Soluble metal porphyrins - Zero-valent zinc system for effective reductive defluorination of branched per and polyfluoroalkyl substances (PFASs).

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 [[meso­tetra(4-carboxyphenyl)porphyrinato]cobalt(III)]Cl·7H2O (CoTCPP), [[meso­tetra(4-sulfonatophenyl) porphyrinato]cobalt(III)]·9H2O (CoTPPS), and [[meso­tetra(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 °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.

Dead in the water - Role of relic DNA and primer choice for targeted sequencing surveys of anaerobic sewage sludge intended for biological monitoring.

DNA-based monitoring of microbial communities that are responsible for the performance of anaerobic digestion of sewage wastes has the potential to improve resource recoveries for wastewater treatment facilities. By treating sludge with propidium monoazide (PMA) prior to amplicon sequencing, this study explored how the presence of DNA from dead microbial biomass carried over with feed sludge may mislead process-relevant biomarkers, and whether primer choice impacts such assessments. Four common primers were selected for amplicon preparation, also to determine if universal primers have sufficient taxonomic or functional coverage for monitoring ecological performance; or whether two domain-specific primers for Bacteria and Archaea are necessary. Anaerobic sludges of three municipal continuously stirred-tank reactors in Victoria, Australia, were sampled at one time-point. A total of 240 amplicon libraries were sequenced on a Miseq using two universal and two domain-specific primer pairs. Untargeted metabolomics was chosen to complement biological interpretation of amplicon gene-based functional predictions. Diversity, taxonomy, phylogeny and functional potentials were systematically assessed using PICRUSt2, which can predict community wide pathway abundance. The two chosen universal primers provided similar diversity profiles of abundant Bacteria and Archaea, compared to the domain-specific primers. About 16 % of all detected prokaryotic genera covering 30 % of total abundances and 6 % of PICRUSt2-estimated pathway abundances were affected by PMA. This showed that dead biomass in the anaerobic digesters impacted DNA-based assessments, with implications for predicting active processes, such as methanogenesis, denitrification or the identification of organisms associated with biological foams. Hence, instead of running two sequencing runs with two different domain-specific primers, we propose conducting PMA-seq with universal primer pairs for routine performance monitoring. However, dead sludge biomass may have some predictive value. In principal component analysis the compositional variation of 239 sludge metabolites resembled that of 'dead-plus-alive' biomass, suggesting that dead organisms contributed to the potentially process-relevant sludge metabolome.

Catalytic dechlorination of 1,2-DCA in nano Cu0-borohydride system: effects of Cu0/Cun+ ratio, surface poisoning, and regeneration of Cu0 sites.

Aqueous-phase catalyzed reduction of organic contaminants via zerovalent copper nanoparticles (nCu0), coupled with borohydride (hydrogen donor), has shown promising results. So far, the research on nCu0 as a remedial treatment has focused mainly on contaminant removal efficiencies and degradation mechanisms. Our study has examined the effects of Cu0/Cun+ ratio, surface poisoning (presence of chloride, sulfides, humic acid (HA)), and regeneration of Cu0 sites on catalytic dechlorination of aqueous-phase 1,2-dichloroethane (1,2-DCA) via nCu0-borohydride. Scanning electron microscopy confirmed the nano size and quasi-spherical shape of nCu0 particles. X-ray diffraction confirmed the presence of Cu0 and Cu2O and x-ray photoelectron spectroscopy also provided the Cu0/Cun+ ratios. Reactivity experiments showed that nCu0 was incapable of utilizing H2 from borohydride left over during nCu0 synthesis and, hence, additional borohydride was essential for 1,2-DCA dechlorination. Washing the nCu0 particles improved their Cu0/Cun+ ratio (1.27) and 92% 1,2-DCA was removed in 7 h with kobs = 0.345 h-1 as compared to only 44% by unwashed nCu0 (0.158 h-1) with Cu0/Cun+ ratio of 0.59, in the presence of borohydride. The presence of chloride (1000-2000 mg L-1), sulfides (0.4-4 mg L-1), and HA (10-30 mg L-1) suppressed 1,2-DCA dechlorination; which was improved by additional borohydride probably via regeneration of Cu0 sites. Coating the particles decreased their catalytic dechlorination efficiency. 85-90% of the removed 1,2-DCA was recovered as chloride. Chloroethane and ethane were main dechlorination products indicating hydrogenolysis as the major pathway. Our results imply that synthesis parameters and groundwater solutes control nCu0 catalytic activity by altering its physico-chemical properties. Thus, these factors should be considered to develop an efficient remedial design for practical applications of nCu0-borohydride.

