Anion Exchange Resin and Inorganic Anion Parameter Determination for Model Validation and Evaluation of Unintended Consequences during PFAS Treatment.

When implementing anion exchange (AEX) for per- and polyfluoroalkyl substances treatment, temporal drinking water quality changes from concurrent inorganic anion (IA) removal can create unintended consequences (e.g., corrosion control impacts). To understand potential effects, four drinking water-relevant IAs (bicarbonate, chloride, sulfate, and nitrate) and three gel-type, strong-base AEX resins were evaluated. Batch binary isotherm experiments provided estimates of IA selectivity with respect to chloride ( K x ∕ C ) for IA/resin combinations where bicarbonate < sulfate ≤ nitrate at studied conditions. A multi-IA batch experiment demonstrated that binary isotherm-determined K x ∕ C values predicted competitive behavior. Subsequent column experiments with and without natural organic matter (NOM) allowed for the validation of a new ion exchange column model (IEX-CM; https://github.com/USEPA/Water_Treatment_Models). IA breakthrough was well-simulated using binary isotherm-determined K x ∕ C values and was minimally impacted by NOM. Initial AEX effluent water quality changes with corrosion implications included increased chloride and decreased sulfate and bicarbonate concentrations, resulting in elevated chloride-to-sulfate mass ratios (CSMRs) and Larson ratios (LRs) and depressed pH until the complete breakthrough of the relevant IA(s). IEX-CM utility was further illustrated by simulating the treatment of low-IA source water and a change in the source water to understand the resulting duration of changes in IAs and water quality parameters.

Strong Base Anion Exchange Selectivity of Nine Perfluoroalkyl Chemicals Relevant to Drinking Water.

Selectivity with respect to chloride (KPFAS∕C) was determined for nine drinking water relevant perfluoroalkyl and polyfluoroalkyl substances (PFAS): perfluoro-2-propoxypropanoic acid (GenX), five perfluoroalkyl carboxylic acids (PFCAs), and three perfluoroalkyl sulfonic acids (PFSAs). Three single-use strong base anion exchange gel resins were investigated, targeting drinking water relevant equilibrium PFAS liquid concentrations (≤500 ng/L). Except for the longest carbon chain PFCA (perfluorodecanoic acid) and PFSA (perfluorooctanesulfonic acid) studied, PFAS followed traditional ion exchange theory (law of mass action), including increasing equilibrium PFAS liquid concentrations with increasing equilibrium chloride liquid concentrations. Overall, KPFAS∕C values were (i) similar among resins for a given PFAS, (ii) 1-5 orders of magnitude greater than the selectivity of inorganic anions (e.g., nitrate) previously studied, (iii) 2 orders of magnitude greater for the same carbon chain length PFSA versus PFCA, (iv) found to proportionally increase with carbon chain length for both PFSAs and PFCAs, and (v) similar for GenX and perfluorohexanoic acid (six-carbon PFCA). A multisolute competition experiment demonstrated binary isotherm-determined KPFAS∕C values could be applied to simulate a multisolute system, extending work previously done with only inorganic anions to PFAS. Ultimately, estimated KPFAS∕C values allow future extension and validation of an open-source anion exchange column model to PFAS.

Practical implications of perfluoroalkyl substances adsorption on bottle materials: Isotherms.

To assess the practical implications of various bottle materials used in anion exchange (IX) or granular activated carbon (GAC) isotherm experiments, adsorption of seven per- and polyfluoroalkyl substances (PFAS) onto three common bottle materials (silanized glass, polypropylene, and high-density polyethylene [HDPE]) were screened. Results were similar between bottle materials; therefore, only HDPE was used in a detailed bottle material isotherm study with 11 PFAS. For each PFAS, an HDPE bottle isotherm was generated with equilibrium liquid phase concentrations relevant to drinking water (<2000 ng/L). Percent PFAS recoveries between 90% and 103%, 85% and 114%, and 54% and 108% were determined for perfluoro-2-propoxypropanoic acid (GenX), five perfluoroalkyl carboxylic acids, and five perfluoroalkyl sulfonic acids (PFSA), respectively. These results indicated only the five PFSA adsorbed to the HDPE bottles in a concentration-dependent manner. Furthermore, linear isomer versions of two PFSA exhibited greater adsorption. For each PFSA studied, a linear isotherm was generated and used to develop guidance for conducting future IX and GAC isotherm studies. Specifically, the minimum initial isotherm concentration was established such that a maximum 1% loss would be expected to the HDPE bottles, resulting in required initial concentrations of the five PFSA between 21 and 75 times that of the design isotherm liquid equilibrium concentration.

