Perfluorooctanoic acid (PFOA) including linear and branched isomers is one of only three PFAS included in the Stockholm convention on Persistent Organic Pollutants. Unfortunately, PFOA branched isomers have received less attention than the linear due to analytical difficulties and perceived lower environmental concentrations. In this study, we revealed a environmentally relevant pathway for the formation of branched PFOA from PFAS precursors. AFFF samples showed a doubling of branched PFOA concentrations (138 mg/L) after TOP assay oxidation (307 mg/L). These findings indicate that branched PFOA may be more pervasive in the environment than previously thought. Additionally, we investigated the reductive degradability of PFOA using vitamin B12 (VB12) (a naturally occurring electron shuttle) in combination with either zero-valent zinc (ZVZ) or zero-valent iron (ZVI). Linear PFOA, as well as two branched isomers (3-methyl PFOA and 5,5-dimethyl PFOA), resisted reductive defluorination under the experimental conditions. However, all other branched isomers degraded within 10 days in the ZVZ-VB12 system. The experimental rate constants for specific PFOA isomers generally correlate with their calculated reduction potentials, except for 6-methyl PFOA. A potential defluorination pathway was proposed based on high-resolution mass spectrometry (LC-Orbitrap) and density functional theory (DFT) studies.

Nano zero-valent metals (nZVMs) have been extensively utilized for decades in the reductive remediation of groundwater contaminated with chlorinated organic compounds, owing to their robust reducing capabilities, simple application, and cost-effectiveness. Nevertheless, there remains a dearth of information regarding the efficient reductive defluorination of linear or branched per- and polyfluoroalkyl substances (PFASs) using nZVMs as reductants, largely due to the absence of appropriate catalysts. In this work, various soluble porphyrin ligands [[meso-tetra(4-carboxyphenyl)porphyrinato]cobalt(III)]Cl.7H2O (CoTCPP), [[meso-tetra(4-sulfonatophenyl) porphyrinato]cobalt(III)].9H2O (CoTPPS), and [[meso-tetra(4-N-methylpyridyl) porphyrinato]cobalt(II)] (I)4.4H2O (CoTMpyP) have been explored for defluorination of PFASs in the presence of the nZn0 as reductant. Among these, the cationic CoTMpyP showed best defluorination efficiencies for br-perfluorooctane sulfonate (PFOS) (94%), br-perfluorooctanoic acid (PFOA) (89%), and 3,7-Perfluorodecanoic acid (PFDA) (60%) after 1 day at 70 degrees C. The defluorination rate constant of this system (CoTMpyP-nZn0) is 88-164 times higher than the VB12-nZn0 system for the investigated br-PFASs. The CoTMpyP-nZn0 also performed effectively at room temperature (55% for br-PFOS, 55% for br-PFOA and 25% for 3,7-PFDA after 1day), demonstrating the great potential of in-situ application. The effect of various solubilizing substituents, electron transfer flow and corresponding PFASs defluorination pathways in the CoTMpyP-nZn0 system were investigated by both experiments and density functional theory (DFT) calculations. SYNOPSIS: Due to the unavailability of active catalysts, available information on reductive remediation of PFAS by zero-valent metals (ZVMs) is still inadequate. This study explores the effective defluorination of various branched PFASs using soluble porphyrin-ZVM systems and offers a systematic approach for designing the next generation of catalysts for PFAS remediation.

Per- and polyfluoroalkyl substances (PFAS) are a class of fluorinated chemicals used widely in consumer and industrial products. Their human toxicity and ecosystem impacts have received extensive public, scientific and regulatory attention. Regulatory PFAS guidance is rapidly evolving, with the inclusion of a wider range of PFAS included in advisories and a continued decrease in what is deemed safe PFAS concentrations. In this study we collated PFAS concentration data for over 45,000 surface and groundwater samples from around the world to assess the global extent of PFAS contamination and their potential future environmental burden. Here we show that a substantial fraction of sampled waters exceeds PFAS drinking water guidance values, with the extent of exceedance depending on the jurisdiction and PFAS source. Additionally, current monitoring practices probably underestimate PFAS in the environment given the limited suite of PFAS that are typically quantified but deemed of regulatory concern. An improved understanding of the range of PFAS embodied in consumer and industrial products is required to assess the environmental burden and develop mitigation measures. While PFAS is the focus of this study, it also highlights society’s need to better understand the use, fate and impacts of anthropogenic chemicals. A global data analysis suggests that a large fraction of surface waters and groundwaters globally have concentrations of per- and polyfluoroalkyl substances (PFAS) that exceed international advisories or national regulations.

