Mid Sweden University

Feature detection plays a crucial role in non-target screening (NTS), requiring careful selection of algorithm parameters to minimize false positive (FP) features. In this study, a stochastic approach was employed to optimize the parameter settings of feature detection algorithms used in processing high-resolution mass spectrometry data. This approach was demonstrated using four open-source algorithms (OpenMS, SAFD, XCMS, and KPIC2) within the patRoon software platform for processing extracts from drinking water samples spiked with 46 per- and polyfluoroalkyl substances (PFAS). The designed method is based on a stochastic strategy involving random sampling from variable space and the use of Pearson correlation to assess the impact of each parameter on the number of detected suspect analytes. Using our approach, the optimized parameters led to improvement in the algorithm performance by increasing suspect hits in case of SAFD and XCMS, and reducing the total number of detected features (i.e., minimizing FP) for OpenMS. These improvements were further validated on three different drinking water samples as test dataset. The optimized parameters resulted in a lower false discovery rate (FDR%) compared to the default parameters, effectively increasing the detection of true positive features. This work also highlights the necessity of algorithm parameter optimization prior to starting the NTS to reduce the complexity of such datasets.

Despite the widespread presence of per- and polyfluoroalkyl substances (PFAS) in freshwater environments, only a few studies have addressed their bioaccumulation in macrophytes and benthic invertebrates. This study therefore aimed at investigating the presence of 40 PFAS in sediments, assessing their bioaccumulation in a rooting macrophyte (Myriophyllum spicatum) and a benthic invertebrate (Lumbriculus variegatus) and examining the effects of the presence and bioturbation activity of the invertebrate on PFAS bioaccumulation in the plants. The macrophytes were exposed to sediments originating from a reference and a PFAS-contaminated site. The worms were introduced in half of the replicates, and at the end of the experiment, PFAS were quantified in all environmental compartments. Numerous targeted PFAS were detected in both sediments and taken up by both organisms, with summed PFAS concentrations in organisms largely exceeding concentrations in the original sediments. Bioaccumulation differed between organisms and the two sediments. The presence of the worms significantly reduced the PFAS concentrations in the plant tissues, but for some compounds, root bioaccumulation increased in the presence of the worms. This effect was most prominent for the degradable PFAS precursors. It is concluded that organisms affect the environmental fate of PFAS, emphasizing that contaminant–macroinvertebrate interactions are two-sided.

Reverse osmosis (RO) is increasingly used in drinking water production to effectively remove micropollutants, such as perfluoroalkyl and polyfluoroalkyl substances (PFAS). However, RO membranes themselves may contain PFAS, which can potentially leach into treated drinking water. Leaching experiments and direct total oxidizable precursor assays revealed the presence and leaching potential of PFOS (branched and linear), PFBA, PFHxA, PFNA, and PFOA in five selected commercial RO membranes. This resulted in the release of tens of milligrams of ΣPFAS per membrane element used in drinking water production. Depending on assumptions made regarding leaching kinetics and volume of produced water per membrane element, predicted concentrations of ΣPFAS in the produced water ranged from less than one up to hundreds of pg/L. These concentrations are two to four orders of magnitude lower than those currently observed in Dutch drinking waters. The origin of PFAS in the membranes remains unclear. Further research is needed to bridge the gap between the laboratory conditions as used in this study and the real-world conditions and for a full understanding of potential leaching scenarios. Such an understanding is critical for water producers using RO technologies to proactively manage and mitigate potential PFAS contamination.

Recent stringent drinking water quality standards create challenges for water utilities to meet these standards. Advanced treatment techniques will have to be applied on many drinking water production locations to meet these quality standards. This study investigated the sorption of per- and polyfluorinated-alkyl substances (PFAS) onto granular activated carbon (GAC). The study was performed at environmentally relevant PFAS concentrations and a realistic water-to-GAC ratio, providing a realism often overlooked in existing studies. Three different forms of GAC were evaluated, differing in micropore and mesopore structures. Tap water spiked with 5 ng/L of each of 31 PFAS was used in the sorption experiments, i.e. perfluorocarboxylic acids (C4–C12), perfluorosulfonic acids (PFSA, C5–C10) including linear and branched isomers, and three groups of PFAS precursors (per-/polyfluoroalkyl ether acids, sulfonamides, and sulfonamide acetic acids).The three studied GAC did not exhibit distinct differences in PFAS sorption. The removal of PFAS was below 50 % for most studied PFAS, except for the short-chain PFAS precursors. Sorption was affected by both the carbon chain length and functional groups for PFAS, while this was not observed for PFAS precursors. The presence of ether linkages and sulfonamide groups notably enhanced sorption. Linear and branched PFSA demonstrated similar sorption behavior, whereas branched isomers of the sulfonamide acetic acid precursors exhibited significantly higher sorption. This indicates that sorption was determined by both hydrophobic and electrostatic interactions.Given the relatively low PFAS removal by GAC under environmentally relevant test conditions, further improvements in sorbents are required to ensure that PFAS concentrations in produced drinking water comply with drinking water standards.

A wide range of PFAS residues were studied in an aquifer used for drinking water production which was affected by historical PFAS contamination from a landfill and military camp. Samples were taken at three monitoring and four pumping wells at different depths ranging from 33 to 147 m below the land surface and analysed for a series of 53 PFAS (C2-C14) and PFAS precursors (C4-C24). A comparison of results to earlier research from 2013, with a more limited range of PFAS, showed decreasing concentrations and migration of PFAS with increasing depth and distance from the contamination source.The PFAS profile and branched/linear isomer ratio are used as source characterization tools. The landfill was confirmed to contaminate the groundwater in both monitoring wells, while the military camp was indicated as a probable source for PFAS observed in the deep sampling points of one of the monitoring wells. Pumping wells used to produce drinking water are not yet affected by these two PFAS sources. In one of the four sampled pumping wells, a different PFAS profile and isomer pattern was observed, which indicated a different but yet unknown source.This work shows the necessity of implementing regular screening to identify potential (historical) PFAS sources to be able to prevent future contaminant migration nearby and towards drinking water abstraction wells.

