Presence of Emerging Per- and Polyfluoroalkyl Substances (PFASs) in River and Drinking Water near a Fluorochemical Production Plant in the Netherlands

Abstract

The present study investigated the presence of legacy and emerging per- and polyfluoroalkyl substances (PFASs) in river water collected in 2016 up- and downstream from a fluorochemical production plant, as well as in river water from control sites, in The Netherlands. Additionally, drinking water samples were collected from municipalities in the vicinity from the production plant, as well as in other regions in The Netherlands. The PFOA replacement chemical GenX was detected at all downstream river sampling sites with the highest concentration (812 ng/L) at the first sampling location downstream from the production plant, which was 13 times higher than concentrations of sum perfluoroalkylcarboxylic acids and perfluoroalkanesulfonates (∑PFCA+∑PFSA). Using high resolution mass spectrometry, 11 polyfluoroalkyl acids belonging to the C_2nH_2nF_2nO₂, C_2nH_2n+2F_2nSO₄ or C_2n+1H_2nF_2n+4SO₄ homologue series were detected, but only in downstream water samples. These emerging PFASs followed a similar distribution as GenX among the downstream sampling sites, suggesting the production plant as the source. Polyfluoroalkyl sulfonates (C_2nH₂F_4nSO₃) were detected in all collected river water samples, and therefore appear to be ubiquitous contaminants in Dutch rivers. GenX was also detected in drinking water collected from 3 out of 4 municipalities in the vicinity of the production plant, with highest concentration at 11 ng/L. Drinking water containing the highest level of GenX also contained two C_2nH_2nF_2nO₂ homologues.

Figure 1

Sampling locations of river water samples (R1–R18) and drinking water samples (D1–D6) collected in The Netherlands in 2016. See SI Table S2 for more sample location details. The location of the fluorochemical production plant is indicated by the red star.

Figure 2

Concentrations of GenX and ∑PFCA (C_4–10) + ∑PFSA (C_4,6,7,8) in ng/L in river water samples (R1–R18) and drinking water samples (D1–D6) collected in 2016 in The Netherlands. Downstream from sampling site R11 the river splits into a “north” and “south” branch, which merge upstream from sampling site R2. Samples from R6 and R9 are collected from rivers merging with “north” or “south” branch. See Table 1 for individual PFCA and PFSA concentrations, and SI Table S2 and Figure 1 for locations of the sampling sites. The fluorochemical production plant is located between sampling sites R13 and R14, and the arrows indicate the general water flow direction.

Figure 3

Relative HRMS instrumental response (with instrumental response at sampling location R13 set at 100%) of detected emerging PFAS homologue series in river water sampled downstream from a fluorochemical production plant (R15–R18 contained no detectable peaks of the homologue series) (left plot), and HRMS area count of emerging and legacy homologue series at sampling location R13 (right plot). See Tables 1 and 2 for individual compounds detected within a homologue series, and SI Table S2 and Figure 1 for more details on sampling locations. The fluorochemical production plant is located between sampling sites R13 and R14.