess phthalate pollution during sampling and analysis, and to produce reliable results. Field blanks were thus collected at the same time as real samples at each sampling point. The contamination detected in field blanks was due to diethyl phthalate (DEP), dibutyl phthalate (DBP), diisobutyl phthalate (DIBP), and di-2-ethylhexyl phthalate (DEHP), which are common phthalate interferences in blanks. Their concentrations were never ten times higher than the limits of quantification (LOQ). In tap water, the most frequently detected compound was DBP, at a maximum concentration of 1300 ng/L. In raw water, however, DEP was the most frequently detected analyte with concentrations ranging from 255 to 406 ng/L, while DIBP was observed at a maximum concentration of 1650 ng/L. It is worth mentioning that DEHP-the most widely used phthalate-was only detected in one sample of raw water. Phthalates are not concentrated in any particular area of France in either raw or treated water.

Barrage fishponds, a funnel effect for metal contaminants on headwater streams.

Fishponds are man-made shallow water bodies that are still little studied because of their small size. They represent high value ecosystems, both environmentally (biodiversity hotspot) and economically (fish production). They can have a high place on the hydrographic network, so their influence on water quality is of first importance for rivers and water bodies located downstream and monitored under the Water Framework Directive. These small water bodies can be a source of contaminants during draining period or an efficient buffer for pesticides. We wanted to evaluate whether these ponds could also be a remediation tool against metals by following the annual evolution of upstream/downstream flows. Cadmium, copper, lead and zinc concentrations were quantified in the dissolved phase upstream and downstream of three ponds, each one having a specific agricultural environment (traditional or organic). Metal concentration was quantified in sediments and water. For the dissolved phase, the predictive non-effect concentration was often exceeded, suggesting an environmental risk. Results highlighted also greater quantity of metals at the downstream of the pond compared to the upstream, suggesting remobilization into the ponds or direct cross-sectional contributions from the watershed (e.g. runoff from crops) or even remobilization. Regarding sediments, minimal contamination was shown but a high mineralogical variability. No buffer effect of ponds, which could reduce the risk of acute or chronic toxicity, was detected.

A novel automated method for the quantification of ten halobenzoquinones in drinking water using online solid-phase extraction coupled with liquid chromatography tandem mass spectrometry.

When assessing occurrence and exposure to toxic chemicals in drinking water, developing methods that are sensitive and efficient is paramount. A new method was developed for the quantification of ten halobenzoquinones (HBQs), a class of disinfection by-products (DBPs) in drinking water, which have been shown to be more toxic than most regulated DBPs. This method uses a small sample volume with online solid phase extraction (SPE) followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Previous methods used offline SPE coupled with standard addition, and a pre-concentration step. This requires larger volumes of sample, solvent, and standards. The current method has comparable limits of quantification (0.2-166 ng/L), requires minimal sample preparation, and analysis is almost entirely automated. It also includes 2,6-dibromo-3­chloro-5-methyl-1,4-benzoquinone which was not included in previous methods. A stability test was conducted over a one-week period with different preservatives, including ascorbic acid, sodium thiosulfate, and formic acid. Method optimization included source temperature, SPE size, sample volume, and SPE loading time. This method was validated using drinking water collected from four different drinking water plants; spike recoveries of HBQs were between 70-111%, relative standard deviations of <20%, and linearity of >0.98. Further, using this method, we report the highest concentration of 2,6-dibromo-1,4-benzoquinone found in drinking water (254 ng/L).

Deep seepage of per- and polyfluoroalkyl substances through the soil of a firefighter training site and subsequent groundwater contamination.

Per- and polyfluoroalkyl substances (PFASs) are utilized in specific firefighting foams. The objectives of this study were i) to map PFAS distribution in the soil and groundwater of a firefighter training site active for more than 3 decades, ii) to locate the main points of entry of PFASs into the aquifer and iii) to identify which PFASs seeped most deeply into the soil. A total of 44 soil cores and 17 groundwater samples were collected. Perfluorooctane sulfonate (PFOS), 6:2 fluorotelomer sulfonic acid (6:2 FTSA) and 6:2 Fluorotelomer sulfonamide alkylbetaine (6:2 FTAB) were the most predominant PFASs in surface soil. The highest total PFAS concentrations (up to 357 µg/g) were measured in two areas. Both areas were considered as potential points of entry of PFASs into the aquifer since PFASs were detected in soil 15 m below the surface, despite the presence of clay layers. The highest total PFAS concentrations were recorded in the monitoring wells located in the perimeter of the firefighter training site and in the spring located downgradient in the direction of groundwater flow. They ranged from 300 to 8300 ng/L. The fluorotelomer 6:2 FTAB was quantified in 6 monitoring wells, suggesting that this FT can reach a water table 20 m below the ground's surface.

