Factors Affecting the Adsorption of Per- and Polyfluoroalkyl Substances (PFAS) by Colloidal Activated Carbon.

The immobilization of per- and polyfluoroalkyl substances (PFAS) by colloidal activated carbon (CAC) barriers has been proposed as a potential in-situ method to mitigate the transport of plumes of PFAS in the subsurface. However, if PFAS are continuously released from a source zone, the adsorptive sites on CAC will eventually become saturated, upon which point the breakthrough of PFAS in the barrier will occur. To predict the long-term effectiveness of CAC barriers, it is important to evaluate the factors that may affect the adsorption of PFAS on CAC. In this study, the adsorption of 7 PFAS on a polymer-stabilized CAC (i.e., PlumeStop®) and on a polymer-free CAC was investigated using batch experiments. The adsorption affinity of PFAS to CAC was in the following order: PFOS > 6:2 FTS > PFHxS > PFOA > PFBS > PFPeA > PFBA. This result indicates that hydrophobic interaction was the predominant adsorption mechanism, and that hydrophilic compounds such as PFBA and PFPeA will break through CAC barriers first. The partition coefficient Kd for the adsorption of PFAS on the polymer-stabilized CAC was 1.3 - 3.5 times smaller than the Kd for the adsorption of PFAS on the polymer-free CAC, suggesting that the polymers decreased the adsorption, presumably due to competitive sorption. Thus, the PFAS adsorption capacity of PlumeStop CAC barriers is expected to increase once the polymers are biodegraded and/or washed away. The affinity of PFOS and PFOA to CAC increased when the ionic strength of the solution increased from 1 to 100 mM, or when the concentration of Ca2+ increased from 0 to 2 mM. In contrast, less PFOS and PFOA were adsorbed in the presence of 1 - 20 mgC/L Suwannee River Fulvic Acid, which represented dissolved organic carbon, or in the presence of 10 - 100 mg/L diethylene glycol butyl ether (DGBE), which is an important component in some aqueous film-forming foam (AFFF) formulations. The presence of 0.5 - 4.8 mg/L benzene or 0.5 - 8 mg/L trichloroethylene, the co-contaminants that may comingle with PFAS at AFFF-impacted sites, diminished PFOS adsorption but had no effect or even slightly enhanced PFOA adsorption. When the initial concentration of TCE was 8 mg/L, the Kd (514 ± 240 L/g) for the adsorption of PFOS was approximately 20 times lower than that in the TCE-free system (Kd = 9,579 ± 829 L/g). The results of this study provided insights into some key factors that may affect the adsorption of PFAS in in-situ CAC barriers.

A field-validated equilibrium passive sampler for the monitoring of per- and polyfluoroalkyl substances (PFAS) in sediment pore water and surface water.

A simple equilibrium passive sampler, consisting of water in an inert container capped with a rate-limiting barrier, for the monitoring of per- and polyfluoroalkyl substances (PFAS) in sediment pore water and surface water was developed and tested through a series of laboratory and field experiments. The objectives of the laboratory experiments were to determine (1) the membrane type that could serve as the sampler's rate-limiting barrier, (2) the mass transfer coefficient of environmentally relevant PFAS through the selected membrane, and (3) the performance reference compounds (PRCs) that could be used to infer the kinetics of PFAS diffusing into the sampler. Of the membranes tested, the polycarbonate (PC) membrane was deemed the most suitable rate-limiting barrier, given that it did not appreciably adsorb the studied PFAS (which have ≤8 carbons), and that the migration of these compounds through this membrane could be described by Fick's law of diffusion. When employed as the PRC, the isotopically labelled PFAS M2PFOA and M4PFOS were able to predict the mass transfer coefficients of the studied PFAS analytes. In contrast, the mass transfer coefficients were underpredicted by Br- and M3PFPeA. For validation, the PC-based passive samplers consisting of these four PRCs, as well as two other PRCs (i.e., M8PFOA and C8H17SO3-), were deployed in the sediment and water at a PFAS-impacted field site. The concentration-time profiles of the PRCs indicated that the samplers deployed in the sediment required at least 6 to 7 weeks to reach 90% equilibrium. If the deployment times are shorter (e.g., 2 to 4 weeks), PFAS concentrations at equilibrium could be estimated based on the concentrations of the PRCs remaining in the sampler at retrieval. All PFAS concentrations determined via this approach were within a factor of two compared to those measured in the mechanically extracted sediment pore water and surface water samples obtained adjacent to the sampler deployment locations. Neither biofouling of the rate-limiting barrier nor any physical change to it was observed on the sampler after retrieval. The passive sampler developed in this study could be a promising tool for the monitoring of PFAS in pore water and surface water.