Green rust (GR) minerals are generally considered to be effective reductants of pollutants and the electron transfer from aqueous Fe(II) to structural Fe(III) in montmorillonite has recently been discovered to be a pathway to GR formation at pH ∼7.8. In this study, we have further delineated the pH conditions and examined the effect of aqueous sulfate concentrations that allow for the formation of sulfate-GR through this unique pathway. Iron(II) sorption experiments demonstrated that the amount of 'sorbed' Fe(II) on montmorillonite semi-quantitatively transformed into sulfate-GR at pH values ≥7.5 in the presence of environmentally-relevant sulfate concentrations (i.e., 10 mM). However, excess sulfate concentrations (100 mM) resulted in comparatively less Fe(II) sorption and sulfate-GR was only observed to form at pH 8. As such, it was concluded that the degree of Fe(II) sorption to montmorillonite is critical to GR formation when aqueous Fe(II) and montmorillonite co-exist. In contrast to sulfate-GR minerals formed through other pathways (e.g., co-precipitation of dissolved Fe(II) and Fe(III) species), this montmorillonite-synthesized GR was significantly less reactive towards nitrate reduction, with <2.5 % of 0.2 mM nitrate being reduced over a 6-day period. This behaviour was correlated to reduction potential and it was, therefore, concluded that the relatively high reduction potential that occurs in the presence of montmorillonite exerts a significant influence on the rate of nitrate reduction by sulfate-GR to the point that it may not be a competitive process to microbiological nitrate denitrification. As such, the environmental relevance of green rust to nitrate reduction cannot be inferred simply by its presence, but rather the reduction potential of the environmental system in which it is found.

In this study, the kinetics and stable isotopic fractionation of nitrate (NO3-) reduction in Fe(II)/Fe(III) homogeneous/heterogeneous systems were investigated at circumneutral pH (i.e., pH 6.5 to 7.5) and ambient temperature (24 degrees C). Of the suite of iron (oxy)(hydr)oxides examined, NO3- reduction by Fe(II) was only significant in the presence of layered double hydroxide green rust (GR) minerals. Comparison of type 1 and type 2 GRs demonstrated that type 1 (GR(Cl-)) had the fastest NO3- reducing ability, with an Fe(II)-normalized pseudo first-order kinetic rate constant of kobs (NO3-) = 16.2 x 101 M-1 d-1. Anion concentrations (SO42-or Cl-) and the ratio of [Fe(II)] to [Fe(III)] also influenced reduction kinetics. Ammonium (NH4+) was the predominant reaction end-product (>50%) with the remaining reduced N spe-cies concluded to be comprised of N2(g) as other intermediates (nitrite (NO2-), nitric oxide (NO) and nitrous oxide (N2O) were not detected during NO3- reduction. Apparent nitrogen (815N-NO3-) isotopic frac-tionation (156) for GR(Cl-) and GR(SO42-) were were calculated to be 12.9 (CI: 8.2, 16)%degrees and 37.9 (CI: 34, 41)%degrees, respectively. Similarly, oxygen (818O-NO3-) isotopic fractionation (186) differed between GR(Cl-) and GR(SO42-): 4.53 (CI: 2.5, 5.8)%degrees and 14.4 (CI: 12, 16)%degrees. However, the ratio of186:156 for both minerals could be fitted to a linear regression of slope 0.369 (CI: 0.361, 0.377). These findings reaffirm the impor-tance of GR minerals to NO3- reduction, especially in iron-rich systems hosting dynamic redox oscilla-tions, including hyporheic zones, estuarine sediments and groundwater aquifers. These results also demonstrate that N and O stable isotope kinetic fractionation analyses as well as the ratio of 186:156 can provide a means to distinguish between this abiotic anoxic reaction from anaerobic bacterial NO3- reduction processes.(c) 2023 Elsevier Ltd. All rights reserved.

This scoping study investigates the ability of an inexpensive, commercially available granular activated carbon (GAC) to sorb and conduct electrical charge to achieve reductive defluorination of PFAS.

