Water quality impacts on sorbent efficacy for per- and polyfluoroalkyl substances treatment of groundwater

Per- and polyfluoroalkyl substances (PFAS) are a large group of synthetic compounds that have emerged as chemicals of concern in drinking water and groundwater. Typically, such waters are treated to remove PFAS by passing the water through a bed of sorbent material (e.g., activated carbon and anion exchange resins [AIX]). However, the efficacy of these sorbents varies depending on the types and concentrations of PFAS, in addition to water quality conditions such as organic matter content and conductivity (ionic strength). The choice of sorbent material to effectively treat PFAS in complex natural waters will, therefore, depend upon site water quality and PFAS conditions. To help inform these decisions, a series of evaluations using a rapid small-scale column test approach was conducted with two sorbent materials (a granulated activated carbon [GAC] and an AIX), individually and combined, under conditions where conductivity, pH, and organic carbon concentrations were varied in a semifactorial approach. Artificial groundwater batches were prepared to meet these test conditions and spiked with six PFAS compounds (perfluorobutane sulfonic acid [PFBS], perfluorobutanoic acid [PFBA], perfluorohexane sulfonic acid [PFHxS], perfluorohexanoic acid [PFHxA], perfluorooctane sulfonic acid [PFOS], and perfluorooctanoic acid [PFOA]), passed through small columns packed with ground sorbent material for ∼30,000 bed volumes of water for single sorbent treatments and ∼20,000 bed volumes for combined sorbent treatments, during which samples of effluent were captured and analyzed to quantify breakthrough of PFAS from the sorbent materials over time. AIX was found to be more effective than GAC at removing the tested perfluoroalkyl sulfonic acids (PFBS, PFHxS, and PFOS), but GAC was similarly or more effective than AIX at removing perfluorocarboxylic acids (PFBA, PFHxA, and PFOA) under high conductivity conditions. Overall, the efficacy of AIX at removing PFAS was more strongly impacted by organic carbon and conductivity than GAC, while pH had less of an effect on either sorbent's efficacy compared to the other test conditions.     

Influence of groundwater conditions and co‐contaminants on sorption of perfluoroalkyl compounds on granular activated carbon

Per and polyfluoroalkyl substances (PFAS) are emerging and persistent organic pollutants that have been detected in many environmental media, humans, and wildlife. A common method to effectively remove PFAS from water is adsorption by activated carbon. Preliminary sorption experiments were conducted using five characterized Calgon Corporation coal‐based granular activated carbon (GAC; F100, F200, F816, F300, and F400), one coconut‐based GAC (CBC‐OLC 12 × 30), and one Jacobi Corporation coal‐based GAC (Omni‐G 12 × 40). Sorption of four representative PFAS onto each GAC was measured to select the most favorable carbon sources. F400 and CBC were chosen based on their performance in preliminary PFAS sorption experiments and contrasting properties. Freundlich and Langmuir isotherm models were developed for perfluorooctanoic acid (PFOA) and perfluorooctanoic sulfonate (PFOS) at an initial concentration of 1 mg/L. Sorption capacities were determined for PFOA and PFOS individually and in the mixture. Individual compounds showed higher sorption than when present in the mixture for both PFOA and PFOS. PFOS showed higher sorption than PFOA both individually and in the mixture and F400 showed higher sorption capacity than CBC. The presence of co‐contaminants (kerosene, trichloroethylene, and ethanol), and variations in groundwater conditions (pH, presence of anions, naturally occurring organic matter, and iron oxides) demonstrated limited impact on the sorption of PFAS onto GAC under the experimental conditions tested.     

Ion exchange resin for PFAS removal and pilot test comparison to GAC

Amec Foster Wheeler and Emerging Compounds Treatment Technologies, Inc. tested pilot‐scale ex situ treatment technologies for treatment of poly‐ and perfluorinated alkyl substances (PFAS) in groundwater. The pilot test compared ion exchange resin to granular activated carbon (GAC) and evaluated in‐place regeneration of the resin to restore PFAS removal capacity. During the pilot test, both resin and GAC removed perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) below U.S. Environmental Protection Agency (USEPA) health advisories (HAs) of 0.070 micrograms per liter (μg/L) combined. Compared at a common empty bed contact time (EBCT) of five minutes, the resin treated over eight times as many bed volumes (BVs) of groundwater as GAC before PFOS exceeded the USEPA HA and six times as many BVs for PFOA. On a mass‐to‐mass basis, resin removed over four times as much total PFAS per gram as GAC before breakthrough was observed at the USEPA HA. A solution of organic solvent and brine was used to regenerate the resin in the lead vessel, which had treated water up to the point of PFOS and PFOA breakthrough exceeding the USEPA HAs. The pilot test demonstrated successful in‐place regeneration of the resin to near‐virgin conditions. The regenerated resin was then used to treat the contaminated groundwater up to the same breakthrough point. Compared to the virgin resin loading cycles, PFAS removal results for the regenerated resin were consistent with virgin resin.     

