PFAS in municipal landfill leachate: Occurrence, transformation, and sources.

To understand sources and processes affecting per- and polyfluoroalkyl substances (PFAS), 32 PFAS were measured in landfill leachate from 17 landfills across Washington State in both pre-and post-total oxidizable precursor (TOP) assay samples, using an analytical method that was the precursor to EPA Draft Method 1633. As in other studies, 5:3FTCA was the dominant PFAS in the leachate, suggesting that carpets, textiles, and food packaging were the main sources of PFAS. Total PFAS concentrations (Σ32PFAS) ranged from 61 to 172,976 ng/L and 580-36,122 ng/L in pre-TOP and post-TOP samples, respectively, suggesting that little or no uncharacterized precursors remained in landfill leachate. Furthermore, due to chain-shortening reactions, the TOP assay often resulted in a loss of overall PFAS mass. Positive matrix factorization (PMF) analysis of the combined pre- and post-TOP samples produced five factors that represent sources and processes. Factor 1 consisted primarily of 5:3FTCA (intermediate of 6:2 fluorotelomer degradation and characteristic of landfill leachate), while factor 2 was dominated by PFBS (degradant of C-4 sulfonamide chemistry) and, to a lesser extent, by several PFCAs and 5:3FTCA. Factor 3 consisted primarily of both short-chain PFCAs (end-products of 6:2 fluorotelomer degradation) and PFHxS (derived from C-6 sulfonamide chemistry), while the main component of factor 4 was PFOS (dominant in many environmental media but minor in landfill leachate, perhaps reflecting a production shift from longer to shorter chain PFAS). Factor 5, highly loaded with PFCAs, was dominant in post-TOP samples and therefore represented the oxidation of precursors. Overall, PMF analysis suggests that the TOP assay approximates some redox processes which occur in landfills, including chain-shortening reactions which yield biodegradable products.

Regulation of Persistent Chemicals in Hazardous Waste: A Case Study of Washington State, USA.

Despite ongoing controversy, several strategic frameworks for defining chemicals of concern (e.g., persistent, bioaccumulative, toxic [PBT]; persistent, mobile, toxic [PMT]; persistent organic pollutant [POP]) share persistence as a key criterion. Persistence should be considered over the entire chemical life cycle from production to disposal, including hazardous waste management. As a case study, we evaluate persistence criteria in hazardous waste regulations in Washington state, USA, illustrate impacts on reported waste, and propose refinements in these criteria. Although Washington state defines persistence based on half-life (>1 y) and specific chemical groups that exceed summed concentration thresholds in waste (i.e., >0.01% halogenated organic compounds [HOCs] and >1.0% polycyclic aromatic hydrocarbons [PAHs]), persistence is typically addressed with HOC and PAH evaluation but seldom with half-life estimation. Notably, persistence is considered (with no specific criteria) in corresponding federal regulations in the United States (Resource Conservation and Recovery Act). Consequently, businesses in Washington state report annual amounts of state hazardous waste (including persistent waste) separately from federal hazardous waste. Total state-only waste, and total state and federal waste combined, nearly doubled (by weight) from 2008 to 2018. For the period 2016 to 2018, persistence criteria captured 17% of state-only waste and 2% of total state and federal waste combined. Two recommendations are proposed to improve persistence criteria in hazardous waste regulations. First, Washington state should consider aligning its half-life criterion with federal and European Union PBT definitions (e.g., 60-120 d) for consistency and provide specific methods for half-life estimation. Second, the state should consider expanding its list of persistent chemical groups (e.g., siloxanes, organometallics) with protective concentration thresholds. Ultimately, to the extent possible, Washington state should strive toward harmonizing persistence in hazardous waste regulations with corresponding criteria in global PBT, PMT, and POP frameworks. Integr Environ Assess Manag 2021;17:455-464. © 2020 SETAC.

Alterations in fingerprints of polychlorinated biphenyls in benthic biota at the Portland Harbor Superfund Site (Oregon, USA) suggest metabolism.

In order to understand the sources and fate of polychlorinated biphenyls (PCBs) in several species of benthic biota, including clams (Corbicula fluminea), oligochaetes (Lumbriculus variegatus), and mussels (Margaritifera falcata and Anodonta nuttalliana) at the Portland Harbor Superfund Site (PHSS), their congener fingerprints were examined. First, diagnostic ratios of congeners known to be metabolizable vs. recalcitrant in the cytochrome P450 (CYP) pathway were significantly lower in biota than in its co-located sediment, indicating metabolism may have occurred. Next, the congener patterns were analyzed using Positive Matrix Factorization (PMF). The dominant fingerprint (by mass) in benthic biota is related to Aroclor 1260 but displays differences in the fingerprint that are consistent with weathering via absorption, distribution, metabolism, and excretion (ADME). This fingerprint is similar to one isolated from PCBs in fish from Washington State, indicative of common metabolic pathways and consistent with CYP metabolism. When metabolism is taken into account, the spatial distribution of the PMF-isolated PCB fingerprints in biota matches well with those from co-located sediment samples, suggesting that the same mix of sources at one location partitions into biota and sediment. In accordance to their higher hydrophobicity, higher molecular weight (MW) PCB formulations were proportionately more abundant in biota than in sediment, although low MW PCBs (e.g., PCBs 4 and 11) do bioaccumulate in benthic organisms and should not be ignored in risk assessment efforts. Finally, fingerprinting suggests potential reasons why lab-based and field-based biota-sediment accumulation factors (BSAFs) differ substantially for bivalves.

Arsenic, lead, and other trace elements in soils contaminated with pesticide residues at the Hanford site (USA).

The primary purpose of this study was to characterize arsenic (As) and lead (Pb) concentrations in former orchard soils contaminated with lead arsenate pesticides at the Hanford site in Washington state (USA). Surface samples (n = 31) were collected from former orchard soils (in cultivation during the pre-Hanford period) at five locations at the 100 Areas and at one location at the Old Hanford Townsite (OHT). Another set of samples (n = 17) was collected over a soil depth interval of 10-50 cm at the four locations with the highest As and Pb surface concentrations. All samples were analyzed for 22 trace elements (including As and Pb) with inductively coupled plasma-atomic emission spectrometry (ICP-AES). The mean, standard deviation, and range for As in the surface soils were 30, 61, and 2.9-270 mg/kg dry wt, respectively. The corresponding statistics for Pb were 220, 460, and 6.5-1900 mg/kg dry wt, respectively. As and Pb concentrations in the surface soils were positively and significantly correlated (r = 0.91, Bonferroni p < 0.05). Descriptive statistics and bivariate correlations were also computed for other trace elements. As and Pb mean concentrations in the surface soils each differed significantly (p < 0.05) among Hanford locations, with the highest concentrations at the 100-H and 100-F Areas. Although both As and Pb mean concentrations decreased with soil depth, regression and correlation coefficients only, for Pb significantly differed from zero (b = -0.0372, r = -0.805, Bonferroni p < 0.05). Compared with data in the literature As and Pb concentrations found in this study exceeded background levels but were typical of orchard soils. Furthermore, mean As and Pb soil concentrations were in the range of various toxicological benchmarks derived for protection of human and ecological receptors.