How does periodic polarity reversal affect the faradaic efficiency and electrode fouling during iron electrocoagulation?

Electrocoagulation (EC) is a promising electrochemical water treatment technology. However, a major challenge to sustaining effective long-term EC operation is controlling the precipitation of materials on the electrodes, commonly referred to as fouling. Periodically reversing electrode polarity has been suggested as an in-situ fouling mitigation strategy and is often implemented in EC field applications. However, the utility of this approach has not been investigated in detail. In this study, the effect of polarity reversal (PR) on the performance of EC using iron electrodes was examined under different water chemistry conditions and at a range of reversal frequencies. It was observed that the faradaic efficiency in PR-EC was always lower than that in the EC systems operated with a direct current (i.e., DC-EC). It was also observed that the faradaic efficiency progressively decreased as the current reversal frequency increased, with the faradaic efficiency dropping as low as 10% when the PR interval was 0.5 min. Results from fouling layer, chronopotentiometric, and cyclic voltammetric investigations indicated that the decrease in the faradaic efficiency was caused by (i) increased electrode fouling by iron precipitates and (ii) electrochemical side reactions at the electrode-electrolyte interface. The extent of these effects was dependent on the solution chemistry; oxyanions and sulfide were found to be particularly detrimental to the performance of PR-EC, causing severe electrode fouling while decreasing the faradaic efficiency. Fouling could be mitigated by increasing the solution convection rate, resulting in a shear on the electrode surface that removed iron and other electrochemically reactive species from the electrodes.

Mitigating Electrode Fouling in Electrocoagulation by Means of Polarity Reversal: The Effects of Electrode Type, Current Density, and Polarity Reversal Frequency.

One of the biggest issues in electrocoagulation (EC) water treatment processes is electrode fouling, which can cause decreased coagulant production, increased ohmic resistance and energy consumption, and reduced contaminant removal efficiency, among other operational problems. While it has been suggested that switching the current direction intermittently (i.e., polarity reversal, PR) can help mitigate electrode fouling, conflicting results about the utility of this approach have been reported in the literature. The objective of this study was to systematically investigate the effects of PR frequency and current density on the performance of Fe-EC and Al-EC. It was found that operating Fe-EC under the PR mode reduced neither electrode fouling nor energy consumption. Notably, the Faradaic efficiency (ϕ) in Fe-EC decreased with increasing PR frequency; ϕ was as low as 10% when a PR frequency of 0.5 minutes was employed. Unlike Fe-EC, operating Al-EC under the PR mode resulted in high coagulant production efficiencies, reduced energy consumption, and diminished electrode fouling. In addition to comparing PR-EC and DC-EC, a novel strategy to minimize electrode fouling was investigated. This strategy involved operating Fe DC-EC and Al DC-EC with a Ti-IrO2 cathode, whose fouling by Ca- and Mg-containing minerals could be readily avoided by periodically switching the current direction.

Treatment of electrochemical plating wastewater by heterogeneous photocatalysis: the simultaneous removal of 6:2 fluorotelomer sulfonate and hexavalent chromium.

