Mark J. Strynar

Stormwater runoff is a significant contributor of phosphorus (P) loading to waterbodies around the world. Green stormwater infrastructure (GSI) that uses filtration media, such as bioretention, can effectively retain suspended solids and associated particulate P, but is commonly less effective for soluble P retention. The addition of aluminum-based drinking water treatment residuals (DWTRs) may increase P-sorbing capacity of GSI media, though guidance is needed for material selection and to reduce risk of potential contamination. This study examined the P removal capacities of DWTRs (n=11) from drinking water treatment plants in the New England region (northeastern USA). DWTRs were compared for P-sorption potential using batch isotherm and column experiments and characterized for several material properties as well as arsenic leaching and per and polyfluoroalkyl substances (PFAS) content. Results indicate that P retention capacity of DWTRs is generally high (>1,000 mg P kg^-1) but varies by approximately one order of magnitude. Lower DWTR bulk density and greater oxalate-extractable Al + Fe were correlated with greater P retention in column experiments. Our findings also indicate that the potential for significant arsenic leaching is low. PFAS were detected in 36% of DWTRs, often at low levels near the method detection limit, with three DWTRs having higher levels of certain PFAS. The addition of DWTRs to GSI is promising for enhanced soluble P removal on a decadal scale (10-90 years), but additional research on As, PFAS, and other contaminants should be pursued prior to use, especially in areas with known or suspected source water contamination. Achieving effective long-term P removal requires selecting DWTRs with favorable material properties (e.g., drier, lower bulk density, greater oxalate-extractable Al + Fe), and mixture with sand at up to 10% DWTR by volume and potentially higher if proven to not impede hydraulic conductivity. Field monitoring of DWTR-enhanced infrastructure at multiple time points postinstallation (e.g., years 1, 5, 10, 20, and 30) is needed to confirm P removal longevity over expected infrastructure lifespans.

With thousands of documented perfluoroalkyl and polyfluoroalkyl substances (PFAS), novel methods are needed to comprehensively characterize these fluorinated compounds in the environment, biota, and humans. Despite being the most common approach, liquid chromatography high-resolution mass spectrometry (LC-HRMS) only covers a fraction of PFAS. To address this gap, we developed a nontargeted gas chromatography high-resolution mass spectrometry (GC-HRMS) workflow to extend coverage of the PFAS chemical space, developing and incorporating the most extensive GC HRMS PFAS libraries to date covering over 1,900 electron ionization (EI) and positive chemical ionization (PCI) predicted and experimental spectra. Five environmental and biological matrices were assessed: aqueous film forming foam (AFFF), industrial outfall, municipal leachate, residential floor dust, and human blood. A novel compound was identified (2-(perfluorohexyl)ethanethiol) in multiple AFFF formulations. A rarely monitored PFAS was additionally detected (N-methyl-N-(2-hydroxyethyl)perfluorooctanesulfonamide, N-MeFOSE) in human blood, industrial outfall, municipal leachate, and residential floor dust at high frequency and abundance. A comparison to LC-HRMS approaches for leachate and blood showed no overlap between annotated PFAS. The nontargeted workflow presented here provides essential tools to expand PFAS monitoring capabilities and identify previously undetected compounds that may pose significant health and environmental risks.

High-resolution accurate mass non-targeted analysis (NTA) is a useful discovery tool for metabolite characterization of in vivo dosing studies since it enables detection of both predicted and unexpected biotransformation products. We used NTA to investigate biotransformation of perfluorohexanesulfonamide (PFHxSA) in plasma and liver from male and female Sprague Dawley rats after a 5-day repeat exposure study. PFHxSA is an emerging per- and polyfluoroalkyl substance (PFAS) with unknown toxicity and a potentially reactive headgroup. NTA revealed the presence of predicted in vivo biotransformation products (BP) such as perfluorohexane sulfonic acid (PFHxS) and perfluorohexanesulfinic acid (PFHxSi). PFHxSi also has unknown toxicity and has not, to our knowledge, been previously reported as a PFHxSA BP in mammals. Multiple perfluoroalkyl ether sulfonamides, associated BPs, and novel PFAS were also detected in rat plasma and liver. We observed sex-specific distributions of the dosed compound and BPs, suggesting different toxicokinetics and biological responses. The presence of a complex mixture of predicted and unexpected PFAS in plasma and liver not only mimics the complexity of environmental exposure but also highlights the need for toxicity testing with mixtures and a more complete assessment of dosing solution purity.

To estimate half-lives for novel fluoroethers, the GenX Exposure Study obtained two serum measurements for per- and polyfluoroalkyl substances (PFAS) for 44 participants of age 12-86 years from North Carolina, collected 5 and 11 months after fluoroether discharges into the drinking water source were controlled. The estimated half-lives for these compounds were 127 days (95% confidence interval (95% CI) = 86, 243 days) for perfluorotetraoxadecanoic acid (PFO4DA), 296 days for Nafion byproduct 2 (95% CI = 176, 924 days), and 379 days (95% CI = 199, 3870 days) for perfluoro-3,5,7,9,11-pentaoxadodecanoic acid (PFO5DoA). Using these estimates and the literature values, a model was built that predicted PFAS half-lives using structural properties. Three chemical properties predicted 55% of the variance of PFAS half-lives based on 15 PFAS. A model with only molecular weight predicted 69% of the variance. Some properties can predict the half-lives of PFAS, but a deeper understanding is needed. These fluoroethers had biological half-lives longer than published half-lives for PFHxA and PFHpA (30-60 days) but shorter than those for PFOA and PFOS (800-1200 days). These are the first and possibly only estimates of human elimination half-lives of these fluoroethers.

Background The intersection of the topics of high-resolution mass spectrometry (HRMS) and per- and polyfluoroalkyl substances (PFAS) bring together two disparate and complex subjects. Recently non-targeted analysis (NTA) for the discovery of novel PFAS in environmental and biological media has been shown to be valuable in multiple applications. Classical targeted analysis for PFAS using LC-MS/MS, though growing in compound coverage, is still unable to inform a holistic understanding of the PFAS burden in most samples. NTA fills at least a portion of this data gap. Objectives Entrance into the study of novel PFAS discovery requires identification techniques such as HRMS (e.g., QTOF and Orbitrap) instrumentation. This requires practical knowledge of best approaches depending on the purpose of the analyses. The utility of HRMS applications for PFAS discovery is unquestioned and will likely play a significant role in many future environmental and human exposure studies. Methods/Results PFAS have some characteristics that make them standout from most other chemicals present in samples. Through a series of tell-tale PFAS characteristics (e.g., characteristic mass defect range, homologous series and characteristic fragmentation patterns), and case studies different approaches and remaining challenges are demonstrated. Impact statement The identification of novel PFAS via non-targeted analysis using high resolution mass spectrometry is an important and difficult endeavor. This synopsis document will hopefully make current and future efforts on this topic easier to perform for novice and experienced alike. The typical time devoted to NTA PFAS investigations (weeks to months or more) may benefit from these practical steps employed.