Removal of PFAS by hydrotalcite: Adsorption mechanisms, effect of adsorbent aging, and thermal regeneration.

Layered double hydroxides (LDH) have been shown to be effective adsorbents, but their utility for the treatment of per- and polyfluoroalkyl substances (PFAS) in water has not been fully explored. In this study, the adsorption of 9 PFAS on hydrotalcite (HT), a type of LDH, was investigated using reaction solutions with environmentally relevant PFAS concentrations. The adsorption of individual PFAS by HT depended upon a range of factors, including the temperature used to pre-treat (i.e., calcine) the HT, aging conditions, and the presence of anions in the solution. HT calcined near 400 °C most effectively adsorbed PFAS, but its ability to adsorb PFAS was sensitive to storage conditions. The adsorption of CO2 and moisture from air, which likely resulted in the re-intercalation of CO32- into the interlayer regions of HT, was observed to reduce PFAS adsorption and may explain performance loss over time. The adsorption trend among 9 PFAS and the influence on this process by Cl-, NO3-, SO42-, and CO32- indicated that adsorption occurred via a combination of ion exchange, electrostatic attraction, and hydrophobic interactions, although the relative importance of each mechanism deserves further investigation. During this study, we also demonstrated for the first time that HT can be thermally regenerated at 400 °C without affecting its ability to adsorb PFOS and PFBA. Overall, our results suggest that HT may serve as an effective alternative for PFAS treatment.

PFAS remediation: Evaluating the infrared spectra of complex gaseous mixtures to determine the efficacy of thermal decomposition of PFAS.

Due to their widespread production and known environmental contamination, the need for the detection and remediation of per- and polyfluoroalkyl substances (PFAS) has grown quickly. While destructive thermal treatment of PFAS at low temperatures (e.g., 200-500 °C) is of interest due to lower energy and infrastructure requirements, the range of possible degradation products remains underexplored. To better understand the low temperature decomposition of PFAS species, we have coupled gas-phase infrared spectroscopy with a multivariate curve resolution (MCR) analysis and a database of high-resolution PFAS infrared reference spectra to characterize and quantify a complex mixture resulting from potassium perfluorooctanesulfonate (PFOS-K) decomposition. Beginning at 375 °C, nine prevalent decomposition products (namely smaller perfluorocarbon species) are identified and quantified.

Sonochemical degradation of PFAS in ion exchange regeneration wastes.

One of the primary technologies currently being deployed for the removal of per- and polyfluoroalkyl substances (PFAS) from water is ion exchange (IX). For regenerable IX resins, concentrated PFAS in the resulting spent brine and/or still bottoms requires further treatment. This research demonstrated that PFAS in spent brine and still bottoms can be effectively degraded sonochemically at 1000 kHz. Overall, PFAS degradation was negatively impacted by high total organic carbon (TOC) and residual methanol (MeOH) solvent (up to 50 g/kg; 5% w:w), but was enhanced by the high chloride. The addition of caustic (up to 1 N NaOH) partially mitigated the inhibition by TOC and MeOH. Sonochemical degradation of individual PFAS compounds resulted in significant mineralization to form inorganic fluoride, but small quantities of volatile organic fluorine species (VOF) were noted. This is believed to be the first report of sonochemical degradation of PFAS in ion exchange regeneration wastes, and indicates the possibility for the application of this technology as part of a complete PFAS capture and destruction treatment train.

Formation of volatile chlorinated and brominated products during low temperature thermal decomposition of the representative PFAS perfluorohexane sulfonate (PFHxS) in the presence of NaCl and NaBr.

Per- and polyfluoroalkyl substances (PFAS) are synthetic organofluorine compounds known for their chemical and physical stability as well as their wide range of uses. Some PFAS are widely distributed in the environment, leading to concerns related to both environmental and human health. High temperature thermal treatment (i.e., incineration) has been utilized for PFAS treatment, but this requires significant infrastructure and energy, prompting interest in lower temperature approaches that may still lead to efficient destruction. Lower treatment temperatures, however, increase the potential for incomplete PFAS mineralization and formation of volatile organofluorine (VOF) products. Herein, we report the formation of novel VOF products that include chlorinated and brominated compounds during the thermal treatment of potassium perfluorohexane sulfonate (PFHxS), a representative perfluoroalkyl acid (PFAA). By comparing the gas chromatography-mass spectrometry (GC-MS) results of known VOF stocks to evolved VOF during thermal treatment of PFAS, the formation of perfluorohexyl chloride and perfluorohexyl bromide was observed when PFHxS was heated at temperatures between 275 and 475 °C in the presence of NaCl and NaBr, respectively. To our knowledge, this is the first report of chlorinated or brominated VOF products during thermal treatment of a PFAA. These findings suggest that a range of mixed halogenated VOF may form during thermal treatment of PFAS at relatively low temperature (e.g., 500 °C) and that these can be a function of salts present in the matrix.

