Identification and quantification of novel per- and polyfluoroalkyl substances (PFAS) contamination in a Great Lakes urban-dominated watershed.

Per- and polyfluoroalkyl substances (PFAS) are a large group of synthetic organic fluoro-compounds that are oil-, water-, and flame-resistant, making them useful in a wide range of commercial and consumer products, as well as resistant to environmental degradation. To assess the impact of urbanization and wastewater treatment processes, surface water and sediment samples were collected at 27 sites within the Great Lakes in the Lake Huron to Lake Erie corridor (HEC), an international waterway including the highly urbanized Detroit and Rouge Rivers. Samples were analyzed for 92 PFAS via UHPLC-MS/MS. Our previous data in the HEC found the highest amount of PFAS contamination at the Rouge River mouth. In addition to evaluating the input of the Rouge River into the HEC, we evaluated the transport of PFAS into the HEC from other major tributaries. PFAS were detected in both surface water and sediment at all sites in this study, with a total of 10 congeners quantified in all surface water samples and 16 congeners quantified in all sediment samples, indicating ubiquitous contamination. Perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) were pervasive in the HEC as these two compounds were detected in all sites and matrices, often at concentrations above the US EPA's recommended lifetime interim updated health advisories. Surface water samples contained more perfluorohexanoic acid (PFHxA) than any other congener, with average aqueous PFHxA across all surface water samples exceeding the average concentration previously reported in the Great Lakes. Sediment samples were dominated by PFOS, but novel congeners, notably 3-Perfluoropentyl propanoic acid (FPePA), were also quantified in sediment. The Rouge River and other tributaries contribute significantly to the PFAS burden in the HEC including Lake Erie. Overall, our results indicate the need for expanding toxicological research and risk assessment focused on congeners such as PFHxA and PFAS mixtures, as well as regulation that is tighter at the onset of production and encompasses PFAS as a group at a national level.

Investigating the partitioning behavior of per- and polyfluoroalkyl substances (PFAS) during thermal landfill leachate evaporation.

Thermal landfill leachate evaporator systems can reduce the volume of leachate by up to 97%, while releasing water vapor and producing residuals (volume-reduced leachate and sludge) that are managed on-site. On-site thermal evaporators offer landfill operators leachate management autonomy without being subject to increasingly stringent wastewater treatment plant requirements. However, little is known about the partitioning of PFAS within these systems, nor the extent to which PFAS may be emitted into the environment via vapor. In this study, feed leachate, residual evaporated leachate, sludge, and condensed vapor were sampled at two active full-scale thermal landfill leachate evaporators and from a laboratory-scale leachate evaporation experiment. Samples were analyzed for 91 PFAS via ultra-high pressure liquid chromatography - tandem mass spectrometry (UHPLC-MS/MS). Similar trends were observed from Evaporator 1, Evaporator 2, and the laboratory-scale evaporator; ∑PFAS were concentrated in the residual evaporated leachate during evaporation by a factor of 5.3 to 20. All condensed vapors sampled (n = 5) contained PFAS, predominantly 5:3 fluorotelomer carboxylic acid (5:3FTCA), (full-scale vapors 729 - 4087 ng/L PFAS; lab-scale vapor 61.0 ng/L PFAS). For Evaporators 1 and 2, an estimated 9 - 24% and 10%, respectively, of the PFAS mass entering the evaporators in leachate was released with vapor during the days of sample collection. '.

Investigating the sources and fate of per- and polyfluoroalkyl substances (PFAS) in food waste compost.