Evaluation of PFAS treatment technology: Alkaline ozonation

A bench‐scale treatability study was performed to evaluate the effectiveness of alkaline ozonation on removing per‐ and polyfluoroalkyl substances (PFAS) present in groundwater at a former industrial site in Michigan. The study involved testing the PFAS‐impacted groundwater under alkaline ozonating conditions under a range of experimental conditions, including modifying pH, hydrogen peroxide‐to‐ozone molar ratio doses, length of ozonation pretreatment times, and sampling techniques. PFAS‐spiked samples were used to determine if inorganic ions such as fluoride (F^?), sulfate (SO₄^2?), formate (HCOO^?), acetate (CH₃COO^?), and trifluoroacetate (CF₃COO^?) were generated or if there were decreases in total organic fluorine resulting from PFAS treatment. The results from all tests indicate that decreases in PFAS concentrations were due to a combination of removal and destructive mechanisms with enhanced removal under acidic pH ozonation pretreatment conditions. Short‐chain PFAS concentrations increased during the experiments followed by an overall decrease in concentration under continuous alkaline ozonation conditions. Reductions in concentrations in perfluorooctane sulfonic acid of 75–97% were observed. Reductions in concentrations were also observed in other PFAS such as 6:2 FTS, PFHxS, PFOA, and PFNA. To our best knowledge, this is the first time that alkaline ozonation has been performed on PFAS‐impacted water while monitoring a larger suite of PFAS analytes in addition to destruction byproducts. Treatment of PFAS under the conditions discussed in this paper suggests that alkaline ozonation may be a viable remediation option for PFAS‐impacted waters.     

Electrochemical oxidation of PFOA and PFOS in concentrated waste streams

The electrochemical oxidation (EO) of environmentally persistent perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) with a Magnéli phase Ti₄O₇ electrode was investigated in this study. After 3 hours (hr) of electrolysis, 96.0 percent of PFOA (10 milligrams per liter [mg/L] in 100 milliliters [mL] 100 millimolar [mM] Na₂SO₄ solution) was removed following pseudo first‐order kinetics (k = 0.0226 per minute [min]) with the degradation half‐life of 30.7 min. Under the same treatment conditions, PFOS (10 mg/L in 100 mL 100 mM Na₂SO₄ solution) removal reached 98.9 percent with a pseudo first‐order degradation rate constant of 0.0491/min and the half‐life of 14.1 min. Although, the degradation of PFOA was slower than PFOS, when subjected to EO treatment in separate solutions, PFOA appeared to degrade faster than PFOS when both are present in the same solution, indicating possible competition between PFOA and PFOS during Ti₄O₇ anode‐based EO treatment with PFOA having the competitive advantage. Moreover, the EO treatment was applied to degrade highly concentrated PFOA (100.5 mg/L) and PFOS (68.6 mg/L) in ion‐exchange resin regenerant (still bottom) with high organic carbon content (15,800 mg/L). After 17‐hr electrolysis, the total removal of PFOA and PFOS was 77.2 and 96.5 percent, respectively, and the fluoride concentration increased from 0.84 mg/L to 836 mg/L. Also, the dark brown color of the original solution gradually faded during EO treatment. In another test using still bottom samples with lower total organic carbon (9,880 mg/L), the PFOA (15.5 mg/L) and PFOS (25.5 mg/L) concentrations were reduced to levels below the limits of quantification after 16‐hr treatment. In addition, the performance of EO treatment using different batch reactor setups was compared in this study, including one‐sided (one anode:one cathode) and two‐sided (one anode:two cathodes) setups. The two‐sided reactor configuration significantly enhanced the degradation efficiency, likely due to the larger anode area available for reactions.     