Application of a multiple lines of evidence approach to document natural attenuation of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in groundwater.

This study utilized innovative analyses to develop multiple lines of evidence for natural attenuation of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in groundwater at the U.S. Department of Energy's Pantex Plant. RDX, as well as the degradation product 4-nitro-2,4-diazabutanal (NDAB; produced by aerobic biodegradation or alkaline hydrolysis) were detected in a large portion of the plume, with lower concentrations of the nitroso-containing metabolites produced during anaerobic biodegradation. 16S metagenomic sequencing detected the presence of bacteria known to aerobically degrade RDX (e.g., Gordonia, Rhodococcus) and NDAB (Methylobacterium), as well as the known anoxic RDX degrader Pseudomonas fluorescens I-C. Proteomic analysis detected both the aerobic RDX degradative enzyme XplA, and the anoxic RDX degradative enzyme XenB. Groundwater enrichment cultures supplied with low concentrations of labile carbon confirmed the potential of the extant groundwater community to aerobically degrade RDX and produce NDAB. Compound-specific isotope analysis (CSIA) of RDX collected at the site showed fractionation of nitrogen isotopes with δ15N values ranging from approximately -5‰ to +9‰, providing additional evidence of RDX degradation. Taken together, these results provide evidence of in situ RDX degradation in the Pantex Plant groundwater. Furthermore, they demonstrate the benefit of multiple lines of evidence in supporting natural attenuation assessments, especially with the application of innovative isotopic and -omic technologies.

Carbon Isotope Fractionation of 1,2-Dibromoethane by Biological and Abiotic Processes.

1,2-Dibromethane (EDB) is a toxic fuel additive that likely occurs at many sites where leaded fuels have impacted groundwater. This study quantified carbon (C) isotope fractionation of EDB associated with anaerobic and aerobic biodegradation, abiotic degradation by iron sulfides, and abiotic hydrolysis. These processes likely contribute to EDB degradation in source zones (biodegradation) and in more dilute plumes (hydrolysis). Mixed anaerobic cultures containing dehalogenating organisms (e.g., Dehaloccoides spp.) were examined, as were aerobic cultures that degrade EDB cometabolically. Bulk C isotope enrichment factors (εbulk) associated with biological degradation covered a large range, with mixed anaerobic cultures fractionating more (εbulk from -8 to -20‰) than aerobic cultures (εbulk from -3 to -6‰). εbulk magnitudes associated with the abiotic processes (dihaloelimination by FeS/FeS2 and hydrolysis) were large but fairly well constrained (εbulk from -19 to -29‰). As expected, oxidative mechanisms fractionated EDB less than dihaloelimination and substitution mechanisms, and biological systems exhibited a larger range of fractionation, potentially due to isotope masking effects. In addition to quantifying and discussing εbulk values, which are highly relevant for quantifying in situ EDB degradation, an innovative approach for constraining the age of EDB in the aqueous phase, based on fractionation during hydrolysis, is described.

Uranium fate in wetland mesocosms: Effects of plants at two iron loadings with different pH values.

Small-scale continuous flow wetland mesocosms (∼0.8 L) were used to evaluate how plant roots under different iron loadings affect uranium (U) mobility. When significant concentrations of ferrous iron (Fe) were present at circumneutral pH values, U concentrations in root exposed sediments were an order of magnitude greater than concentrations in root excluded sediments. Micro X-ray absorption near-edge structure (µ-XANES) spectroscopy indicated that U was associated with the plant roots primarily as U(VI) or U(V), with limited evidence of U(IV). Micro X-ray fluorescence (µ-XRF) of plant roots suggested that for high iron loading at circumneutral pH, U was co-located with Fe, perhaps co-precipitated with root Fe plaques, while for low iron loading at a pH of ∼4 the correlation between U and Fe was not significant, consistent with previous observations of U associated with organic matter. Quantitative PCR analyses indicated that the root exposed sediments also contained elevated numbers of Geobacter spp., which are likely associated with enhanced iron cycling, but may also reduce mobile U(VI) to less mobile U(IV) species.

Uranium Redistribution Due to Water Table Fluctuations in Sandy Wetland Mesocosms.