Composting municipal food waste is a key strategy for beneficially reusing methane-producing waste that would otherwise occupy landfill space. However, land-applied compost can cycle per- and polyfluoroalkyl substances (PFAS) back into the food supply and the environment. We partnered with a pilot-scale windrow composting facility to investigate the sources and fate of 40 PFAS in food waste compost. A comparison of feedstock materials yielded concentrations of ∑PFAS under 1 ng g-1 in mulch and food waste and at 1380 ng g-1 in leachate from used compostable food contact materials. Concentrations of targeted ∑PFAS increased with compost maturity along the windrow (1.85-23.1 ng g-1) and in mature stockpiles of increasing curing age (12.6-84.3 ng g-1). Among 15 PFAS quantified in compost, short-chain perfluorocarboxylic acids (PFCAs) - C5 and C6 PFCAs in particular - led the increasing trend, suggesting biotransformation of precursor PFAS into these terminal PFAS through aerobic decomposition. Several precursor PFAS were also measured, including fluorotelomer carboxylic acids (FTCAs) and polyfluorinated phosphate diesters (PAPs). However, since most targeted analytical methods and proposed regulations prioritize terminal PFAS, testing fully matured compost would provide the most relevant snapshot of PFAS that could be land applied. In addition, removing co-disposed food contact materials from the FW feedstock onsite yielded only a 37 % reduction of PFAS loads in subsequent compost, likely due to PFAS leaching during co-disposal. Source-separation of food contact materials is currently the best management practice for meaningful reduction of PFAS in food waste composts intended for land application.

Species-specific profiles of per- and polyfluoroalkyl substances (PFAS) in small coastal sharks along the South Atlantic Bight of the United States.

Per- and polyfluoroalkyl substances (PFAS) have gained widespread commercial use across the globe in various industrial and consumer products, such as textiles, firefighting foams, and surface coating materials. Studies have shown that PFAS exhibit a strong tendency to accumulate within aquatic food webs, primarily due to their high bioaccumulation potential and resistance to degradation. Despite such concerns, their impact on marine predators like sharks remains underexplored. This study aimed to investigate the presence of 34 PFAS in the plasma (n = 315) of four small coastal sharks inhabiting the South Atlantic Bight of the United States (U.S). Among the sharks studied, bonnetheads (Sphyrna tiburo) had the highest ∑PFAS concentration (3031 ± 1674 pg g - 1 plasma, n = 103), followed by the Atlantic sharpnose shark (Rhizoprionodon terraenovae, 2407 ± 969 pg g - 1, n = 101), blacknose shark (Carcharhinus acronotus, 1713 ± 662 pg g - 1, n = 83) and finetooth shark (Carcharhinus isodon, 1431 ± 891 pg g - 1, n = 28). Despite declines in the manufacturing of perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), the long-chain (C8 - C13) perfluoroalkyl acids (PFAAs) were frequently detected, with PFOS, perfluorodecanoic acid (PFDA), and perfluorotridecanoic acid (PFTrDA) present as the most dominant PFAS. Furthermore, males exhibited significantly higher ∑PFAS concentrations than females in bonnetheads (p < 0.01), suggesting possible sex-specific PFAS accumulation or maternal offloading in some species. The results of this study underscore the urgency for more extensive biomonitoring of PFAS in aquatic/marine environments to obtain a comprehensive understanding of the impact and fate of these emerging pollutants on marine fauna.

Assessing construction and demolition wood-derived biochar for in-situ per- and polyfluoroalkyl substance (PFAS) removal from landfill leachate.

With regulations for per-and polyfluoroalkyl substances (PFAS) impending, the abundance of these chemicals of emerging concern in municipal solid waste (MSW) landfill leachate increasingly challenges landfill operators to seek on-site leachate pre-treatment options. This two-staged study explores the potential reuse of biochar derived from construction and demolition debris (CDD) wood as an in-situ PFAS sorbent for application within MSW landfill leachate collection systems. Batch leaching tests were first used to examine the feasibility of capturing PFAS from landfill leachate using two sources of CDD-wood-derived biochar. Then, columns were used to test the in-situ sorption capabilities of the same biochars under simulated landfill conditions. All leachates were characterized for pH, chemical oxygen demand, ammonia-nitrogen, and 92 PFAS. Seventeen PFAS were detected in the batch leaching experiment, and nine PFAS were detected in column leachates. In the batch leaching scenario, Biochar 1 achieved a maximum of 29% PFAS reduction compared to controls. Columns containing Biochar 1 generated leachates with PFAS concentrations 50% to 80% higher than those in control columns for the duration of the experiment. Columns containing Biochar 2 generated leachates with PFAS concentrations 44% less than controls in week 1 and similar concentrations in weeks 2, 3, and 4. In this study, PFAS removal from landfill leachate using biochar derived from CDD wood was not significant. Further research on biochar derived from CDD wood is needed before it can be recommended as an in-situ landfill leachate pre-treatment method.

