Immobilization of per- and polyfluoroalkyl substances (PFAS): Comparison of leaching behavior by three different leaching tests.

The evaluation of PFAS immobilization performance in laboratory experiments, especially the long-term stability, is a challenge. To contribute to the development of adequate experimental procedures, the impact of experimental conditions on the leaching behavior was studied. Three experiments on different scales were compared: batch, saturated column, and variably saturated laboratory lysimeter experiments. The Infinite Sink (IS) test - a batch test with repeated sampling - was applied for PFAS for the first time. Soil from an agricultural field amended with paper-fiber biosolids polluted with various perfluoroalkyl acids (PFAAs; 655 µg/kg ∑18PFAAs) and polyfluorinated precursors (1.4 mg/kg ∑18precursors) was used as the primary material (N-1). Two types of PFAS immobilization agents were tested: treatment with activated carbon-based additives (soil mixtures: R-1 and R-2), and solidification with cement and bentonite (R-3). In all experiments, a chain-length dependent immobilization efficacy is observed. In R-3, the leaching of short-chain PFAAs was enhanced relative to N-1. In column and lysimeter experiments with R-1 and R-2, delayed breakthrough of short-chain PFAAs (C4) occurred (> 90 days; in column experiments at liquid-to-solid ratio (LS) > 30 L/kg) with similar temporal leaching rates suggesting that leaching in these cases was a kinetically controlled process. Observed differences between column and lysimeter experiments may be attributed to varying saturation conditions. In IS experiments, PFAS desorption from N-1, R-1, and R-2 is higher than in the column experiments (N-1: +44 %; R-1: +280 %; R-2: +162 %), desorption of short-chain PFAS occurred predominantly in the initial phase (< 14 days). Our findings demonstrate that sufficient operating times are essential in percolation experiments, e.g., in column experiments >100 days and LS > 30 L/kg. IS experiments may provide a faster estimate for nonpermanent immobilization. The comparison of experimental data from various experiments is beneficial to evaluate PFAS immobilization and to interpret leaching characteristics.

Can determination of extractable organofluorine (EOF) be standardized? First interlaboratory comparisons of EOF and fluorine mass balance in sludge and water matrices.

The high proportion of unidentified extractable organofluorine (EOF) observed globally in humans and the environment indicates widespread occurrence of unknown per- and polyfluoroalkyl substances (PFAS). However, efforts to standardize or assess the reproducibility of EOF methods are currently lacking. Here we present the first EOF interlaboratory comparison in water and sludge. Three participants (four organizations) analyzed unfortified and PFAS-fortified ultrapure water, two unfortified groundwater samples, unfortified wastewater treatment plant effluent and sludge, and an unfortified groundwater extract. Participants adopted common sample handling strategies and target lists for EOF mass balance but used in-house combustion ion-chromatography (CIC) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) methods. EOF accuracy ranged from 85-101% and 76-109% for the 60 and 334 ng L-1 fluorine (F) - fortified water samples, respectively, with between-laboratory variation of 9-19%, and within-laboratory variation of 3-27%. In unfortified sludge and aqueous samples, between-laboratory variation ranged from 21-37%. The contribution from sum concentrations of 16 individual PFAS (∑PFAS-16) to EOF ranged from 2.2-60% but extended analysis showed that other targets were prevalent, in particular ultra-short-chain perfluoroalkyl acids (e.g. trifluoroacetic acid) in aqueous samples and perfluoroalkyl acid-precursors (e.g. polyfluoroalkyl phosphate diesters) in sludge. The EOF-CIC method demonstrated promising accuracy, robustness and reporting limits but poor extraction efficiency was observed for some targets (e.g. trifluoroacetic acid).

Extending the knowledge about PFAS bioaccumulation factors for agricultural plants - A review.