To understand better the fate and stability of immobilized uranium (U) in wetland sediments, and how intermittent dry periods affect U stability, we dosed saturated sandy wetland mesocosms planted with Scirpus acutus with low levels of uranyl acetate for 4 months before imposing a short drying and rewetting period. Concentrations of U in mesocosm effluent increased after drying and rewetting, but the cumulative amount of U released following the dry period constituted less than 1% of the total U immobilized in the soil during the 4 months prior. This low level of remobilization suggests, and XANES analyses confirm, that microbial reduction was not the primary means of U immobilization, as the U immobilized in mesocosms was primarily U(VI) rather than U(IV). Drying followed by rewetting caused a redistribution of U downward in the soil profile and to root surfaces. Although the U on roots before drying was primarily associated with minerals, the U that relocated to the roots during drying and rewetting was bound diffusely. Results show that short periods of drought conditions in a sandy wetland, which expose reduced sediments to air, may impact U distribution without causing large releases of soil-bound U to surface waters.

Spectroscopic evidence of uranium immobilization in acidic wetlands by natural organic matter and plant roots.

Biogeochemistry of uranium in wetlands plays important roles in U immobilization in storage ponds of U mining and processing facilities but has not been well understood. The objective of this work was to study molecular mechanisms responsible for high U retention by Savannah River Site (SRS) wetland sediments under varying redox and acidic (pH = 2.6-5.8) conditions using U L3-edge X-ray absorption spectroscopy. Uranium in the SRS wetland sediments existed primarily as U(VI) bonded as a bidentate to carboxylic sites (U-C bond distance at ∼2.88 Å), rather than phenolic or other sites of natural organic matter (NOM). In microcosms simulating the SRS wetland processes, U immobilization on roots was 2 orders of magnitude higher than on the adjacent brown or more distant white sands in which U was U(VI). Uranium on the roots were both U(IV) and U(VI), which were bonded as a bidentate to carbon, but the U(VI) may also form a U phosphate mineral. After 140 days of air exposure, all U(IV) was reoxidized to U(VI) but remained as a bidentate bonding to carbon. This study demonstrated NOM and plant roots can highly immobilize U(VI) in the SRS acidic sediments, which has significant implication for the long-term stewardship of U-contaminated wetlands.

Retention and chemical speciation of uranium in an oxidized wetland sediment from the Savannah River Site.

Uranium speciation and retention mechanisms onto Savannah River Site (SRS) wetland sediments was studied using batch (ad)sorption experiments, sequential extraction, U L3-edge X-ray absorption near-edge structure (XANES) spectroscopy, fluorescence mapping and µ-XANES. Under oxidized conditions, U was highly retained by the SRS wetland sediments. In contrast to other similar but much lower natural organic matter (NOM) sediments, significant sorption of U onto the SRS sediments was observed at pH < 4 and pH > 8. Sequential extraction indicated that the U species were primarily associated with the acid soluble fraction (weak acetic acid extractable) and organic fraction (Na-pyrophosphate extractable). Uranium L3-edge XANES spectra of the U-bound sediments were nearly identical to that of uranyl acetate. Based on fluorescence mapping, U and Fe distributions in the sediment were poorly correlated, U was distributed throughout the sample and did not appear as isolated U mineral phases. The primary oxidation state of U in these oxidized sediments was U(VI), and there was little evidence that the high sorptive capacity of the sediments could be ascribed to abiotic or biotic reduction to the less soluble U(IV) species or to secondary mineral formation. Collectively, this study suggests that U may be strongly bound to wetland sediments, not only under reducing conditions by reductive precipitation, but also under oxidizing conditions through NOM-uranium bonding.

Isotope effect of mercury diffusion in air.

Identifying and reducing impacts from mercury sources in the environment remains a considerable challenge and requires process based models to quantify mercury stocks and flows. The stable isotope composition of mercury in environmental samples can help address this challenge by serving as a tracer of specific sources and processes. Mercury isotope variations are small and result only from isotope fractionation during transport, equilibrium, and transformation processes. Because these processes occur in both industrial and environmental settings, knowledge of their associated isotope effects is required to interpret mercury isotope data. To improve the mechanistic modeling of mercury isotope effects during gas phase diffusion, an experimental program tested the applicability of kinetic gas theory. Gas-phase elemental mercury diffusion through small bore needles from finite sources demonstrated mass dependent diffusivities leading to isotope fractionation described by a Rayleigh distillation model. The measured relative atomic diffusivities among mercury isotopes in air are large and in agreement with kinetic gas theory. Mercury diffusion in air offers a reasonable explanation of recent field results reported in the literature.