Emerging polycyclic aromatic hydrocarbon (PAH) and trace metal leachability from reclaimed asphalt pavement (RAP).

The environmental risks associated with the storage, reuse, and disposal of unencapsulated reclaimed asphalt pavement (RAP) has been previously examined, but because of a lack of standardized column testing protocols and recent interest on emerging constituents with higher toxicity, questions surrounding leaching risks from RAP continue. To address these concerns, RAP from six, discrete stockpiles in Florida was collected and leach tested following the most up-to-date, standard column leaching protocol - United States Environmental Protection Agency (US EPA) Leaching Environmental Assessment Framework (LEAF) Method 1314. Sixteen EPA priority polycyclic aromatic hydrocarbons (PAHs), 23 emerging PAHs, identified through relevance in literature, and heavy metals were investigated. Column testing showed minimal leaching of PAHs; only eight compounds, three priority PAHs and five emerging PAHs, were released at quantifiable concentrations, and where applicable, were below US EPA Regional Screening Levels (RSL). Though emerging PAHs were identified more frequently, in most cases, priority compounds dominated contributions to overall PAH concentration and benzo(a)pyrene (BaP) equivalent toxicity. Except for arsenic, molybdenum, and vanadium in two samples, metals were found below limits of detection (LOD) or below risk thresholds. Arsenic and molybdenum concentrations diminished over time with increased exposure to liquid, but elevated vanadium concentrations persisted in one sample. Further batch testing linked vanadium to the aggregate component of the sample, unlikely to be encountered in typical RAP sources. As demonstrated by generally low constituent mobility observed during testing, the leaching risks associated with the beneficial reuse of RAP are limited, and under typical reuse conditions, factors of dilution and attenuation would likely reduce leached concentrations below relevant risk-based thresholds at a point of compliance. When considering emerging PAHs with higher toxicities, analyses indicated minimal impact to overall leachate toxicity, further suggesting that with proper management, this heavily recycled waste stream is unlikely to pose leaching risk.

Up in the air: Polyfluoroalkyl phosphate esters (PAPs) in airborne dust captured by air conditioning (AC) filters.

Per- and polyfluoroalkyl substances (PFAS) are ubiquitously present in our indoor living environments. Dust is thought to accumulate PFAS released indoors and serve as an exposure pathway for humans. Here, we investigated whether spent air conditioning (AC) filters can be exploited as opportunistic samplers of airborne dust for assessing PFAS burden in indoor environments. Used AC filters from campus facilities (n = 19) and homes (n = 11) were analyzed for 92 PFAS via targeted ultra-high pressure liquid chromatography - tandem mass spectrometry (UHPLC-MS/MS). While 27 PFAS were measured (in at least one filter), the predominant species were polyfluorinated dialkylated phosphate esters (diPAPs), with the sum of 6:2-, 8:2-, and 6:2/8:2diPAPs accounting for approximately 95 and 98 percent of ∑27PFAS in campus and household filters, respectively. Exploratory screening of a subset of the filters revealed the presence of additional species of mono-, di-, and tri-PAPs. Considering the constant human exposure to dust indoors and the potential of PAPs to degrade into terminal species with well-established toxicological risks, assessing dust for these precursor PFAS warrants further investigation with respect to both human health and PFAS loading to landfills from this under studied waste stream.