Air-water interfacial collapse and rate-limited solid desorption control Perfluoroalkyl acid leaching from the vadose zone.

Some Per- and polyfluoroalkyl substances (PFAS) are strongly retained in the vadose zone due to their sorption to both soils and air-water interfaces. While significant research has been dedicated to understanding equilibrium behavior for these multi-phase retention processes, leaching and desorption from aqueous film-forming foam (AFFF) impacted soils under field relevant conditions can exhibit significant deviations from equilibrium. Herein, laboratory column studies using field collected AFFF-impacted soils were employed to examine the leaching of perfluoroalkyl acids (PFAAs) under simulated rainfall conditions. The HYDRUS 1-D model was calibrated to estimate the unsaturated hydraulic properties of the soil in a layered system using multiple boundary condtions. Forward simulations of equilibrium PFAS partitioning using the HYDRUS model and simplified mass balance calculations showed good agreement with the net PFAS mass flux out of the column. However, neither were able to predict the PFAS concentrations in the leached porewater. To better understand the mechanisms controlling the leaching behavior, the HYDRUS 1-D two-site leaching model incorporating solid phase rate limitation and equilibrium air-water interfacial partitioning was employed. Three variations of the novel model incorporating different forms of equilibrium air-water interfacial partitioning were considered using built-in numerical inversion. Results of numerical inversion show that a combination of air-water interfacial collapse and rate-limited desorption from soils can better predict the unique leaching behavior exhibited by PFAAs in AFFF-impacted soils. A sensitivity analysis of the initial conditions and rate-limited desorption terms was conducted to assess the agreement of the model with measured data. The models demonstrated herein show that, under some circumstances, laboratory equilibrium partitioning data can provide a reasonable estimation of total mass leaching, but fail to account for the significant rate-limited, non-Fickian transport which affect PFAA leaching to groundwater in unsaturated soils.

PFAS Porewater concentrations in unsaturated soil: Field and laboratory comparisons inform on PFAS accumulation at air-water interfaces.

Poly- and perfluoroalkyl substance (PFAS) leaching from unsaturated soils impacted with aqueous film-forming foams (AFFFs) is an environmental challenge that remains difficult to measure and predict. Complicating measurements and predictions of this process is a lack of understanding between the PFAS concentrations measured in a collected environmental unsaturated soil sample, and the PFAS concentrations measured in the corresponding porewater using field-deployed lysimeters. The applicability of bench-scale batch testing to assess this relationship also remains uncertain. In this study, field-deployed porous cup suction lysimeters were used to measure PFAS porewater concentrations in unsaturated soils at 5 AFFF-impacted sites. Field-measured PFAS porewater concentrations were compared to those measured in porewater extracted in the laboratory from collected unsaturated soil cores, and from PFAS concentrations measured in the laboratory using batch soil slurries. Results showed that, despite several years since the last AFFF release at most of the test sites, precursors were abundant in 3 out of the 5 sites. Comparison of field lysimeter results to laboratory testing suggested that the local equilibrium assumption was valid for at least 3 of the sites and conditions of this study. Surprisingly, PFAS accumulation at the air-water interface was orders of magnitude less than expected at two of the test sites, suggesting potential gaps in the understanding of PFAS accumulation at the air-water interface at AFFF-impacted sites. Finally, results herein suggest that bench-scale testing on unsaturated soils can in some cases be used to inform on PFAS in situ porewater concentrations.

Life cycle assessment and life cycle cost analysis of anion exchange and granular activated carbon systems for remediation of groundwater contaminated by per- and polyfluoroalkyl substances (PFASs).