Although evidence has indicated that the biogeochemical coupling of Fe and N redox reactions has potentially important impacts on the cycling of N in the environment, the relevance of abiotic Fe and N redox transformations remain unclear, especially in acid sulfate soil (ASS) environments where biological denitrification processes are considered to be hindered under such acidic conditions. Considering natural conditions and one of the main Fe mineral components of ASS, we have evaluated the effect of low to circumneutral pH on NO3- chemodenitrification by mackinawite (FeS) at ambient temperature and investigated the isotopic fractionation of this N reduction pathway. At equal FeS concentrations, optimal NO3- reduction occurred at pH 3.5, where microbial denitrification is widely considered to be at its slowest and decreased as pH increased to 7. In all cases, NO3- chemodenitrification reactions had ceased within 24 h. At most, 10% of the NO3- was reduced to NH4+, and through a process of elimination, N2(g) was identified as the major reduced N product. Nitrate chemodenitrification resulted in FeS oxidation to greigite (Fe3S4), elemental sulfur (S0), thiosulfate (S2O32-), and SO42-, indicating oxidation of both Fe and S. As was the case for pH, an inverse relationship existed between the reduction potential and NO3- chemodenitrification, suggesting either the possible involvement of reduced aqueous sulfur species, such as H2S or S2O32-, in catalyzing NO3- reduction or mineral surface passivation inhibiting electron transfer processes at higher pH values. Nevertheless, in the presence of a large excess of FeS (82 mM), these kinetic differences were less pronounced. Stable N and O isotope measurements during NO3- reduction demonstrated that there were no kinetic isotope effects for either delta 15N or delta 18O in the residual NO3- pool. These results suggest that the kinetics of NO3- (re)population of reduction site(s) is exceedingly slow, compared to electron transfer, and this rate-limiting step prevents kinetic isotopic discrimination during reduction. This study demonstrates that NO3- chemodenitrification may be relevant in anoxic environments where FeS is abundant, like ASS that is found in subtropical/tropical climates. Furthermore, this NO3- chemodenitrification pathway does not contribute to the formation of the greenhouse gas N2O(g). However, the first step of NO3- reduction by FeS does not produce any significant effects on delta 15N-NO3- and delta 18O-NO3- and so is largely "invisible" to stable isotope analyses of the residual NO3- pool. As a result, its contribution to NO3- reduction, in the presence of other biotic/abiotic pathways, could be underestimated when using stable isotope measurements of NO3-.

Vitamin B12 (VB12) has been reported to degrade PFOS in the presence of TiIII citrate at 70 °C. Porphyrin-based catalysts have emerged as VB12 analogues and have been successfully used in various fields of research due to their interesting structural and electronic properties. However, there is inadequate information on the use of these porphyrin-based metal complexes in the defluorination of PFOS. We have therefore explored a series of porphyrin-based metal complexes for the degradation of PFOS. CoII-5,10,15,20-tetraphenyl-21H,23H-porphyrin (CoII-TPP), CoII-5,10,15,20-tetrakis(4-methoxyphenyl)-21H,23H-porphyrin (CoII-M-TPP), and CoIII-M-TPP exhibited efficient reductive defluorination of the branched PFOS. Within 5-8 h, these compounds achieved the same level of PFOS defluorination as VB12 achieved in 7-10 days. For branched isomers, the specific removal rate of the CoII-TPP-TiIII citrate system is 64-105 times higher than that for VB12-TiIII citrate. Moreover, the CoII-TPP-TiIII citrate system displayed efficient (51%) defluorination for the branched PFOS (br-PFOS) in 1 day even at room temperature (25 °C). The effects of the iron and cobalt metal centers, reaction pH, and several reductants (NaBH4, nanosized zerovalent zinc (nZn0), and TiIII citrate) were systematically investigated. Based on the analysis of the products and previously published reports, a new possible defluorination pathway of branched PFOS is also proposed.

Iron (Fe) is the fourth most abundant element in the earth's crust and plays important roles in both biological and chemical processes. The redox reactivity of various Fe(II) forms has gained increasing attention over recent decades in the areas of (bio) geochemistry, environmental chemistry and engineering, and material sciences. The goal of this paper is to review these recent advances and the current state of knowledge of Fe(II) redox chemistry in the environment. Specifically, this comprehensive review focuses on the redox reactivity of four types of Fe(II) species including aqueous Fe(II), Fe(II) complexed with ligands, minerals bearing structural Fe(II), and sorbed Fe(II) on mineral oxide surfaces. The formation pathways, factors governing the reactivity, insights into potential mechanisms, reactivity comparison, and characterization techniques are discussed with reference to the most recent breakthroughs in this field where possible. We also cover the roles of these Fe(II) species in environmental applications of zerovalent iron, microbial processes, biogeochemical cycling of carbon and nutrients, and their abiotic oxidation related processes in natural and engineered systems.