6:2 fluorotelomer sulfonate (6:2 FtS) is being widely used as a mist suppressant in the chromate (Cr(vi)) plating process. As a result, it is often present alongside Cr(vi) in the chromate plating wastewater (CPW). While the removal of Cr(vi) from CPW has been studied for decades, little attention has been paid to the treatment of 6:2 FtS. In this study, the removal of Cr(vi) and 6:2 FtS by Ga2O3, In2O3, and TiO2 photocatalysts was investigated. In the Ga2O3/UVC system, over 95% of Cr(vi) was reduced into Cr(iii) after only 5 min. Simultaneously, 6:2 FtS was degraded into F- and several perfluorocarboxylates. The predominant reactive species responsible for the degradation of 6:2 FtS in the Ga2O3 system were identified to be hVB + and O2˙-. In addition, it was observed that the presence of Cr(vi) helped accelerate the degradation of 6:2 FtS. This synergy between Cr(vi) and 6:2 FtS was attributable to the scavenging of eCB - by Cr(vi), which retarded the recombination of eCB - and hVB +. The In2O3/UVC system was also capable of removing Cr(vi) and 6:2 FtS, although at significantly slower rates. In contrast, poor removal of 6:2 FtS was achieved with the TiO2/UVC system, because Cr(iii) adsorbed on TiO2 and inhibited its reactivity. Based on the results of this study, it is proposed that CPW can be treated by a treatment train that consists of an oxidation-reduction step driven by Ga2O3/UVC, followed by a neutralization step that converts dissolved Cr(iii) into Cr(OH)3(S).

Activation of Hydrogen Peroxide by a Titanium Oxide-Supported Iron Catalyst: Evidence for Surface Fe(IV) and Its Selectivity.

Iron immobilized on supports such as silica, alumina, titanium oxide, and zeolite can activate hydrogen peroxide (H2O2) into strong oxidants. However, the role of the support and the nature of the oxidants produced in this process remain elusive. This study investigated the activation of H2O2 by a TiO2-supported catalyst (FeTi-ox). Characterizing the catalyst surface in situ using X-ray absorption spectroscopy (XAS), together with X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR), revealed that the interaction between H2O2 and the TiO2 phase played a key role in the H2O2 activation. This interaction generated a stable peroxo-titania ≡Fe(III)-Ti-OOH complex, which reacted further with H2O to produce a surface oxidant, likely ≡Fe[IV] ═ O2+. The oxidant effectively degraded acetaminophen, even in the presence of chloride, bicarbonate, and organic matter. Unexpectedly, contaminant oxidation continued after the H2O2 in the solution was depleted, owing to the decomposition of ≡Fe(III)-Ti-OOH by water. In addition, the FeTi-ox catalyst effectively degraded acetaminophen over five testing cycles. Overall, new insights gained in this study may provide a basis for designing more effective catalysts for H2O2 activation.

Treatment of sulfolane in groundwater: A critical review.

This review critically examined the existing technologies for the treatment of sulfolane, which is an emerging groundwater contaminant. In general, sulfolane plumes are difficult to contain and mitigate because sulfolane is highly mobile and does not biodegrade to an appreciable extent under anoxic conditions typical of many subsurface environments. Several studies have shown that sulfolane biodegradation can be enhanced in the presence of oxygen, suggesting that in situ biosparging or ex-situ (i.e., pump and treat) aerobic biodegradation can potentially be effective means of remediating sulfolane-contaminated sites. While highly reactive species such as SO4•- and •OH radicals have been shown to oxidize sulfolane, whether sulfolane can be effectively treated by ex situ advanced oxidation processes (AOPs) or by in situ chemical oxidation (ISCO) needs to be further examined. Besides chemical and biological treatments, pump and treat by adsorption on granular activated carbon (GAC) has been applied to remove sulfolane at several sites. To optimize the treatment as well as to identify more effective adsorbents, additional research is needed to investigate the mechanism and factors affecting sulfolane adsorption. In addition to assessing the treatment of sulfolane, this review also discussed the analytical methods for the quantification of sulfolane in the context that guidelines for sulfolane will likely become more stringent and, therefore, analytical methods with lower detection limit will be needed for future research.

Reduction of chlorendic acid by zero-valent iron: Kinetics, products, and pathways.

Chlorendic acid (CA) is a recalcitrant groundwater contaminant for which an effective treatment technology does not currently exist. In this study, a series of batch experiments were conducted to investigate the treatment of CA by zero-valent iron (ZVI) under various water chemistry conditions. It was observed that CA was removed by ZVI via both adsorption and degradation, with the degradation rate being proportional to the fraction of CA adsorbed onto ZVI. The rate of CA degradation decreased as pH increased, presumably due to the passivation of ZVI and diminishing CA adsorption. Chloride (Cl-) did not appreciably affect CA adsorption and degradation, while sulfate (SO42-) significantly inhibited both processes because SO42- competed with CA for ZVI adsorptive sites. The rate of CA degradation was significantly accelerated by ZVI-associated Fe(II). Nine byproducts of CA transformation were identified by high-resolution mass spectrometry. The formation and subsequent degradation of these products revealed that the transformation of CA by ZVI occurred via a step-wise reductive dechlorination pathway. Overall, this study suggests that ZVI may be effective at remediating CA-contaminated sites.