Poly- and Perfluoroalkyl Substances in Runoff Water and Wastewater Sampled at a Firefighter Training Area.

Per- and polyfluoroalkyl substances (PFASs) are key ingredients of firefighting foams designed to suppress fires involving flammable and combustible liquids. Such foams are used by firefighters during fire training at dedicated sites. Because PFASs are very persistent chemicals, substantial soil and groundwater contamination has been observed in the vicinity of firefighter training areas. However, very few data are available on PFAS contamination of wastewater and runoff water on such sites. The purpose of this study was to evaluate the occurrence of more than 50 PFASs in 43 water samples (effluent from a wastewater treatment plant (WWTP), lagoon, runoff water, and wastewater drained from firefighter training areas) collected from a large firefighter training site, using target and suspect screening. A comparison of the PFAS classes analyzed revealed the overwhelming contribution of fluorotelomers. This indicates that the PFAS emission from the use of firefighting foams cannot be monitored only by measuring perfluoroalkyl acids. Based on the PFAS concentrations measured through target screening, the PFAS mass discharged into the river receiving WWTP effluent and the lagoon was on average 387 ± 183 kg and 56 ± 15 kg per year respectively. Due to the unavailability of standards, it was impossible to take into account the PFASs detected with suspect screening. The present study emphasizes that, above and beyond soil and groundwater contamination, such sites also contribute to the PFAS burden of surface water.

Per- and polyfluoroalkyl substances in firefighting foam concentrates and water samples collected near sites impacted by the use of these foams.

To extinguish large-scale fuel fires, fluorosurfactant based foams (FSBFs) were developed in the 1960s and have been used ever since. In this study, 154 per- and polyfluoroalkyl substances (PFASs) including 122 emerging PFASs used as surfactants in FSBFs were sought in nine different foam concentrates. Field investigations were also carried out in the vicinity of four sites where FSBFs are or were intensively used (two airports, a training center for firefighters and an oil storage depot after a large explosion). In the foam concentrates, only three PFASs were quantified with concentrations ranging from 22,500 to 3,188,000 µg/L. Thirteen emerging PFASs were also identified in these samples based on their mass transitions and intensities. Overall, each foam was a mixture of at least two classes of PFASs. In three concentrates, none of the 122 emerging PFASs were identified as the main ingredient. A perfluoroalkyl acid precursor oxidation assay was therefore performed, and revealed the presence of high amounts of unidentified PFASs. In the vicinity of the four investigated sites, several PFASs were systematically quantified in all of the samples collected downstream of the sites. PFAS profiles were heavily influenced by parameters such as route of PFAS transport after use (runoff, seepage, direct discharge), time elapsed since the cessation of firefighting activities, and firefighting foam composition. The PFAS concentrations found around the investigated sites are the highest recorded in France and resulted in the closure of certain drinking water resources.

Tissue Uptake, Distribution, and Elimination of Perfluoroalkyl Substances in Juvenile Perch through Perfluorooctane Sulfonamidoethanol Based Phosphate Diester Dietary Exposure.

Perfluorooctane sulfonamidoethanol based phosphate diester (SAmPAP) is a potential perfluorooctanesulfonate (PFOS) precursor. To examine whether SAmPAP exposure would result in fish contamination by perfluoroalkyl and polyfluoroalkyl substances (PFASs), juvenile Eurasian perch were dietarily exposed to this compound (dosed group) or exposed to the same tank water but fed control feed (control group). SAmPAP and metabolites were monitored in the muscle, liver, and serum during the 45-day exposure phase and 35-day depuration phase. SAmPAP was only detected in the dosed group and the absorption efficiency (0.04-2.25%) was very low, possibly related to its low bioavailability in the gastrointestinal tract, steric constraints in crossing biological membranes, and clearing by enterohepatic circulation. Although SAmPAP was biotransformed and eliminated at a slow rate (t1/2 > 18 days), its biomagnification factor was low. The observed metabolites in fish were N-ethyl perfluorooctane sulfonamidoacetic acid, perfluorooctane sulfonamidoacetic acid, perfluorooctane sulfonamide, and PFOS. Considering that SAmPAP was the only source of PFASs in the tanks, the occurrence of metabolites indicates that SAmPAP could be biotransformed in fish and contribute to PFOS bioaccumulation. However, levels of metabolites were not significantly different in the dosed and control groups, indicating that metabolite excretion followed by re-exposure to these metabolites from water was the main uptake route.

Validation of a method to monitor the occurrence of 20 relevant pharmaceuticals and personal care products in 167 bottled waters.