Residual organic fluorinated compounds from thermal treatment of PFOA,PFHxA and PFOS adsorbed onto granular activated carbon (GAC)

Perfluorooctanoic acid (PFOA), perfluorohexanoic acid (PFHxA) and perfluorooctane sulfonate (PFOS) adsorbed onto granular activated carbon (GAC) were thermally treated in N₂ gas stream. The purpose was to assess the fate of perfluoroalkyl and polyfluoroalkyl substances (PFASs) during thermal regeneration of GAC, which had been used for water treatment. Mineralized F, residual PFASs including short-chained species, and volatile organic fluorine (VOF) were determined. In a temperature condition of 700 °C, VOF were 13.2, 4.8, and 5.9 % as for PFOA, PFHxA, and PFOS. However, the VOF decreased to 0.1 %, if the GAC and off-gas were kept at 1000 °C. No PFASs remained in GAC at 700–1000 °C; at the same time, short-chained PFASs were slightly detected in the aqueous trapping of off-gas at 800 and 900 °C conditions. The destruction of PFASs on GAC could be perfect if the temperature is higher than 700 °C; however, the process is competitive against volatile escape from GAC. Destruction in gaseous phase needs a temperature as high as 1000 °C. Destruction of PFASs on the surface of GAC, volatile escape from the site, and thermolysis in gas phase should be considered, as to thermal regeneration of GAC.     

In Situ treatment of PFAS‐impacted groundwater using colloidal activated Carbon

Poly‐ and perfluoroalkyl substances (PFASs) have been identified by many regulatory agencies as contaminants of concern within the environment. In recent years, regulatory authorities have established a number of health‐based regulatory and evaluation criteria with groundwater PFAS concentrations typically being less than 50 nanograms per liter (ng/L). Subsurface studies suggest that PFAS compounds are recalcitrant and widespread in the environment. Traditionally, impacted groundwater is extracted and treated on the surface using media such as activated carbon and exchange resins. These treatment technologies are generally expensive, inefficient, and can take decades to reach treatment objectives. The application of in situ remedial technologies is common for a wide variety of contaminants of concern such as petroleum hydrocarbons and volatile organic compounds; however, for PFASs, the technology is currently emerging. This study involved the application of colloidal activated carbon at a site in Canada where the PFASs perfluorooctanoate (PFOA) and perfluorooctane sulfonic acid (PFOS) were detected in groundwater at concentrations up to 3,260 ng/L and 1,450 ng/L, respectively. The shallow silty‐sand aquifer was anaerobic with an average linear groundwater velocity of approximately 2.6 meters per day. The colloidal activated carbon was applied using direct‐push technology and PFOA and PFOS concentrations below 30 ng/L were subsequently measured in groundwater samples over an 18‐month period. With the exception of perfluoroundecanoic acid, which was detected at 20 ng/L and perfluorooctanesulfonate which was detected at 40 ng/L after 18 months, all PFASs were below their respective method detection limits in all postinjection samples. Colloidal activated carbon was successfully distributed within the target zone of the impacted aquifer with the activated carbon being measured in cores up to 5 meters from the injection point. This case study suggests that colloidal activated carbon can be successfully applied to address low to moderate concentrations of PFASs within similar shallow anaerobic aquifers.     

Evaluating the longevity of a PFAS in situ colloidal activated carbon remedy

The remediation of per‐ and polyfluoroalkyl substances by injection of colloidal activated carbon (CAC) at a contaminated site in Central Canada was evaluated using various visualization and modeling methods. Radial diagrams were used to illustrate spatial and temporal trends in perfluoroalkyl acid (PFAA) concentrations, as well as various redox indicators. To assess the CAC adsorption capacity for perfluorooctane sulfonate (PFOS), laboratory Freundlich isotherms were derived for PFOS mixed with CAC in two solutions: (1) PFOS in a pH 7.5 synthetic water that was buffered by 1 millimolar NaHCO₃ (K_f = 142,800 mg^1‐a L^a/kg and a = 0.59); and (2) a groundwater sample (pH = 7.4) containing PFOS among other PFAS from a former fire‐training area in the United States (K_f = 4,900 mg^1‐a L^a/kg and a = 0.24). A mass balance approach was derived to facilitate the numerical modeling of mass redistribution after CAC injection, when mass transitions from a two‐phase system (aqueous and sorbed to organic matter) to a three‐phase system that also includes mass sorbed to CAC. An equilibrium mixing model of mass accumulation over time was developed using a finite‐difference solution and was verified by intermodel comparison for prediction of CAC longevity in the center of a source area. A three‐dimensional reactive transport model (ISR‐MT3DMS) was used to indicate that the CAC remedy implemented at the site is likely to be effective for PFOS remediation for decades. Model results are used to recommend remedial design and monitoring alternatives that account for the uncertainty in long‐term performance predictions.     