Iron (Fe) is the fourth most abundant element in the earth's crust and plays important roles in both biological and chemical processes. The redox reactivity of various Fe(II) forms has gained increasing attention over recent decades in the areas of (bio) geochemistry, environmental chemistry and engineering, and material sciences. The goal of this paper is to review these recent advances and the current state of knowledge of Fe(II) redox chemistry in the environment. Specifically, this comprehensive review focuses on the redox reactivity of four types of Fe(II) species including aqueous Fe(II), Fe(II) complexed with ligands, minerals bearing structural Fe(II), and sorbed Fe(II) on mineral oxide surfaces. The formation pathways, factors governing the reactivity, insights into potential mechanisms, reactivity comparison, and characterization techniques are discussed with reference to the most recent breakthroughs in this field where possible. We also cover the roles of these Fe(II) species in environmental applications of zerovalent iron, microbial processes, biogeochemical cycling of carbon and nutrients, and their abiotic oxidation related processes in natural and engineered systems.

The reactivity and early strength of cement:slag binders is usefully enhanced by the addition of sodium sulfate though the underlying mechanisms of the relationship between the enhanced hydration reactions and the structural aspects of the strength behavior remain unclear. In this study, microstructural development in the presence of Na2SO4 was investigated utilizing mercury intrusion porosimetry (MIP), NMR relaxometry, and XRD. Increased rates of early strength development and decreased rates of late strength development due to the presence of added Na2SO4 were linked to effects on capillary porosity refinement. While degree of hydration at later age was shown to have been lower in the presence of Na2SO4, and may have been responsible for the higher capillary porosity, a clear alteration in the pathway of microstructural development had occurred with inhibition to hydration of the slag component due to earlier microstructural development proposed.

Ferrihydrite (Fh) is a major Fe(III)-(oxyhydr)oxide nanomineral distinguished by its poor crystallinity and thermodynamic metastability. While it is well known that in suboxic conditions aqueous Fe(II) rapidly catalyzes Fh transformation to more stable crystalline Fe(III) phases such as lepidocrocite (Lp) and goethite (Gt), because of the low solubility of Fe(III) the mass transfer pathways enabling these rapid transformations have remained unclear for decades. Here, using a selective extractant, we isolated and quantified a critical labile Fe(III) species, one that is more reactive than Fe(III) in Fh, formed by the oxidation of aqueous Fe(II) on the Fh surface. Experiments that compared time-dependent concentrations of solid-associated Fe(II) and this labile Fe(III) against the kinetics of phase transformation showed that its accumulation is directly related to Lp/Gt formation in a manner consistent with the classical nucleation theory. 57Fe isotope tracer experiments confirm the oxidized Fe(II) origin of labile Fe(III). The transformation pathway as well as the accelerating effect of Fe(II) can now all be explained on a unified basis of the kinetics of Fe(III) olation and oxolation reactions necessary to nucleate and sustain growth of Lp/Gt products, rates of which are greatly accelerated by labile Fe(III).

The action of added sodium sulfate (Na2SO4) leading to increased reactivity and early strength in slag: cement binders remains unclear. In this study, early hydration reactions and resultant compressive strength in a 50:50 slag:cement binder in the presence of Na2SO4 were investigated. Early strength increases in the presence of Na2SO4 were shown to be due to a combination of increased alite hydration and increased slag dissolution. Increased alite hydration was due to neither reduced dissolved Al concentration nor increased alite under-saturation but related to increased ionic strength. Increased slag dissolution was associated with both increased pH and decreased Ca activity with the two being connected through the portlandite solubility limit. Na2SO4 was shown to substantially enhance slag dissolution at fixed pH 13 with this action attributed to greater under-saturation of slag as a result of ettringite formation. Na2SO4 was shown to be superior to alternate activators in a slag:cement binder.

Unacceptably high uranium concentrations in decentralized and remote potable groundwater resources, especially those of high hardness (e.g ., high Ca2+, Mg2+, and CO32- concentrations), are a common worldwide problem. The complexation of alkali earth metals, carbonate, and uranium(VI) results in the formation of thermodynamically stable ternary aqueous species that are predominantly neutrally charged (e.g ., Ca2(UO2)(CO3)30). The removal of the uncharged (nonadsorbing) complexes is a problematic issue for many water treatment technologies. As such, we have evaluated the efficacy of a recently developed electrochemical technology, termed flow-electrode capacitive deionization (FCDI), to treat a synthetic groundwater, the composition of which is comparable to groundwater resources in the Northern Territory, Australia (and elsewhere worldwide). Theoretical calculations and time-resolved laser fluorescence spectroscopy analyses confirmed that Ca2(UO2)(CO3)30 was the primary aqueous species followed by Ca(UO2)(CO3)32- (at circumneutral pH values). Results under different operating conditions demonstrated that FCDI is versatile in reducing uranium concentrations to <10 μg L-1 with low electrical consumption (e.g ., ∼0.1 kWh m-3). It is concluded that the capability of FCDI to remove uranium under these common conditions depends on the dissociation kinetics of the Ca2(UO2)(CO3)30 complex in the electrical field. The subsequent formation of the negatively charged Ca(UO2)(CO3)32- species results in the efficient transport of uranium across the anion exchange membrane followed by immobilization on the positively charged flow (anode) electrode.