A main source of perfluoroalkyl and polyfluoroalkyl substances (PFASs) residues in agricultural plants is their uptake from contaminated soil. Bioaccumulation factors (BAFs) can be an important tool to derive recommendations for cultivation or handling of crops prior consumption. This review compiles >4500 soil-to-plant BAFs for 45 PFASs from 24 studies involving 27 genera of agricultural crops. Grasses (Poaceae) provided most BAFs with the highest number of values for perfluorooctanoic acid and perfluorooctane sulfonic acid. Influencing factors on PFAS transfer like compound-specific properties (hydrophobicity, chain length, functional group, etc.), plant species, compartments, and other boundary conditions are critically discussed. Throughout the literature, BAFs were higher for vegetative plant compartments than for reproductive and storage organs. Decreasing BAFs per additional perfluorinated carbon were clearly apparent for aboveground parts (up to 1.16 in grains) but not always for roots (partly down to zero). Combining all BAFs per single perfluoroalkyl carboxylic acid (C4-C14) and sulfonic acid (C4-C10), median log BAFs decreased by -0.25(±0.029) and -0.24(±0.013) per fluorinated carbon, respectively. For the first time, the plant uptake of ultra-short-chain (≤ C3) perfluoroalkyl acids (PFAAs) was reviewed and showed a ubiquitous occurrence of trifluoroacetic acid in plants independent from the presence of other PFAAs. Based on identified knowledge gaps, it is suggested to focus on the uptake of precursors to PFAAs, PFAAs ≤C3, and additional emerging PFASs such as GenX or fluorinated ethers in future research. Studies regarding the uptake of PFASs by sugar cane, which accounts for about one fifth of the global crop production, are completely lacking and are also recommended. Furthermore, aqueous soil leachates should be tested as an alternative to the solvent extraction of soils as a base for BAF calculations.

Air-drying of soil samples - A crucial step in the determination of leachable concentrations of per- and polyfluoroalkyl substances.

Batch leaching tests at a liquid to solid ratio of 2 L/kg are a valuable tool for the assessment of low PFAS levels in soils. Data from different monitoring programs comprising samples without known local source of PFAS contamination showed that soil-sample drying at ambient temperature or at 40 °C prior to the leaching process leads to higher PFAS leachate levels compared to non-dried samples. The effect was greater for perfluoroalkyl carboxylic acids (PFCAs) than for perfluoroalkyl sulfonic acids (PFSAs). In a controlled field study comparing field-fresh (frozen to -18 °C and thawed) samples with air-dried (room temperature) samples median levels after drying increased to 140%-470% for C4 to C10 PFCAs and to 130%-200% for C4, C6, and C8 PFSAs, respectively. Thus, using field-fresh samples for batch leaching tests might underestimate the leachable fraction of PFAA in the field, where drying and leaching periods alternate.

Closing the gap - inclusion of ultrashort-chain perfluoroalkyl carboxylic acids in the total oxidizable precursor (TOP) assay protocol.

An improved protocol of the total oxidizable precursor (TOP) assay was developed for precursors to C2-C14 perfluoroalkyl carboxylic acids (PFCAs) and C4-C8 and C10 perfluoroalkyl sulfonic acids (PFSAs). The proposed protocol was tested and validated for contaminated soil samples. The perfluoroalkyl acids (PFAAs) present in the soil extract solutions after oxidation with persulfate were separated from the inorganic salts by vacuum-assisted drying of the digestion solution followed by solid-liquid extraction of the PFAAs with acetonitrile from the dry residue. Ion chromatography (for C2-C4 PFCAs) and reversed phase liquid chromatography (for all other PFASs), both coupled to tandem mass spectrometry, were used for quantification. High procedural recoveries of PFAAs between 68% and 123% with RSDs between 0.2% and 25% (n = 3) were achieved. The method was validated using selected polyfluoroalkyl phosphoric acid esters (PAPs) and bis-[2-(N-ethyl perfluorooctane-1-sulfonamido)ethyl] phosphoric acid ester (diSAmPAP) as model precursors in pure solutions and in the presence of soil matrix. The oxidation led to characteristic and reproducible PFCA patterns (in the case of PAPs) or PFOA (in the case of diSAmPAP) with total reaction yields between 92 ± 4% and 123 ± 13% (n = 3). The impact of the soil matrix on transformation yields was negligible. In a soil core from a PFAS-polluted agricultural site, precursors were concentrated in the upper 40 cm with long-chain precursors being prevalent. After oxidative digestion, the total molar PFAA-concentrations increased by factors of 1.6 to 5.0. More than 40 cm below ground precursors of TFAA, PFPrA and PFBA accounted for ∼50% of the reaction products, underlining the importance of their inclusion in mass balances based on the TOP assay.

Small, mobile, persistent: Trifluoroacetate in the water cycle - Overlooked sources, pathways, and consequences for drinking water supply.

Elevated concentrations of trifluoroacetate (TFA) of more than 100 µg/L in a major German river led to the occurrence of more than 20 µg/L TFA in bank filtration based tap waters. Several spatially resolved monitoring programs were conducted and discharges from an industrial company were identified as the point source of TFA contamination. Treatment options for TFA removal were investigated at full-scale waterworks and in laboratory batch tests. Commonly applied techniques like ozonation or granulated activated carbon filtration are inappropriate for TFA removal, whereas TFA was partly removed by ion exchange and completely retained by reverse osmosis. Further investigations identified wastewater treatment plants (WWTPs) as additional TFA dischargers into the aquatic environment. TFA was neither removed by biological wastewater treatment, nor by a retention soil filter used for the treatment of combined sewer overflows. WWTP influents can even bear a TFA formation potential, when appropriate CF3-containing precursors are present. Biological degradation and ozonation batch experiments with chemicals of different classes (flurtamone, fluopyram, tembotrione, flufenacet, fluoxetine, sitagliptine and 4:2 fluorotelomer sulfonate) proved that there are yet overlooked sources and pathways of TFA, which need to be addressed in the future.