Adsorption of Geosmin and MIB on Activated Carbon Fibers–Single and Binary Solute System

The adsorption of two taste- and odor-causing compounds, namely MIB (2-methyl isoborneol—C₁₁H₂₀O) and geosmin (C₁₂H₂₂O) on activated carbon was investigated in this study. The impact of adsorbent pore size distribution on adsorption of MIB and geosmin was evaluated through single solute and multicomponent adsorption of these compounds on three types of activated carbon fibers (ACFs) and one granular activated carbon (GAC). The ACFs (ACC-15, ACC-20, and ACC-25) with different degrees of activation had narrow pore size distributions and specific critical pore diameters whereas the GAC (F-400) had a wider pore size distribution and lesser microporosity. The effect of the presence of natural organic matter (NOM) on MIB and geosmin adsorption was also studied for both the single solute and binary systems. The Myers equation was used to evaluate the single solute isotherms as it converges to Henry’s law at low coverage and also serves as an input for predicting multicomponent adsorption. The single solute adsorption isotherms fit the Myers equation well and pore size distribution significantly influenced adsorption on the ACFs and GAC. The ideal adsorbed solute theory (IAST), which is a well-established thermodynamic model for multicomponent adsorption, was used to predict the binary adsorption of MIB and geosmin. The IAST predicted well the binary adsorption on the ACFs and GAC. Binary adsorption isotherms were also conducted in the presence of oxygen (oxic) and absence of oxygen (anoxic). There were no significant differences in the binary isotherm between the oxic and anoxic conditions, indicating that adsorption was purely through physical adsorption and no oligomerization was taking place. Binary adsorptions for the four adsorbents were also conducted in the presence of humic acid to determine the effect of NOM and to compare with IAST predictions. The presence of NOM interestingly resulted in deviation from IAST behavior in case of two adsorbents, ACC-15 and F-400.     

In-situ application of colloidal activated carbon for PFAS-contaminated soil and groundwater: A Swedish case study

Soil and groundwater contamination by per- and polyfluoroalkyl substances (PFAS) has been a significant concern to human health and environmental quality. Remediation of contaminated sites is crucial to prevent plume expansion but can prove challenging due to the persistent nature of PFAS combined with their high aqueous mobility. In this case study, we investigated the potential of colloidal activated carbon (CAC) for soil stabilization at the pilot scale, aiming to entrap PFAS and prevent their leaching from soil into groundwater. Monitoring of the site revealed the presence of two potential sources of PFAS contamination at concentrations up to 23 μg L⁻¹ for ∑₁₁PFAS in groundwater. After CAC application, initial results indicated a 76% reduction of ∑₁₁PFAS and high removal rates for long-chain PFAS, such as perfluorooctane sulfonic acid and perfluorooctanoic acid. A spike in concentrations was noticed 6 months after injection of CAC, showing a rebound of the plume and a reduction of treatment effectiveness. Based on long-term monitoring data, the treatment effectiveness for ∑₁₁PFAS dropped to 52%. The rebound of concentrations was attributed to the plume bypass of the barrier due to the presence of high conductivity zones, which likely occurred because of seasonal changes in groundwater flow directions or the CAC application at the site. This demonstrates the need for a detailed and accurate hydrogeological understanding of contaminated sites before designing and applying stabilization techniques, especially at sites with high geologic and hydrologic complexity. The results herein can serve as a guideline for treating similar sites and help avoid potential pitfalls of remedial efforts.     

Selection of adsorbents for treatment of leachate: batch studies of simultaneous adsorption of heavy metals

The simultaneous adsorption of copper (Cu), cadmium (Cd), nickel (Ni), and lead (Pb) ions from spiked deionized water and spiked leachate onto natural materials (peat A and B), by-product or waste materials (carbon-containing ash, paper pellets, pine bark, and semi-coke), and synthetic materials (based on urea-formaldehyde resins, called blue and red adsorbents) or mixtures thereof was investigated. The adsorbents that gave the highest metal removal efficiencies were peat A, a mixture of peat B and carbon-containing ash, and a mixture of peat A and blue. At an initial concentration of 5 mg/l for each metal, the removal of each species of metal ion from spiked water and spiked leachate solutions was very good (>90%) and good (>75%), respectively. When the initial concentration of each metal in the solutions was twenty times higher (100 mg/l), there was a noticeable decrease in the removal efficiency of Cu²⁺, Cd²⁺, and Ni²⁺, but not of Pb²⁺. Langmuir monolayer adsorption capacities, q_m, on peat A were found to be 0.57, 0.37, and 0.36 mmol/g for Pb²⁺, Cd²⁺, and Ni²⁺, respectively. The order of metal adsorption capacity on peat A was the same in the case of competitive multimetal adsorption conditions as it was for single-element adsorption, namely Pb²⁺ > Cd²⁺ ≥ Ni²⁺. The results show that peat alone (an inexpensive adsorbent) is a good adsorbent for heavy metal ions.     