The application of nanoscale zero-valent iron (nZVI) for the degradation of contaminants has been extensively investigated, however, few studies have focused on degradation in high salinity environments. In this study, the ability of bare and carboxymethyl cellulose (CMC)-coated bimetallic Pd-nZVI particles to degrade 33′44′-tetrachlorobiphenyl in high saline water (SW) is examined with particular attention given to the effects of ethylenediaminetetraacetic acid (EDTA) on the rate of degradation. EDTA enhances the reactivity of Pd-nZVI in SW, with evidence provided to link this to the removal of the passivating layer. Additionally, a conceptual model is proposed which provides a quantitative description of the removal of these iron oxide layers in the presence of EDTA. An optimum EDTA to bare Pd-nZVI molar ratio of 0.1 exists, with insufficient EDTA unable to remove the passivating layer whilst excess EDTA results in Fe loss and enhanced agglomeration due to magnetic attraction of the bare Fe(0) particles. In contrast, CMC-coating of Pd-nZVI assemblages actually impedes degradation, despite the coated particles displaying a smaller average size compared to uncoated particles, with even the presence of EDTA in this case not significantly improving degradation. The reduced reactivity in the presence of CMC is primarily attributed to the effect of CMC on the association of Pd with nZVI particles. In particular, the presence of CMC reduced the total amount of Pd incorporated with the stabilized particles compared to the non-stabilized particles. Additionally, the presence of CMC results in less Pd present in its reactive zero-valent oxidation state.

Iron (oxyhydr)oxides are widespread in natural and engineered systems, potent adsorbents of contaminants and a source of energy for iron-reducing bacteria. Microbial reduction of iron (oxyhydr)oxides results in the formation of Fe(II) which can induce the transformation of these iron minerals, typically from less crystalline to more crystalline forms, affecting the biogeochemical cycling of iron and the behavior of any species adsorbed to the iron (oxyhydr)oxides. Factors influencing the transformation rate of the poorly crystalline iron (oxyhydr)oxide, ferrihydrite, to more crystalline forms in the presence of the iron reducing bacterium Shewanella oneidensis MR-1 are investigated under controlled laboratory conditions in this work. In particular, the amount of Fe(II) produced increased the transformation rate while increasing concentrations of the electron donor, lactate, decreased the rate. Using kinetic parameters determined from abiotic controls, the results of transformation experiments in the presence of Shewanella oneidensis were modeled with this exercise revealing that less goethite and more lepidocrocite formed than expected. Conversely, studies using the Shewanella exudate only, containing biogenic Fe(II), displayed rates of transformation that were satisfactorily modeled using these abiotic control kinetic parameters. This result suggests that the physical presence of the microbes is pivotal to the reduction in ferrihydrite transformation rate observed in the biotic experiments relative to the analogous abiotic controls.

The oxidation of hydroquinones is of interest both due to the generation of reactive oxygen species (ROS) and to the implications to trace metal redox state. Menadione (MNQ), a typical toxicant quinone used extensively for studying the mechanisms underlying oxidative stress, is known to be an effective source of exogenous ROS. In this study, the kinetics and mechanism of the oxidation of menadiol (MNH2Q, the reduced form of MNQ) in the absence and presence of copper (Cu) over the pH range 6.0–7.5 was examined. The autoxidation rate increased with increasing pH and concentration of O2 and also slightly increased with increasing concentration of MNH2Q and MNQ with Cu shown to play a significant role in catalysing the oxidation of MNH2Q. A kinetic model showed that the mono-deprotonated menadiol, MNHQ−, accounted for the pH dependence of the autoxidation rate. In this proposed mechanism, both MNH2Q and MNHQ− species were oxidized quickly by Cu(II), generating menadione semiquinone (MNSQ•−) and superoxide (O2•−) and the reduced form of Cu, Cu(I). Oxygen not only facilitated the catalytic role of Cu(II) by rapidly regenerating Cu(II) but also effectively removed MSNQ•−, generating the important chain-propagating species O2•−. The model demonstrated that Cu(I) was a significant sink of O2•− resulting in the generation of H2O2 with subsequent generation of highly oxidative intermediates including Cu(III). These results provide considerable insight into the clinical significance of the biological activation and detoxification of MNQ with the kinetic model developed of use in identifying key processes in the generation of harmful oxidants in living systems.