C. Eschauzier

Impact of Treatment Processes on the Removal of Perfluoroalkyl Acids from the Drinking Water Production Chain

The behavior of polyfluoralkyl acids (PFAAs) from intake (raw source water) to finished drinking water was assessed by taking samples from influent and effluent of the several treatment steps used in a drinking water production chain. These consisted of intake, coagulation, rapid sand filtration, dune passage, aeration, rapid sand filtration, ozonation, pellet softening, granular activated carbon (GAC) filtration, slow sand filtration, and finished drinking water. In the intake water taken from the Lek canal (a tributary of the river Rhine), the most abundant PFAA were PFBA (perfluorobutanoic acid), PFBS (perfluorobutane sulfonate), PFOS (perfluorooctane sulfonate), and PFOA (perfluorooctanoic acid). During treatment, longer chain PFAA such as PFNA (perfluorononanoic acid) and PFOS were readily removed by the GAC treatment step and their GAC effluent concentrations were reduced to levels below the limits of quantitation (LOQ) (0.23 and 0.24 ng/L for PFOS and PFNA, respectively). However, more hydrophilic shorter chain PFAA (especially PFBA and PFBS) were not removed by GAC and their concentrations remained constant through treatment. A decreasing removal capacity of the GAC was observed with increasing carbon loading and with decreasing carbon chain length of the PFAAs. This study shows that none of the treatment steps, including softening processes, are effective for PFAA removal, except for GAC filtration. GAC can effectively remove certain PFAA from the drinking water cycle.The enrichment of branched PFOS and PFOA isomers relative to non branched isomers during GAC filtration was observed during treatment. The finished water contained 26 and 19 ng/L of PFBA and PFBS. Other PFAAs were present in concentrations below 4.2 ng/L The concentrations of PFAA observed in finished waters are no reason for concern for human health as margins to existing guidelines are sufficiently large.

Perfluorinated compounds in infiltrated river Rhine water and infiltrated rainwater in coastal dunes

Different studies have shown that surface waters contain perfluorinated compounds (PFCs) in the low ng/L range. Surface waters are used to produce drinking water and PFCs have been shown to travel through the purification system and form a potential threat to human health. The specific physicochemical properties of PFCs cause them to be persistent and some of them to be bioaccumulative and toxic in the environment. This study investigates the evolvement of PFC concentrations in Rhine water and rainwater during dune water infiltration processes over a transect in the dune area of the western part of The Netherlands. The difference between infiltrated river water and rainwater in terms of PFC composition was investigated. Furthermore, isomer profiles were investigated. The compound perfluorobutanesulfonate (PFBS) was found at the highest concentrations of all PFCs investigated, up to 37 ng/L in infiltrated river water (71 ± 13% of ΣPFCs). This is in contrast with the predominant occurrence of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonate (PFOS) reported in literature. The concentrations of PFBS found in infiltrated river Rhine water were significantly higher than those in infiltrated rainwater. For perfluorohexanesulfonate (PFHxS) the opposite was found: infiltrated rainwater contained more than infiltrated river water. The concentrations of PFOA, perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), PFBS, PFOS, and PFHxS in infiltrated river water showed an increasing trend with decreasing age of the water. The relative contribution of the branched PFOA and PFOS isomers to total concentrations of PFOA and PFOS showed a decreasing trend with decreasing age of the water.

Perfluorinated alkylated acids in groundwater and drinking water: identification, origin and mobility

Human exposure to perfluorinated alkylated acids (PFAA) occurs primarily via the dietary intake and drinking water can contribute significantly to the overall PFAA intake. Drinking water is produced from surface water and groundwater. Waste water treatment plants have been identified as the main source for PFAA in surface waters and corresponding drinking water. However, even though groundwater is an important source for drinking water production, PFAA sources remain largely uncertain. In this paper, we identified different direct and indirect sources of PFAA to groundwater within the catchment area of a public supply well field (PSWF) in The Netherlands. Direct sources were landfill leachate and water draining from a nearby military base/urban area. Indirect sources were infiltrated rainwater. Maximum concentrations encountered in groundwater within the landfill leachate plume were 1.8 μg/L of non branched perfluorooctanoic acid (L-PFOA) and 1.2 μg/L of perfluorobutanoic acid (PFBA). Sum concentrations amounted to 4.4 μg/L total PFAA. The maximum concentration of ΣPFAA in the groundwater originating from the military camp was around 17 ng/L. Maximum concentrations measured in the groundwater halfway the landfill and the PWSF (15 years travel distance) were 29 and 160 ng/L for L-PFOA and PFBA, respectively. Concentrations in the groundwater pumping wells (travel distance >25 years) were much lower: 0.96 and 3.5 ng/L for L-PFOA and PFBA, respectively. The chemical signature of these pumping wells corresponded to the signature encountered in other wells sampled which were fed by water that had not been in contact with potential contaminant sources, suggesting a widespread diffuse contamination from atmospheric deposition.

Presence and sources of anthropogenic perfluoroalkyl acids in high-consumption tap-water based beverages.