The in situ treatment of TCE and PFAS in groundwater within a silty sand aquifer

Chlorinated ethenes such as trichloroethene (TCE), cis‐1,2‐dichloroethene (cis‐1,2‐DCE), and vinyl chloride along with per‐ and polyfluoroalkyl substances (PFAS) have been identified as chemicals of concern in groundwater; with many of the compounds being confirmed as being carcinogens or suspected carcinogens. While there are a variety of demonstrated in‐situ technologies for the treatment of chlorinated ethenes, there are limited technologies available to treat PFAS in groundwater. At a former industrial site shallow groundwater was impacted with TCE, cis‐1,2‐DCE, and vinyl chloride at concentrations up to 985, 258, and 54 µg/L, respectively. The groundwater also contained maximum concentrations of the following PFAS: 12,800 ng/L of perfluoropentanoic acid, 3,240 ng/L of perfluorohexanoic acid, 795 ng/L of perfluorobutanoic acid, 950 ng/L of perfluorooctanoic acid, and 2,140 ng/L of perfluorooctanesulfonic acid. Using a combination of adsorption, biotic, and abiotic degradation in situ remedial approaches, the chemicals of concern were targeted for removal from the groundwater with adsorption being utilized for PFAS whereas adsorption, chemical reduction, and anaerobic biodegradation were used for the chlorinated ethenes. Sampling of the groundwater over a 24‐month period indicated that the detected PFAS were treated to either their detection, or below the analytical detection limit over the monitoring period. Postinjection results for TCE, cis‐1,2‐DCE, and vinyl chloride indicated that the concentrations of the three compounds decreased by an order of magnitude within 4 months of injection, with TCE decreasing to below the analytical detection limit over the 24‐month monitoring period. Cis‐1,2‐DCE, and vinyl chloride concentrations decreased by over 99% within 8 months of injections, remaining at or below these concentrations during the 24‐month monitoring period. Analyses of Dehalococcoides, ethene, and acetylene over time suggest that microbiological and reductive dechlorination were occurring in conjunction with adsorption to attenuate the chlorinated ethenes and PFAS within the aquifer. Analysis of soil cores collected pre‐ and post‐injection, indicated that the distribution of the colloidal activated carbon was influenced by small scale heterogeneities within the aquifer. However, all aquifer samples collected within the targeted injection zone contained total organic carbon at concentrations at least one order of magnitude greater than the preinjection total organic carbon concentrations.     