Anion exchange resin (AER) and granular activated carbon (GAC) have emerged as prominent technologies for treatment of waters contaminated with per- and polyfluoroalkyl substances (PFASs). This study compares the life cycle environmental impacts and life cycle costs of remediating PFAS-contaminated groundwater with these competing technologies, using field pilot data to inform model inputs. Comparative analysis indicates that AER systems employing single-use "PFAS-selective" resins have lower environmental impacts and costs than systems using regenerable resins or GAC adsorbents, supporting its use in future remediation efforts. Use of GAC operated as a single-use adsorbent led to the highest emissions as well as the highest treatment costs, with thermally-reactivated GAC proving to be less impactful than regenerable AER treatment. Sensitivity analyses highlighted the dominance of media usage rate (MUR), which is highly dependent on the selected PFAS treatment goals, to determine environmental impacts and costs over a 30-year system life cycle. Selection of very stringent changeout criteria (e.g., detection of any PFASs in effluent) significantly reduces the advantages of single-use resins. For regenerable AER, environmental impacts were dominated by management of the PFAS-contaminated brine/co-solvent waste stream used to regenerate the adsorbent, as well as the cosolvent content of the regenerant mixture and the cosolvent recovery efficiency achieved via on-site distillation. High impacts estimated for GAC adsorption, the result of high MUR relative to ion exchange media, can be significantly reduced if spent adsorbents are reused after thermal reactivation, but impacts are still greater than those predicted for single-use ion exchange systems. Findings are expected to hold across a range of diverse sites, including drinking water systems treating more dilute sources of PFAS contamination, as PFAS breakthrough was not found to be highly sensitive to sourcewater PFAS concentrations.

Removal and destruction of perfluoroalkyl ether carboxylic acids (PFECAs) in an anion exchange resin and electrochemical oxidation treatment train.

Perfluoroalkyl ether carboxylic acids (PFECAs) are a group of emerging recalcitrant contaminants that are being developed to replace legacy per- and polyfluoroalkyl substances (PFAS) in industrial applications and that are generated as by-products in fluoropolymer manufacturing. Here, we report on the removal and destruction of four structurally different PFECAs using an integrated anion exchange resin (AER) and electrochemical oxidation (ECO) treatment train. Results from this work illustrated that (1) flow-through columns packed with PFAS-selective AERs are highly effective for the removal of PFECAs and (2) PFECA affinity is strongly correlated with their hydrophobic features. Regeneration of the spent resin columns revealed that high percentage (e.g., 80%) of organic cosolvent is necessary for achieving 60-100% PFECA release, and regeneration efficiency was higher for a macroporous resin than a gel-type resin. Treatment of spent regenerants showed (1) >99.99% methanol removal was achieved by distillation, (2) >99.999% conversion of the four studied PFECAs was achieved during the ECO treatment of the still bottoms after 24 hours with an energy per order of magnitude of PFECA removal (EE/O) <1.03 kWh/m3 of total groundwater treated, and (3) >85% of the organic fluorine was recovered as inorganic fluoride. Trifluoroacetic acid (TFA), perfluoropropionic acid (PFPrA), and perfluoro-2-methoxyacetic acid (PFMOAA) were confirmed via high-resolution mass spectrometry as transformation products (TPs) in the treated still bottoms, and two distinctive degradation schemes and four reaction pathways are proposed for the four PFECAs. Lastly, dissolved organic matter (DOM) inhibited uptake, regeneration, and oxidation of PFECAs throughout the treatment train, suggesting pretreatment steps targeting DOM removal can enhance the system's treatment efficiency. Results from this work provide guidelines for developing effective separation-concentration-destruction treatment trains and meaningful insights for achieving PFECA destruction in impacted aquatic systems.

Pilot study comparison of regenerable and emerging single-use anion exchange resins for treatment of groundwater contaminated by per- and polyfluoroalkyl substances (PFASs).