Design and evaluation of degassed anaerobic membrane biofilm reactors for improved methane recovery.

Anaerobic treatment of domestic wastewater (DWW) produces dissolved methane that needs to be recovered for use as an energy product. Membrane-based recovery systems have been reported in the literature but are often limited by fouling. The objective of this study was to develop a methane producing biofilm on the shell side surface a membrane to allow for immediate recovery of methane as it was produced, negating mass transfer resistance caused by fouling. Between 89 and 96% of total methane produced was recovered via in-situ degassing without the need for fouling control or cleaning throughout 72 weeks of operation. High methane recovery efficiencies led to predictions of net positive energy yield in one reactor and a 32-61% reduction in energy demand in the others compared to the control. This research demonstrates the feasibility and usefulness of combining attached growth anaerobic wastewater treatment processes with hollow fiber membrane methane recovery systems for improved operation.

Occurrence of Per- and Polyfluoroalkyl Substances (PFAS) in Source Water and Their Treatment in Drinking Water.

Per-and polyfluoroalkyl substances (PFAS) occurrence in drinking water and treatment methods for their removal are reviewed. PFAS are fluorinated substances whose unique properties make them effective surface-active agents with uses ranging from stain repellants to fire-fighting foams. In response to concerns about drinking water contamination and health risks from PFAS exposure, the United States Environmental Protection Agency published Health Advisories (HAs) for perfluorooctanoic acid and perfluorooctane sulfonic acid. The occurrence of six PFAS in drinking water has been reported in the Third Unregulated Contaminant Monitoring Rule (UCMR3), and subsequent analysis of the dataset suggested that four percent of water systems reported at least one detectable PFAS compound and 1.3 percent of water systems reported results above the HAs. Many treatment technologies have been evaluated in the literature, with the most promising and readily applied treatment technologies being activated carbon, anion exchange resins, and high-pressure membrane systems. From these data and literature reports, research and data gaps were identified and suggestions for future research are provided.

Significance of dissolved methane in effluents of anaerobically treated low strength wastewater and potential for recovery as an energy product: A review.

The need for energy efficient Domestic Wastewater (DWW) treatment is increasing annually with population growth and expanding global energy demand. Anaerobic treatment of low strength DWW produces methane which can be used to as an energy product. Temperature sensitivity, low removal efficiencies (Chemical Oxygen Demand (COD), Suspended Solids (SS), and Nutrients), alkalinity demand, and potential greenhouse gas (GHG) emissions have limited its application to warmer climates. Although well designed anaerobic Membrane Bioreactors (AnMBRs) are able to effectively treat DWW at psychrophilic temperatures (10-30 °C), lower temperatures increase methane solubility leading to increased energy losses in the form of dissolved methane in the effluent. Estimates of dissolved methane losses are typically based on concentrations calculated using Henry's Law but advection limitations can lead to supersaturation of methane between 1.34 and 6.9 times equilibrium concentrations and 11-100% of generated methane being lost in the effluent. In well mixed systems such as AnMBRs which use biogas sparging to control membrane fouling, actual concentrations approach equilibrium values. Non-porous membranes have been used to recover up to 92.6% of dissolved methane and well suited for degassing effluents of Upflow Anaerobic Sludge Blanket (UASB) reactors which have considerable solids and organic contents and can cause pore wetting and clogging in microporous membrane modules. Microporous membranes can recover up to 98.9% of dissolved methane in AnMBR effluents which have low COD and SS concentrations. Sequential Down-flow Hanging Sponge (DHS) reactors have been used to recover between 57 and 88% of dissolved methane from Upflow Anaerobic Sludge Blanket (UASB) reactor effluent at concentrations of greater than 30% and oxidize the rest for a 99% removal of total dissolved methane. They can also remove 90% of suspended solids and COD in UASB effluents and produce a high quality effluent. In situ degassing can increase process stability, COD removal, biomass retention, and headspace methane concentrations. A model for estimating energy consumption associated with membrane-based dissolved methane recovery predicts that recovered dissolved and headspace methane may provide all the energy required for operation of an anaerobic system treating DWW at psychrophilic temperatures.