Six pilot‐scale studies evaluating the in situ treatment of PFAS in groundwater

Per‐ and polyfluoroalkyl substances (PFAS) have been identified by many regulatory agencies as emerging contaminants of concern in a variety of media including groundwater. Currently, there are limited technologies available to treat PFAS in groundwater with the most frequently applied approach being extraction (i.e., pump and treat). While this approach can be effective in containing PFAS plumes, previous studies of pump and treat programs have met with limited remedial success. In situ treatment studies of PFAS have been limited to laboratory and a few field studies. Six pilot‐scale field studies were conducted in an unconfined sand aquifer coimpacted by petroleum hydrocarbon along with PFAS to determine if a variety of reagents could be used to attenuate dissolved phase PFAS in the presence of petroleum hydrocarbons. The six reagents consisted of two chemical oxidants, hydrogen peroxide (H₂O₂) and sodium persulfate (Na₂S₂O₈), and four adsorbents, powdered activated carbon (PAC), colloidal activated carbon (CAC), ion‐exchange resin (IER), and biochar. The reagents were injected using direct push technology in six permeable reactive zone (PRZ) configurations. Groundwater concentrations of various PFAS entering the PRZs ranged up to 24,000 µg/L perfluoropentanoic acid, up to 6,200 µg/L pentafluorobenzoic acid, up to 16,100 µg/L perfluorohexanoic acid, up to 6,080 µg/L perfluoroheptanoic acid, up to 450 µg/L perfluorooctanoic acid, and up to 140 µg/L perfluorononanoic acid. Performance groundwater sampling within and downgradient of the PRZs occurred for up to 18 months using single and multilevel monitoring wells. Results of groundwater sampling indicated that the PFAS were not treated by either the persulfate nor the peroxide and, in some cases, the PFAS increased in concentration immediately following the injection of peroxide and persulfate. Concentrations of PFAS in groundwater sampled within the PAC, CAC, IER, and biochar PRZs immediately after the injection were determined to be less than the method detection limits. Analyses of groundwater samples over the 18‐month monitoring period, indicated that all the PRZs exhibited partial or complete breakthrough of the PFAS over the 18‐month monitoring period, except for the CAC PRZ which showed no PFAS breakthrough. Analysis of cores for the CAC, PAC, and biochar PRZs suggested that the CAC was uniformly distributed within the target injection zone, whereas the PAC and biochar showed preferential injection into a thin coarse‐sand seam. Similarly, analysis of the sand packs of monitoring wells installed before the injection of the CAC, PAC, and biochar indicated that the sand packs of the PAC and biochar preferentially accumulated the reagents compared with the reagent concentrations within the surrounding aquifer by up to 18 times.     

The development of low cost adsorbents from clay and waste materials: a review

Increased energy consumption due to industrial growth has increased the levels of carbon dioxide (CO₂) emission being released into the atmosphere. CO₂ emission is a type of greenhouse gas which is a major cause of global warming. Since the issue of CO₂ emissions has drawn much attention in recent years, the development of CO₂ capture technology has become a necessity. Although CO₂ adsorbents are still at the early development stage, it has been suggested that CO₂ adsorbents are the most effective technology in controlling CO₂ emissions. Solid adsorbents have great potential as an alternative method to conventional adsorbents in adsorbing CO₂. In this paper, low cost adsorbents including activated carbon, zeolites, mesoporous silica and clays are discussed in terms of adsorbent preparation methods and CO₂ adsorption capacity. The low cost adsorbents are mainly derived from waste materials such as fly ash, steel slag, red mud, bagasses wastes and wood wastes. Besides that, natural resources such as clays have also been applied as low cost CO₂ adsorbents. Surface modifications have also been applied to the low cost adsorbents, including metal ion exchange and amine impregnation to enhance CO₂ adsorption capacity. In the last section, the current status of CO₂ adsorbents is summarized and future trends are discussed briefly to predict the potential materials which can be applied as CO₂ adsorbents.     

Technology review and evaluation of different chemical oxidation conditions on treatability of PFAS

Per‐ and polyfluoroalkyl substances (PFAS) are a class of stable compounds widely used in diverse applications. These emerging contaminants have unique properties due to carbon–fluorine (C–F) bonds, which are some of the strongest bonds in chemistry. High energy is required to break C–F bonds, which results in this class of compounds being recalcitrant to many degradation processes. Many technologies studied that have shown treatment effectiveness for PFAS cannot be implemented in situ. Chemical oxidation is a demonstrated remediation technology for in situ treatment of a wide range of organic environmental contaminants. An overview of relevant literature is presented, summarizing the use of single or combined reagent chemical oxidation processes that offer insight into oxidation–reduction chemistries potentially capable of PFAS degradation. Based on the observations and results of these studies, bench‐scale treatability tests were designed and performed to establish optimal conditions for the formation of specific free radical species, including superoxide and sulfate radicals, via various combinations of oxidants, catalysts, pH buffers, and heat to assess PFAS treatment by chemical oxidants. The study also suggests the possible abiotic transformations of some PFAS when chemical oxidation is or was used for treatment of primary organic contaminants (e.g., petroleum or chlorinated organic compounds) at a site. The bench‐scale tests utilized field‐collected samples from a firefighter training area. Much of the available data related to chemical oxidation of PFAS has only been reported for one or both of the two more commonly discussed PFAS (perfluorooctane sulfonic acid and/or perfluorooctanoic acid). In contrast, this treatability study evaluates oxidation of a diverse list of PFAS analytes. The results of this study and published literature conclude that heat‐activated persulfate is the oxidation method with the best degradation of PFAS. Limited reduction of reported PFAS concentrations in this study was observed in many oxidation reactors; however, unknown mass of PFAS (such as precursors of perfluoroalkyl acids) that cannot be identified in a field collected sample complicated quantification of how much oxidative destruction of PFAS actually occurred.     