This study reports the results of an 8-month pilot study comparing both regenerable and emerging single-use anion exchange resins (AERs) for treatment of per- and polyfluoroalkyl substances (PFASs) at a source zone impacted by historical use of aqueous film-forming foam (AFFF). Two regenerable (Purolite A860 and A520E) and three single-use (Purolite PFA694E, Calgon CalRes 2301, and Dowex PSR2+) AERs were tested in parallel, collecting effluent samples after treatment for 30-sec and 2-min total empty bed contact time (EBCT). Results demonstrate that single-use AERs significantly outperform regenerable resins, particularly for treatment of long-chain perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkyl sulfonic acids (PFSAs). No detectable concentrations of ≥C7 PFCAs or PFSAs were observed within 150,000 bed volumes (BVs) after treatment with the single-use resins (2-min EBCT). Analysis of effluent samples following 30-sec EBCT treatment shows that even the shortest-chain PFSAs do not reach 50% breakthrough within the first 350,000 BVs, though differences in removal of short-chain PFCAs was less dramatic. The regenerable polyacrylic A860 resin performed very poorly compared to all polystyrene resins, with >90% breakthrough of all PFASs occurring within 10,000 BVs. The greater affinity of polystyrene resins is attributed to increased hydrophobic interactions in addition to electrostatic ion exchange. Analysis of breakthrough profiles reveals empirical correlation with ion exchange affinity coefficients (logKex) measured in batch experiments. Postmortem analysis of PFASs extracted from spent resins revealed chromatographic elution behavior and competition among PFASs for adsorption to the resins. PFSAs and long-chain PFCAs were preferentially adsorbed to earlier sections in the AER columns, whereas short-chain PFCAs were competitively displaced towards the later sections of the columns and into the effluent, consistent with effluent concentrations of the latter structures exceeding influent values. These results provide insights into the mechanisms that govern PFAS adsorption to AERs in real multisolute groundwater matrices and support findings from other diverse sites regarding PFAS affinity, elution behavior, and competition for exchange sites.

Life cycle environmental impacts of regeneration options for anion exchange resin remediation of PFAS impacted water.

Although anion exchange resin (AER) treatment is considered an effective technology for removing per- and polyfluoroalkyl substances (PFASs) from impacted water, the environmental impacts associated with AER regeneration have not been systematically explored. In particular, the trade-offs of altering the composition of the regeneration solution and disposing of or recycling the waste regeneration solution are not known. To fill these important gaps in the literature, this research conducted a comparative life cycle assessment (LCA) of an AER-based PFAS remediation system with different regeneration scenarios including disposing of waste regeneration solution via incineration, reusing the organic cosolvent and brine fractions of the waste regeneration solution, and altering the composition of the regeneration solution to avoid organic cosolvent or NaCl. The results show that disposing of waste regeneration solution via incineration, without recycling organic cosolvent or brine, had the greatest environmental impact, and that incineration accounted for the greatest impact among contributing processes. Recycling of the cosolvent (or cosolvent and brine) fraction of the waste regeneration solution resulted in lower environmental impacts due to reduced mass of waste disposed of via incineration. Replacing NaCl in the brine with an alternative salt resulted in higher environmental impacts, with salts derived from chemical production, such as ammonium chloride and potassium carbonate, showing the largest increases in impacts. The results of this research highlight the importance of understanding the fate of PFASs during incineration, and the need for PFAS destruction technologies that can be coupled to AER regeneration to avoid incineration.

Anion exchange resin removal of per- and polyfluoroalkyl substances (PFAS) from impacted water: A critical review.

A key gap in the literature on the treatment of per- and polyfluoroalkyl substances (PFAS) in impacted water is the absence of a review article dedicated to anion exchange resin (AER) treatment. This gap is important because previous research has consistently shown adsorption by AER to be one of the most effective treatment processes for PFAS removal from impacted water, and AER is one of the most commonly deployed technologies in the field. Given the scope of the previous review articles on PFAS removal by various adsorbent types, the sections on AER do not explore the full depth of PFAS and AER interactions nor cover the breadth of AER testing conditions. Accordingly, the goal of this paper was to critically review the available peer-reviewed literature on PFAS removal from water by AER. The specific objectives of the review were to synthesize the previous literature results on (1) batch adsorption behavior, (2) impact of water chemistry conditions, (3) continuous-flow adsorption, (4) adsorption modeling, (5) regeneration, and (6) weak-base AER. Following from critical review of the literature, the future research priorities discussed include: (i) improving the underlying science that governs PFAS-resin interactions, (ii) improving methods for resin regeneration and management of PFAS-contaminated concentrate streams, and (iii) comparative life cycle environmental and economic analyses for ion exchange treatment systems relative to competing technologies.