Research on emerging substances in drinking water presents major interest and the possibility of trace contamination has seen increasing concern from the scientific community and the public authorities. More particularly, residues of pharmaceuticals and personal care products (PPCPs) in bottled water are a very important issue due to societal concerns and potential media impact. In this context, it has become necessary to carry out reliable monitoring. This requires measurements of high quality with demonstration of accuracy and well-defined uncertainty. In this study, 20 pharmaceutical compounds were targeted for the first time in 167 bottled waters from France and other European countries. An isotope dilution-solid phase extraction-liquid chromatography mass spectrometry method, together with stringent quality control and quality assurance protocols, was developed and validated according to French mandatory standards. Recoveries between 87% and 112% were obtained with coefficient of variation below 20%. Operational limits of quantification (LOQ) were comprised between 5 and 30ngL-1. Expanded uncertainties (k=2) ranged between 16% and 43% and were below 35% for half of the compounds. The survey showed only four positive quantifications, thereby highlighting the rarity of contamination.

Concentrations and patterns of perfluoroalkyl and polyfluoroalkyl substances in a river and three drinking water treatment plants near and far from a major production source.

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are emerging contaminants that have been detected in the environment, biota and humans. Drinking water is a route of exposure for populations using water contaminated by PFAS discharges. This research entailed measuring concentrations, mass flows and investigating the fate of dozens PFASs in a river receiving effluents from a fluorochemical manufacturing facility. To measure the total concentration of perfluoroalkyl carboxylic acid (PFCA) precursors, an oxidative conversion method was used. Several dozen samples were collected in the river (water and sediment), in drinking water resources and at different treatment steps on four sampling dates. One PFCA and three fluorotelomers (FTs) were detected up to 62km downstream from the manufacturing facility. 6:2 Fluorotelomer sulfonamide alkylbetaine (6:2 FTAB) was the predominant PFAS with a mass flow of 3830g/day 5.2km downstream from the facility. At all sampling points, PFAS concentrations in sediment were quite low (<6ng/g dw). Five of the 11 investigated wells showed detectable concentrations of PFASs. Interestingly, their profile patterns were different from those observed in the river, suggesting a transformation of PFCA precursors in the sediments of alluvial groundwater. Conventional drinking water treatments (aeration, sand or granular activated carbon filtration, ozonation or chlorination) did not efficiently remove PFASs. Furthermore, an increase in concentration of certain PFASs was observed after ozonation, suggesting that some FTs such as 6:2 FTAB can break down. Only nanofiltration was able to remove all the analyzed PFASs. In the treated water, total PFAS concentrations never exceeded 60ng/L. The oxidative conversion method revealed the presence of unidentified PFCA precursors in the river. Therefore, 18 to 77% of the total PFCA content after oxidation consisted of unidentified chemical species. In the treated water, these percentages ranged from 0 to 29%, relatively and reassuringly low values.

The impact of two fluoropolymer manufacturing facilities on downstream contamination of a river and drinking water resources with per- and polyfluoroalkyl substances.

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are emerging contaminants that have been detected in the environment, biota, and humans. Drinking water is a route of exposure for populations consuming water contaminated by PFAS discharges. This research study reports environmental measurement concentrations, mass flows, and the fate of dozens of PFASs in a river receiving effluents from two fluoropolymer manufacturing facilities. In addition to quantified levels of PFASs using LC- and GC-MS analytical methods, the total amount of unidentified PFASs and precursors was assessed using two complementary analytical methods, absorbable organic fluorine (AOF) determination and oxidative conversion of perfluoroalkyl carboxylic acid (PFCA) precursors. Several dozen samples were collected in the river (water and sediment) during four sampling campaigns. In addition, samples were collected in two well fields and from the outlet of the drinking water treatment plants after chlorination. We estimated that 4295 kg PFHxA, 1487 kg 6:2FTSA, 965 kg PFNA, 307 kg PFUnDA, and 14 kg PFOA were discharged in the river by the two facilities in 2013. High concentrations (up to 176 ng/g dw) of odd long-chain PFASs (PFUnDA and PFTrDA) were found in sediment samples. PFASs were detected in all 15 wells, with concentrations varying based on the location of the well in the field. Additionally, the presence of previously discharged PFASs was still measurable. Significant discrepancies between PFAS concentration profiles in the wells and in the river suggest an accumulation and transformation of PFCA precursors in the aquifer. Chlorination had no removal efficiency and no unidentified PFASs were detected in the treated water with either complementary analytical method. Although the total PFAS concentrations were high in the treated water, ranging from 86 to 169 ng/L, they did not exceed the currently available guideline values.

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 facility's 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.

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.