Nickel-Nickel oxide nanocomposite as a magnetically separable persulfate activator for the nonradical oxidation of organic contaminants.

The nanocomposite of metallic nickel and nickel oxide (denoted as Ni-NiO), synthesized by a simple sol-gel method, was found to activate peroxydisulfate (PDS), resulting in the effective oxidation of phenolic compounds and selected pharmaceuticals. A nonradical mechanism was proposed to explain the activation of PDS by Ni-NiO, in which organic contaminants are believed to be oxidized through an electron abstraction pathway mediated by the reactive complexes formed between PDS and the Ni-NiO surface. This mechanism was supported by multiple lines of evidence including radical scavenger experiments, the oxidation products, linear sweep voltammetry, and electron paramagnetic resonance spectroscopy. The Ni-NiO/PDS system exhibited a PDS utilization efficiency (expressed by the ratio of degraded organic contaminant to decomposed PDS) that was over 80%, and Ni-NiO showed a greater activity for PDS activation than a commercial nanoparticulate nickel oxide. This improved performance of Ni‒NiO was attributed to the disproportioned incorporation of the metallic Ni into the NiO matrix, creating more sites with oxygen vacancy. Also owing to the metallic Ni, Ni-NiO possessed magnetic properties and therefore could be easily separated and reused.

Effective removal of silica and sulfide from oil sands thermal in-situ produced water by electrocoagulation.

Effective removal of silica and sulfide from oil sands thermal in-situ produced water can reduce corrosion and scaling of steam generators, enhancing water recycling and reuse in the industry. The removal of these two solutes as well as calcium and magnesium (i.e., the solutes that can also cause scaling) from synthetic and authentic produced waters by electrocoagulation (EC) was investigated in this study. In Fe0-EC, the precipitation of FeS minerals resulted in a rapid removal of sulfide and adsorption of silica onto FeS. In Al0-EC, silica was removed via adsorption onto aluminum hydroxides, but sulfide was poorly removed. In both EC systems, Ca2+ and Mg2+ were removed from the organic-free synthetic produced water but not from the authentic water, likely due to the influence of organic species. Contaminant removals in Fe0-EC were controlled by charge density (q, C/L) but not current density (i, mA/cm2). Overall, this research suggests that EC can be a promising technology for the treatment of thermal in-situ produced water. Fe0-EC appears to be a better choice than Al0-EC considering that Fe0-EC was more effective at removing sulfide, and that Fe0 anodes are usually less expensive.

In-situ chemical oxidation of chlorendic acid by persulfate: Elucidation of the roles of adsorption and oxidation on chlorendic acid removal.

The oxidation of chlorendic acid (CA), a polychlorinated recalcitrant contaminant, by heat-, mineral-, and base-activated persulfate was investigated. In pH 3-12 homogeneous (i.e., solid-free) solutions, CA was oxidized by •OH and SO4•- radicals, resulting in a nearly stoichiometric production of Cl-. The rate constants for the reaction between these radicals and CA were measured at different temperatures by electron pulse radiolysis, and were found to be kOH = (8.71 ±â€¯0.17) × 107 M-1s-1 and kSO4 = (6.57 ±â€¯0.83) × 107 M-1s-1 at 24.5 °C for •OH and SO4•-, respectively. CA was oxidized at much slower rates in solutions containing iron oxyhydroxide or aquifer soils, partially due to the adsorption of CA on these solids. To gain further insight into the effect of solids during in-situ remediation of CA, the adsorption of CA onto iron (hydr)oxide, manganese dioxide, silica, alumina, and aquifer soils was investigated. The fraction of CA that was adsorbed on these materials increased as the solution pH decreased. Given that the solution pH can decrease dramatically in persulfate-based remedial systems, adsorption may reduce the ability of persulfate to oxidize CA. Overall, the results of this study provide important information about how persulfate can be used to remediate CA-contaminated sites. The results also indicate that the groundwater pH and geology of the subsurface can have a significant influence on the mobility of CA.