Fungal biotransformation of 6:2 fluorotelomer alcohol

Fungal degradation of 6:2 fluorotelomer alcohol (6:2 FTOH, C₆F₁₃CH₂CH₂OH) by two wood‐decaying fungal strains and six fungal isolates from a site contaminated with per‐ and polyfluoroalkyl substances (PFASs) was investigated. 6:2 FTOH is increasingly being used in FTOH‐based products, and previous reports on the microbial fate of 6:2 FTOH have focused on bacteria and environmental microbial consortia. Prior to this study, one report demonstrated that the 6:2 FTOH biotransformation by the wood‐decaying fungus, Phanerochaete chrysosporium, generated more polyfluoroalkyl substances, such as 5:3 acid (F(CF₂)₅CH₂CH₂COOH), and diverted away from producing the highly stable perfluorocarboxylic acids (PFCAs). Most of the fungi (Gloeophyllum trabeum and isolates TW4‐2, TW4‐1, B79, and B76) examined in this study showed similar degradation patterns, further demonstrating that fungi yield more 5:3 acid (up to 51 mol% of initial 6:2 FTOH dosed) relative to other metabolites (up to 12 mol% total PFCAs). However, medium amendments can potentially improve 6:2 FTOH biotransformation rates and product profiles. The six fungal isolates tolerated up to 100 or 1,000 milligrams per liter of perfluorooctanoic acid and perfluorooctane sulfonic acid, and some isolates experienced increased growth with increasing concentrations. This study proposes that fungal pathways must be considered for the biotransformation of potential PFAS precursors, such as 6:2 FTOH, and suggests the basis for selecting proper microorganisms for remediation of fluoroalkyl‐contaminated sites.     

Effect of Sediment Humic Substances on Sorption of Selected Endocrine Disruptors

Characterizing sorption processes is essential to understand the environmental distribution and toxicity potential of endocrine disruptors in terrestrial and aquatic systems. The sorption behaviors of three endocrine disruptors (bisphenol A (BPA), 17β-estradiol (E2), and 17α-ethynylestradiol (EE2)) on sediments were investigated using batch techniques. Samples were taken from some representative reaches in several major Chinese rivers. More attention has been paid to the effect of sediment organic components on the sorption of BPA, E2, and EE2. The results show that the sediment organic carbon-normalized partition coefficients (K _oc (sed)) for three endocrine disruptors are in the order of EE2 > E2 > BPA, which corresponds to the octanol-water partitioning coefficients (logK _ow) of the compounds. Moreover, the K _oc values for humic substances (K _oc (hs)) are comparable with the K _oc (sed) values and highly dependent on the physico-chemical properties of humic substances in sediments. The UV absorptivity at 272 nm (A ₂₇₂), which suggests the abundance of aromatic rings in humic substance structure, correlates well with the K _oc (hs) values. In addition, the infrared spectra of the humic substances extracted from sediments show four strong bands centered at 3,400 cm⁻¹, 1,625 cm⁻¹, 1,390 cm⁻¹, and 1,025 cm⁻¹. The K _oc (hs) values have a positive linear relation with the peak area ratio for peak at 1,025 cm⁻¹ and a negative linear relation with the peak area ratio between peaks at 1,625 cm⁻¹ and 1,025 cm⁻¹. Hence, the hydrogen bonds play a critical role to the sorption of selected endocrine disruptors.     

Adsorptive Separation of Lysozyme from Aqueous Solutions Using Sulphonyl and Carboxyl Functionalized Stearyl Alcohol Grafted Epichlorohydrin

In the present work ability of the two novel adsorbents, sulphonyl and carboxyl functionalized stearyl alcohol-grafted epichlorohydrin, SA-g-E-SO₃H, SA-g-E-COOH; to remove lysozyme (LYZ) from aqueous solution was assessed. The adsorbent characterization was done using FTIR, XRD, SEM and TGA analyses. The adsorption efficiency was influenced by solution pH and the optimum operating pH was found to be 4.0 for SA-g-E-SO₃H and 5.0 for SA-g-E-COOH and their adsorption efficiency was evaluated using the various isotherm and kinetics models. The Sips isotherm model and pseudo-second-order kinetic model were found to be the best for describing the equilibrium and kinetic behaviors of the adsorption process. Batch adsorption/desorption studies in acidic medium, for over six cycles showed excellent regeneration capability of the adsorbents and could lead to the development of viable and promising technology for the adsorptive recovery of LYZ from aqueous solutions. The efficiency of the adsorbents for the LYZ adsorption was verified using egg white. The result obtained from this study revealed that adsorption ability of 25 mg of SA-g-E-COOH is 98.4 % which is more than that of SA-g-E-SO₃H (96.2 %). The efficiency of SA-g-E-SO₃H to remove LYZ from aqueous solution was found to be higher compared to SA-g-E-COOH.     