Removal of Per- and Polyfluoroalkyl Substances (PFASs) in Aqueous Film-Forming Foam (AFFF) Using Ion-Exchange and Nonionic Resins.

Despite benefits to the firefighting industry, the release of per- and polyfluoroalkyl substances (PFASs) from aqueous film-forming foam (AFFF) into aquatic systems poses significant risks to human health and other organisms. While anion-exchange technologies have proven to be effective for removing perfluoroalkyl acids (PFAAs) from water, their effectiveness for removing the diverse PFAS structures discovered in AFFF remains unknown. Here, we report on the adsorption of 75 PFASs, including 63 polyfluorinated substances, in a diluted AFFF mixture using 14 commercially available ion-exchange (IX)/nonionic resins and granular activated carbon (GAC). Results showed that anion-exchange resins (AERs) exhibited significant adsorption of PFASs compared to cation-exchange resins (CERs), nonionic resins (NIRs), and GAC regardless of the PFAS's predicted charge. Isotherm data showed that macroporous AERs have a higher PFAS adsorption capacity compared to gel-type AERs. Cross-correlation comparison of PFAS/Cl- selectivity coefficients (Kex) for each PFAS-AER combination showed that the hydrophobicity of the AER functional group, and polymer matrix played a dominant role in determining resin affinity for PFASs. PFAS structural characteristics also significantly affected adsorption, with increasing chain length and a net negative charge increasing the extent of adsorption. Results from this study provide guidelines for the selection of resins to adsorb a wider range of PFASs and meaningful insights for the development of quantitative models for IX treatment of AFFF-impacted water.

A novel phase change coolant promoted quality attributes and glutamate accumulation in postharvest shiitake mushrooms involved in energy metabolism.

Cold chain transportation is an important link in postharvest logistics of agricultural products. In current study, we developed a novel water-based phase change coolant (PCC), which showed longer effectiveness in maintaining low temperature condition compared with ice, and applied in preserving the postharvest mushrooms. The results showed that the novel PCC effectively inhibited water loss, as well as maintained quality attributes including firmness, color, phenolics, flavonoids, and thus prolonged the shelf-life of mushrooms. Low temperature condition created by the novel PCC treatment maintained high level of energy charge by activating the activities of SDH, CCO, H+-ATPase and Ca2+-ATPase, resulting in the delay of postharvest senescence. In addition, sufficient energy supply decreased the consumption of glutamate as carbon skeleton by inhibiting GDH activity, improved glutamate accumulation, and therefore maintained sensory properties as a result. Thus, the novel PCC might be an excellent substitute for ice in cold chain transportation of mushrooms.

Influence of terminal electron-accepting conditions on the soil microbial community and degradation of organic contaminants of emerging concern.

Better understanding of the fate and persistence of trace organic contaminants of emerging concern (CEC) in agricultural soils is critical for assessing the risks associated with using treated wastewater effluent to irrigate crops and land application of wastewater biosolids. This study reports on the influence of prevailing terminal electron-accepting processes (TEAPs, i.e., aerobic, nitrate-reducing, iron(III)-reducing, and sulfate-reducing conditions) and exposure to a mixture of nine trace CEC (90 ng/g each) on both the microbial community structure and CEC degradation in agricultural soil. DNA analysis revealed significant differences in microbial community composition following establishment of different TEAPs, but no significant change upon exposure to the mixture of CEC. The largest community shift was observed after establishing nitrate-reducing conditions and the smallest shift for sulfate-reducing conditions. Two of the CEC (atrazine and sulfamethoxazole) showed significant degradation in both bioactive and abiotic (i.e., sterilized) conditions, with half-lives ranging from 1 to 64 days for different TEAPs, while six of the CEC (amitriptyline, atenolol, trimethoprim, and three organophosphate flame retardants) only degraded in bioactive samples, with half-lives ranging from 27 to 90 days; carbamazepine did not degrade appreciably within 90 days in any of the incubations. Amplicon sequence variants (ASVs) from Firmicutes Hydrogenispora, Gemmatimonadetes Gemmatimonadaceae, and Verrucomicrobia OPB34 soil group were identified as potentially responsible for the biodegradation of organophosphate flame retardants, and ASVs from other taxa groups were suspected to be involved in biodegrading the other target CEC. These results demonstrate that CEC fate and persistence in agricultural soils is influenced by the prevailing TEAPs and their influence on the microbial community, suggesting the need to incorporate these factors into contaminant fate models to improve risk assessment predictions.