Oxidation of benzoic acid by heat-activated persulfate: Effect of temperature on transformation pathway and product distribution.

Heat activates persulfate (S2O82-) into sulfate radical (SO4-), a powerful oxidant capable of transforming a wide variety of contaminants. Previous studies have shown that an increase in temperature accelerates the rates of persulfate activation and contaminant transformation. However, few studies have considered the effect of temperature on contaminant transformation pathway. The objective of this study was to determine how temperature (T = 22-70 °C) influences the activation of persulfate, the transformation of benzoic acid (i.e., a model compound), and the distribution of benzoic acid oxidation products. The time-concentration profiles of the products suggest that benzoic acid was transformed via decarboxylation and hydroxylation mechanisms, with the former becoming increasingly important at elevated temperatures. The pathway through which the products were further oxidized was also influenced by the temperature of persulfate activation. Our findings suggest that the role of temperature in the persulfate-based treatment systems is not limited only to controlling the rates of sulfate and hydroxyl radical generation. The ability of sulfate radical to initiate decarboxylation reactions and, more broadly, fragmentation reactions, as well as the effect of temperature on these transformation pathways could be important to the transformation of a number of organic contaminants.

Influence of Sulfide Nanoparticles on Dissolved Mercury and Zinc Quantification by Diffusive Gradient in Thin-Film Passive Samplers.

Diffusive gradient in thin-film (DGT) passive samplers are frequently used to monitor the concentrations of metals such as mercury and zinc in sediments and other aquatic environments. The application of these samplers generally presumes that they quantify only the dissolved fraction and not particle-bound metal species that are too large to migrate into the sampler. However, metals associated with very small nanoparticles (smaller than the pore size of DGT samplers) can be abundant in certain environments, yet the implications of these nanoparticles for DGT measurements are unclear. The objective of this study was to determine how the performance of the DGT sampler is affected by the presence of nanoparticulate species of Hg and Zn. DGT samplers were exposed to solutions containing known amounts of dissolved Hg(II) and nanoparticulate HgS (or dissolved Zn(II) and nanoparticulate ZnS). The amounts of Hg and Zn accumulated onto the DGT samplers were quantified over hours to days, and the rates of diffusion of the dissolved metal (i.e., the effective diffusion coefficient D) into the sampler's diffusion layer were calculated and compared for solutions containing varying concentrations of nanoparticles. The results suggested that the nanoparticles deposited on the surface of the samplers might have acted as sorbents, slowing the migration of the dissolved species into the samplers. The consequence was that the DGT sampler data underestimated the dissolved metal concentration in the solution. In addition, X-ray absorption spectroscopy was employed to determine the speciation of the Hg accumulated on the sampler binding layer, and the results indicated that HgS nanoparticles did not appear to directly contribute to the DGT measurement. Overall, our findings suggest that the deployment of DGT samplers in settings where nanoparticles are relevant (e.g., sediments) may result in DGT data that incorrectly estimated the dissolved metal concentrations. Models for metal uptake into the sampler may need to be reconsidered.

Kinetics and efficiency of H2O2 activation by iron-containing minerals and aquifer materials.

To gain insight into factors that control H(2)O(2) persistence and ·OH yield in H(2)O(2)-based in situ chemical oxidation systems, the decomposition of H(2)O(2) and transformation of phenol were investigated in the presence of iron-containing minerals and aquifer materials. Under conditions expected during remediation of soil and groundwater, the stoichiometric efficiency, defined as the amount of phenol transformed per mole of H(2)O(2) decomposed, varied from 0.005 to 0.28%. Among the iron-containing minerals, iron oxides were 2-10 times less efficient in transforming phenol than iron-containing clays and synthetic iron-containing catalysts. In both iron-containing mineral and aquifer materials systems, the stoichiometric efficiency was inversely correlated with the rate of H(2)O(2) decomposition. In aquifer materials systems, the stoichiometric efficiency was also inversely correlated with the Mn content, consistent with the fact that the decomposition of H(2)O(2) on manganese oxides does not produce ·OH. Removal of iron and manganese oxide coatings from the surface of aquifer materials by extraction with citrate-bicarbonate-dithionite slowed the rate of H(2)O(2) decomposition on aquifer materials and increased the stoichiometric efficiency. In addition, the presence of 2 mM of dissolved SiO(2) slowed the rate of H(2)O(2) decomposition on aquifer materials by over 80% without affecting the stoichiometric efficiency.