Removal of mercury from flue gas using sewage sludge-based adsorbents

Mercury from coal-fired utility boilers, as the largest atmospheric mercury emission source, imposes serious environmental risks and health concerns. In order to explore the possibility of reducing costs of activated carbon injection, we investigated the most promising mercury control technology, Hg⁰ removal using ZnCl₂-impregnated adsorbents derived from sewage sludge. The results demonstrated that sludge-based adsorbents (SBAs) had fairly high mercury adsorption capacity over a wide range of temperatures (80–170 °C). Oxidizing atmosphere could improve the adsorption of Hg⁰ and weaken the inhibition of SO₂ on mercury adsorption to some extent. NO exhibited no obvious impact on mercury removal performance. In addition, to clarify whether oxygen- or chlorine-containing functional groups attributed to good mercury adsorption capacity of SBAs, the oxygen-containing functional groups were removed using Boehm’s method, and a temperature-programmed decomposition desorption experiment was conducted. The results suggest that chlorine-containing functional groups played a significant role in the removal process of mercury from flue gas using SBAs.     

Estimation of transport parameters of phenolic compounds and inorganic contaminants through composite landfill liners using one-dimensional mass transport model

One-dimensional (1D) advection–dispersion transport modeling was conducted as a conceptual approach for the estimation of the transport parameters of fourteen different phenolic compounds (phenol, 2-CP, 2-MP, 3-MP, 4-MP, 2-NP, 4-NP, 2,4-DNP, 2,4-DCP, 2,6-DCP, 2,4,5-TCP, 2,4,6-TCP, 2,3,4,6-TeCP, PCP) and three different inorganic contaminants (Cu, Zn, Fe) migrating downward through the several liner systems. Four identical pilot-scale landfill reactors (0.25 m³) with different composite liners (R1: 0.10 + 0.10 m of compacted clay liner (CCL), L_e = 0.20 m, k_e = 1 × 10⁻⁸ m/s, R2: 0.002-m-thick damaged high-density polyethylene (HDPE) geomembrane overlying 0.10 + 0.10 m of CCL, L_e = 0.20 m, k_e = 1 × 10⁻⁸ m/s, R3: 0.002-m-thick damaged HDPE geomembrane overlying a 0.02-m-thick bentonite layer encapsulated between 0.10 + 0.10 m CCL, L_e = 0.22 m, k_e = 1 × 10⁻⁸ m/s, R4: 0.002-m-thick damaged HDPE geomembrane overlying a 0.02-m-thick zeolite layer encapsulated between 0.10 + 0.10 m CCL, L_e = 0.22 m, k_e = 4.24 × 10⁻⁷ m/s) were simultaneously run for a period of about 540 days to investigate the nature of diffusive and advective transport of the selected organic and inorganic contaminants. The results of 1D transport model showed that the highest molecular diffusion coefficients, ranging from 4.77 × 10⁻¹⁰ to 10.67 × 10⁻¹⁰ m²/s, were estimated for phenol (R4), 2-MP (R1), 2,4-DNP (R2), 2,4-DCP (R1), 2,6-DCP (R2), 2,4,5-TCP (R2) and 2,3,4,6-TeCP (R1). For all reactors, dispersion coefficients of Cu, ranging from 3.47 × 10⁻⁶ m²/s to 5.37 × 10⁻² m²/s, was determined to be higher than others obtained for Zn and Fe. Average molecular diffusion coefficients of phenolic compounds were estimated to be about 5.64 × 10⁻¹⁰ m²/s, 5.37 × 10⁻¹⁰ m²/s, 2.69 × 10⁻¹⁰ m²/s and 3.29 × 10⁻¹⁰ m²/s for R1, R2, R3 and R4 systems, respectively. The findings of this study clearly indicated that about 35–50% of transport of phenolic compounds to the groundwater is believed to be prevented with the use of zeolite and bentonite materials in landfill liner systems.