Selective oxidation of colour-inducing constituents in raw sugar cane juice with potassium permanganate.

Colour removal in raw sugar remains a crucial but expensive process in the sugar industry. In this report, permanganate (MnO4-) oxidation is explored as an alternative method to remove colour-inducing constituents in sugar cane juice/produced raw sugar. Experiments indicated alum, an inexpensive coagulant, was able to remove residual Mn species produced after MnO4- treatment. The optimal dosages of MnO4- and alum for decoloration of a 17 wt% raw sugar solution (70 °C) was found to be 4 mM and 2 g/l, respectively. Removal of colour and Mn removal were further improved at ambient temperature. Sucrose, the major component of raw sugar, was not affected during treatment with MnO4- and alum. Two-phase kinetic behaviour for MnO4- oxidation was observed, where an initial rapid oxidation phase is followed by a second slower reaction phase. These results suggest permanganate oxidation is a promising alternative for accomplishing the decoloration of raw sugar solutions.

Changes in Quality and Microbial Succession of Lightly Salted and Sugar-Salted Blunt Snout Bream ( Megalobrama amblycephala) Fillets Stored at 4°C.

The effect of a low concentration of salt and sugar on the quality and microbial succession in blunt snout bream ( Megalobrama amblycephala) fillets was assessed by sensory analysis, total volatile basic nitrogen, biogenic amines, K value, total viable counts, 16S rRNA gene analysis, and Illumina MiSeq PE300 high-throughput sequencing. Fish samples were left untreated (control), treated with 1.8% salt (T1), or treated with 1.8% salt plus 0.9% sugar (T2). Consequently, salted and sugar-salted treatments extended the shelf life of bream fillets by 2 days, which retarded the increase of total volatile basic nitrogen, putrescine, cadaverine, and total viable counts. The putrescine and cadaverine concentrations of T2 were significantly ( P < 0.05) higher than T1 after day 10. Brachybacterium was the major initial microbiota of bream fillets. As storage time progressed, Pseudomonas and Shewanella were major genera in the spoiled control group. Pseudomonas, Shewanella, and Pseudoalteromonas became the main spoilers in the T1 and T2 groups.

Mineral- and Base-Catalyzed Hydrolysis of Organophosphate Flame Retardants: Potential Major Fate-Controlling Sink in Soil and Aquatic Environments.

The ubiquitous occurrence of organophosphate flame retardants (OPFRs) in aquatic and soil environments poses significant risks to human health and ecosystems. Here, we report on the hydrolysis of six OPFRs and three structural analogues in the absence and presence of metal (hydr)oxide minerals. Eight of the target compounds showed marked degradation in alkaline solutions (pH 9-12) with half-lives ranging from 0.02-170 days. Kinetics follow a second-order rate law with apparent rate constants for base-catalyzed hydrolysis (kB) ranging from 0.69-42 000 M-1 d-1. Although hydrolysis in homogeneous solution at circumneutral pH is exceedingly slow (t1/2 > 2 years, except for tris(2,2,2-trichloroethy) phosphate), rapid degradation is observed in the presence of metal (hydr)oxide minerals, with half-lives reduced to <10 days for most of the target OPFRs in mineral suspensions (15 m2/L mineral surface area loading). LC-qToF-MS analysis of transformation products confirmed ester hydrolysis as the active degradation pathway. Values of kB for individual OPFRs are highly variable and correlate with acid dissociation constants (pKa) of the corresponding alcohol leaving groups. In contrast, kinetic parameters for mineral-catalyzed reactions are much less sensitive to OPFR structure, indicating that other factors like mineral-OPFR interactions are rate controlling. Given the documented recalcitrance of OPFRs to biodegradation and photodegradation, these results suggest that mineral-catalyzed hydrolysis may be a major fate-controlling sink in natural environments.