This study investigates the presence and sources of perfluorinated alkyl acids (PFAAs) in tap water and corresponding tap-water based beverages such as coffee and cola collected in the city of Amsterdam, The Netherlands. Exposure pathways studies have shown that low concentrations of PFAA in tap water already may pose a high contribution to daily human exposure. Tap water samples (n=4) had higher concentrations of PFAAs than the corresponding post-mixed cola (n=4). The lower PFAA levels in the cola were attributed to the pre-treatment of tap water in the mixing machines and dilution with cola syrup. In coffee samples from a coffee machine perfluorooctanoic acid (PFOA) at 4 ng L(-1) was the dominating analyte (n=12). The concentrations of PFHpA, PFOA and non branched PFOS were found to be significantly higher in manually (self) brewed coffee than in the corresponding tap water (n=4). The contribution from short-chain PFAA analogs could not be quantified due to low recoveries. Leaching experiments at different temperatures were performed with fluoropolymers-containing tubes to investigate the potential of leaching from tubes used in beverage preparation (n=16). Fluoropolymer tubes showed leaching of PFAAs at high (80°C) temperature but its relevance for contamination of beverages in practice is small. The specific contribution from perfluoropolymer tubing inside the beverage preparation machines could not be assessed since no information was available from the manufacturers. The present study shows that although different beverage preparation processes possibly affect the concentrations of PFAAs encountered in the final consumed product, the water used for preparation remains the most important source of PFAAs. This in turn has implications for areas where drinking water is contaminated. Tap-water based beverages will possibly be an additional source of human exposure to PFAAs and need to be considered in exposure modeling.

Polyfluorinated chemicals in European surface waters, ground- and drinking waters

Polyfluorinated chemicals (PFCs), especially short chain fluorinated alkyl sulfonates and carboxylates, are ubiquitously found in the environment. This chapter aims at giving an overview of PFC concentrations found in European surface, ground- and drinking waters and their behavior during conventional water treatment steps. Main PFC sources to the aquatic environment are municipal and industrial wastewater treatment plants. Treated landfill leachates also showed to be an important source of PFCs to surface waters. Existing data suggest central and south European rivers to have higher concentrations and mass discharges of PFCs than Northern European countries. However, this conclusion might be an artifact due to differences of monitoring activities in different regions. High PFC levels in groundwater are often restricted to some contaminated areas, e.g., due to illegal waste deposition on agricultural land or in the vicinity of a fluoropolymer producing factory. Sites with former fire-fighting activities are also potential “hot spot” areas. Concentrations encountered in drinking water remain fairly low on average. Typical concentrations are in the low ng/L range with the exception of highly contaminated areas, like in the Mohne and Ruhr area in Germany. The encountered concentrations in drinking water depend on the treatment technologies used to purify the water. Drinking water prepared with activated carbon or reverse osmosis will in general contain lower concentrations in tap water than in the raw water. However, the efficiency of water treatment depends much on the local boundary conditions.

Acute and chronic toxicity of short chained perfluoroalkyl substances to Daphnia magna.

The aim of this study was to evaluate the aquatic toxicity of a C4-C6 chemistry based fluoroalkylated polymer and the perfluoroalkyl carboxylic acids, PFBA, PFHxA and PFOA to Daphnia magna. The acute toxicity decreased with decreasing carbon chain length, but the polymer did not show a dose related effect. In a chronic toxicity test performed with PFHxA, mortality was observed at similar concentrations as in the acute toxicity test, indicating that toxicity did not increase with increasing exposure time. Effects on mortality, reproduction and population growth rate occurred at similar concentrations, indicating no specific effect of PFHxA on sublethal endpoints. C4-C6 chemistry is thus less hazardous to daphnids than C7-C8 chemistry. Yet, these compounds are persistent, hard to remove from the environment and production volumes are increasing.

Occurrence of selected perfluorinated alkyl acids in lunch meals served at school canteens in Italy and their relevance for children’s intake

Ready-to-eat servings may be more contaminated with perfluorinated alkyl acids (PFAAs) than the corresponding unprocessed foods due to the presence of PFAAs in and transfer from food contact materials (FCM) and cookware. Therefore, the presence of selected PFAAs in meals served weekly at lunch time in six Italian school canteens was assessed. Five towns were selected representing different areas with local water and food supply. Daily lunch menus were sampled and pooled to form a composite. Analyses were carried out on the weekly composite from each canteen. UPLC-MS/MS quantification limits were in the 6.0–12 pg g–1 range for the selected PFAAs (PFHxA, PFOA, PFNA, PFDA, PFUnDA, PFHxS, branched and non-branched PFOS). Non-branched PFOS was quantified in four out of six composites, with levels ranging from 14 to 25 pg g–1, while PFOA and PFDA were determined in two out of six in the range 6.5–8.2 pg g–1. Theoretical estimates and analytical results in the same order of magnitude indicate a negligible contribution from food processing and serving to meal contamination. When composite analytical data are transposed into dietary estimates, it is shown that Italian school-age children have intakes in the range of 0.3–1.1 and 0.5–1.4 ng kg–1 bw day–1 for PFOA and PFOS respectively, well below the corresponding tolerable daily intakes (TDIs).