Dissolution of Mesoporous Silica Supports in Aqueous Solutions: Implications for Mesoporous Silica-based Water Treatment Processes.

Under pH 7 - 10 conditions, the mesoporous silica supports proposed for use in water treatment are relatively unstable. In batch experiments conducted in pH 7 solutions, the commonly used support SBA-15 dissolved quickly, releasing approximately 30 mg/L of dissolved silica after 2 hours. In column experiments, more than 45% of an initial mass of 0.25 g SBA-15 dissolved within 2 days when a pH 8.5 solution flowed through the column. In a mixed iron oxide/SBA-15 system, the dissolution of SBA-15 changed the iron oxide reactivity toward H(2)O(2) decomposition, because dissolved silica deposited on iron oxide surface and changed its catalytic active sites. As with SBA-15, other mesoporous silica materials including HMS, MCM-41, four types of functionalized SBA-15, and two types of metal oxide-containing SBA-15 also dissolved under circumneutral pH solutions. The dissolution of mesoporous silica materials raises questions about their use under neutral and alkaline pH in aqueous solutions, because silica dissolution might compromise the behavior of the material.

Inhibitory effect of dissolved silica on H2O2 decomposition by iron(III) and manganese(IV) oxides: implications for H2O2-based in situ chemical oxidation.

The decomposition of H(2)O(2) on iron minerals can generate •OH, a strong oxidant that can transform a wide range of contaminants. This reaction is critical to In Situ Chemical Oxidation (ISCO) processes used for soil and groundwater remediation, as well as advanced oxidation processes employed in waste treatment systems. The presence of dissolved silica at concentrations comparable to those encountered in natural waters decreases the reactivity of iron minerals toward H(2)O(2), because silica adsorbs onto the surface of iron minerals and alters catalytic sites. At circumneutral pH values, goethite, amorphous iron oxide, hematite, iron-coated sand, and montmorillonite that were pre-equilibrated with 0.05-1.5 mM SiO(2) were significantly less reactive toward H(2)O(2) decomposition than their original counterparts, with the H(2)O(2) loss rates inversely proportional to SiO(2) concentrations. In the goethite/H(2)O(2) system, the overall •OH yield, defined as the percentage of decomposed H(2)O(2) producing •OH, was almost halved in the presence of 1.5 mM SiO(2). Dissolved SiO(2) also slowed H(2)O(2) decomposition on manganese(IV) oxide. The presence of dissolved SiO(2) results in greater persistence of H(2)O(2) in groundwater and lower H(2)O(2) utilization efficiency and should be considered in the design of H(2)O(2)-based treatment systems.

A silica-supported iron oxide catalyst capable of activating hydrogen peroxide at neutral pH values.

Iron oxides catalyze the conversion of hydrogen peroxide (H(2)O(2)) into oxidants capable of transforming recalcitrant contaminants. Unfortunately, the process is relatively inefficient at circumneutral pH values because of competing reactions that decompose H(2)O(2) without producing oxidants. Silica- and alumina-containing iron oxides prepared by sol-gel processing of aqueous solutions containing Fe(ClO(4))(3), AlCl(3), and tetraethyl orthosilicate efficiently catalyzed the decomposition of H(2)O(2) into oxidants capable of transforming phenol at circumneutral pH values. Relative to hematite, goethite, and amorphous FeOOH, the silica-iron oxide catalyst exhibited a stoichiometric efficiency, defined as the number of moles of phenol transformed per mole of H(2)O(2) consumed, which was 10-40 times higher than that of the iron oxides. The silica-alumina-iron oxide catalyst had a stoichiometric efficiency that was 50-80 times higher than that of the iron oxides. The significant enhancement in oxidant production is attributable to the interaction of Fe with Al and Si in the mixed oxides, which alters the surface redox processes, favoring the production of strong oxidants during H(2)O(2) decomposition.