This study investigates human exposure to per- and polyfluoroalkyl substances (PFAS) via drinking water and evaluates human health risks. An analytical method for 56 target PFAS, including ultrashort-chain (C2–C3) and branched isomers, was developed. The limit of detection (LOD) ranged from 0.009 to 0.1 ng/L, except for trifluoroacetic-acid and perfluoropropanoic-acid with higher LODs of 35 and 0.24 ng/L, respectively. The method was applied to raw and produced drinking water from 18 Dutch locations, including groundwater or surface water as source, and applied various treatment processes. Ultrashort-chain (300 to 1100 ng/L) followed by the group of perfluoroalkyl-carboxylic-acids (PFCA, ≥C4) (0.4 to 95.1 ng/L) were dominant. PFCA and perfluoroalkyl-sulfonic-acid (≥C4), including precursors, showed significantly higher levels in drinking water produced from surface water. However, no significant difference was found for ultrashort PFAS, indicating the need for groundwater protection. Negative removal of PFAS occasionally observed for advanced treatment indicates desorption and/or degradation of precursors. The proportion of branched isomers was higher in raw and produced drinking water as compared to industrial production. Drinking water produced from surface water, except for a few locations, exceed non-binding provisional guideline values proposed; however, all produced drinking waters met the recent soon-to-be binding drinking-water-directive requirements.

Perfluoroalkane substances (PFAS) comprise a large family of chemicals of environmental concern and are subject to chemical analyses, international regulation, and risk assessments. Environmental samples including air, water, sediment, and soil as abiotic matrices, food samples comprising fish, meat (beef, sheep, chicken), egg, butter, and milk as well as human milk samples were assessed using uni- and multivariate methods. Participating countries were asked to provide baseline samples and not target potential hotspots. Chemometric analysis was possible for only three of the 15 PFAS monitored, namely perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and perfluorohexane sulfonic acid (PFHxS). The assessments showed that PFAS contamination in developing countries and in all matrices considered was almost equally attributed to PFOS and PFOA; PFHxS did not play a role. Subsequently, across all samples, PFOS and PFOA were strongly negatively correlated (spearman correlation coefficient r = −0.94). The measured values showed moderate positive correlation between PFOS and PFOA (r = 0.76) indicating common sources or environmental behavior. No clear pattern could be observed for geographic locations nor for transfers between matrices. Whereas the abiotic samples—soil, sediment, air—gave a very heterogenous picture (very small p-values) and had wide ranges and outliers, the measured values of the biota samples were not significantly different between matrices.

Within the global monitoring plan (GMP) established by article 16 of the Stockholm Convention on Persistent Organic Pollutants, perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and perfluorohexane sulfonic acid (PFHxS) are recommended for analysis in core matrices to assess occurrence and changes geographically and with time. In 101 samples consisting of 86 national pools and 15 pools from States in Brazil obtained between 2008 and 2019, PFHxS was detected in 17% of the national pools and none in Brazil. PFOA and PFOS had a detection frequency of 100% and 92%, respectively. Other perfluoroalkane substances (PFAS) had either low detection frequencies and median values of zero (carboxylic acids C4–C11; except PFOA) or could not be quantified in any sample (sulfonic acids, C4–C10, and long-chain carboxylic acids, C12–C14). Correlation between PFOA and PFOS was moderately (r = 0.58). Whereas median values were almost identical (18.9 pg/g f.w. for PFOS; 18.6 pg/g f.w. for PFOA), PFOS showed larger ranges (< 6.2 pg/g f.w.−212 pg/g f.w.) than PFOA (< 6.2 pg/g f.w.−63.4 pg/g f.w.). It was shown that wealthier countries had higher PFOA concentrations than poorer countries. No difference in concentrations was found for samples collected in countries having or not having ratified the Stockholm Convention amendments to list PFOS or PFOA. The goal to achieve 50% decrease in concentrations within ten years was met by Antigua and Barbuda, Kenya, and Nigeria for PFOS and by Antigua and Barbuda for PFOA. In a few cases, increases were observed; one country for PFOS, four countries for PFOA.

The global monitoring plan (GMP) established under the Stockholm Convention on Persistent Organic Pollutants (POPs) had defined ambient air, human milk or blood, and water as core matrices to be analyzed and assessed for spatial and temporal distribution. Within projects coordinated by the United Nations Environment Programme (UNEP), developing countries were offered to have other matrices analyzed for perfluoroalkane substances (PFAS) in one experienced laboratory. A total of 266 samples from 26 countries located in Africa, Asia, and Latin America were collected during 2018–2019 and analyzed for 15 PFAS. The limits of quantification were 6.2 pg/g fresh weight for most PFAS. The statistical assessment of 262 samples, four were excluded due to extreme values, showed that across abiotic and biota samples, perfluorooctane sulfonic acid (PFOS) had the highest detection frequency (80%) and the highest median value (19.2 pg/g), followed by perfluorooctanoic acid (PFOA) with 73% and a median value of 7.67 pg/g. Among the matrices, water (55%), sediment (49%) and fish (44%) had the most complex pattern, i.e., number of PFAS quantified. Dairy products and chicken meat had less PFAS present. From the 137 foods, fish, meat, eggs, analyzed in this study, only two fish samples would exceed one of the limit values proposed by the European Commission. To assess human exposure, we suggest including dairy products and drinking water since selective and sensitive methods would allow quantification of the four proposed PFAS.