Structural elucidation of main ozonation products of the artificial sweeteners cyclamate and acesulfame.

PURPOSE: The two artificial sweeteners cyclamate (CYC) and acesulfame (ACE) have been detected in wastewater and drinking water treatment plants. As in both facilities ozonation might be applied, it is important to find out if undesired oxidation products (OPs) are formed. METHODS: For the separation and detection of the OPs, several analytical techniques, including nuclear magnetic resonance experiments, were applied. In order to distinguish between direct ozone reaction and a radical mechanism, experiments were carried out at different pH values with and without scavenging OH radicals. Kinetic experiments were used for confirmation that the OPs are formed during short ozone contact time applied in waterworks. Samples from a waterworks using bank filtrate as raw water were analyzed in order to prove that the identified OPs are formed in real and full-scale ozone applications. RESULTS: In the case of CYC, oxidation mainly occurs at the carbon atom, where the sulfonamide moiety is bound to the cyclohexyl ring. Consequently, amidosulfonic acid and cyclohexanone are formed as main OPs of CYC. When ozone reacts at another carbon atom of the ring a keto moiety is introduced into the CYC molecule. Acetic acid and the product ACE OP170, an anionic compound with m/z=170 and an aldehyde hydrate moiety, were identified as the main OPs for ACE. The observed reaction products suggest an ozone reaction according to the Criegee mechanism due to the presence of a C=C double bond. ACE OP170 was also detected after the ozonation unit of a full-scale drinking water treatment plant which uses surface water-influenced bank filtrate as raw water. CONCLUSIONS: Acesulfame can be expected to be found in anthropogenic-influenced raw water used for drinking water production. However, when ACE OP170 is formed during ozonation, it is not expected to cause any problem for drinking water suppliers, because the primary findings suggest its removal in subsequent treatment steps, such as activated carbon filters.

Correlation of six anthropogenic markers in wastewater, surface water, bank filtrate, and soil aquifer treatment.

Six trace contaminants (acesulfame (ACE), sucralose (SUC), carbamazepine (CBZ), diatrizoic acid (DTA), 1H-benzotriazole (BTZ) and its 4-methyl analogue (4-TTri)) were traced from wastewater treatment plants (WWTPs) to receiving waters and further to riverbank filtration (RBF) wells to evaluate their prediction power as potential wastewater markers. Furthermore, the persistence of some compounds was investigated in advanced wastewater treatment by soil aquifer treatment (SAT). During wastewater treatment in four conventional activated sludge WWTPs ACE, SUC, and CBZ showed a pronounced stability expressed by stable concentration ratios in influent (in) and effluent (out) (ACE/CBZ: in45, out40; SUC/CBZ: in1.8, out1.7; and ACE/SUC: in24, out24). In a fifth WWTP, additional treatment with powdered activated carbon led to a strong elimination of CBZ, BTZ, and 4-TTri of about 80% and consequently to a distinctive shift of their ratios with unaffected compounds. Data from a seven month monitoring program at seven sampling locations at the rivers Rhine and Main in Germany revealed the best concentration correlation for ACE and CBZ (r(2) = 0.94) and also a good correlation of ACE and CBZ concentrations to BTZ and 4-TTri levels (r(2) = 0.66 to 0.82). The comparison of ratios at different sampling sites allowed for the identification of a CBZ point source. Furthermore, in Switzerland a higher consumption of SUC compared to Germany can be assumed, as a steadily increasing ACE/SUC ratio along the river Rhine was observed. In RBF wells a good correlation (r(2) = 0.85) was again observed for ACE and CBZ. Both also showed the highest stability at a prolonged residence time in the subsurface of a SAT field. In the most peripheral wells ACE and CBZ were still detected with mean values higher than 36 µg L(-1) and 1.3 µg L(-1), respectively. Although SUC concentrations in wastewater used for SAT decreased by more than 80% from about 18 µg L(-1) to 2.1 µg L(-1) and 3.5 µg L(-1) in these outlying wells, the compound was still adequate to indicate a wastewater impact in a qualitative way.