A fundamental model for calculating interfacial adsorption of complex ionic and nonionic PFAS mixtures in the presence of mixed salts.

Per- and polyfluoroalkyl substances (PFAS) are emerging contaminants that have been used extensively as firefighting agents and in a wide range of commercial applications around the world. As many of the most-common PFAS components are surfactants, they readily accumulate at interfaces, a process that can govern their environmental fate. There are thousands of PFAS compounds, and they have nearly always been used as mixtures, so it is common to find many different PFAS components present together in the environment. Furthermore, the interfacial behavior of ionic PFAS can be strongly influenced by the presence of salts, with adsorption dependent on both the composition and concentration of salts present. Any predictions of PFAS interfacial behavior made without considering both the mixed nature of PFAS present, as well as the composition of the salts present, have the potential to be off by orders of magnitude. To date, models capable of making predictions of PFAS interfacial adsorption when both mixed PFAS and mixed salts are present have not been presented. The work described here addresses this need by extending a mass-action model developed previously by the authors to allow predictions in cases where complex combinations of mixed PFAS and mixed salts are present. Predictions of PFAS interfacial affinity for a range of PFAS mixture conditions and ionic strengths are verified using experimentally-measured surface tension data. The new model provides physically-realistic prediction of interfacial adsorption of a wide range of PFAS mixtures over a wide range of salt concentrations and compositions. The model is capable of predicting interfacial adsorption of ionic/nonionic PFAS mixtures in the presence of salts, and can also make predictions when there is competitive adsorption between different PFAS components, a common case in PFAS source zones where high concentrations of multiple components are present and in foam fractionation reactors.

Calculating PFAS interfacial adsorption as a function of salt concentration using model parameters determined from chemical structure.

Per- and polyfluoroalkyl substances (PFAS) are widely-detected environmental contaminants known to concentrate at surfaces and interfaces. Many of the most commonly-detected PFAS function as ionic surfactants under environmental conditions. The interfacial behaviors of ionic surfactants, including PFAS, are strongly dependent on salt concentration and composition, with interfacial affinity potentially varying by orders of magnitude for the same compound under different conditions. The work described here presents a tool for predicting the salt-dependent adsorption of PFAS compounds based entirely on chemical structure, something of great value for predicting the real-world environmental behavior of many of the large numbers of PFAS compounds for which experimental data are not available. The approach combines two different previously-developed models, one a mass-action model designed to predict the effects of salts on interfacial adsorption of ionic PFAS (the UNSW-OU salt model), and the second a group-contribution model designed to predict interfacial adsorption of PFAS in the absence of salt based on chemical structure. The challenge of combining the two models comes from the fact that both are based on different isotherms. The salt model can produce sigmoidal isotherms under salt-limited conditions (an isotherm shape that is supported by experimental evidence), while the group-contribution model can generate Langmuir parameters from calculations based on chemical structure. Equations were derived to determine salt model isotherm parameters from Langmuir parameters (either from the group-contribution model or experimental sources) by matching surface tension curves in the vicinity of the concentration of highest second derivative. Refined group-contribution model parameters were determined based on data from an additional 40 surface tension curves to allow improved structure-based predictions for important classes of PFAS that were not sufficiently well-represented in the original model. The resulting equations provide a tool allowing quantitative predictions of PFAS behavior under realistic environmental conditions for compounds for which little or no experimental data are available.

Efficient Reductive Defluorination of Branched PFOS by Metal-Porphyrin Complexes.

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.

A new conceptual framework for the transformation of groundwater dissolved organic matter.

Groundwater comprises 95% of the liquid fresh water on Earth and contains a diverse mix of dissolved organic matter (DOM) molecules which play a significant role in the global carbon cycle. Currently, the storage times and degradation pathways of groundwater DOM are unclear, preventing an accurate estimate of groundwater carbon sources and sinks for global carbon budgets. Here we reveal the transformations of DOM in aging groundwater using ultra-high resolution mass spectrometry combined with radiocarbon dating. Long-term anoxia and a lack of photodegradation leads to the removal of oxidised DOM and a build-up of both reduced photodegradable formulae and aerobically biolabile formulae with a strong microbial signal. This contrasts with the degradation pathway of DOM in oxic marine, river, and lake systems. Our findings suggest that processes such as groundwater extraction and subterranean groundwater discharge to oceans could result in up to 13 Tg of highly photolabile and aerobically biolabile groundwater dissolved organic carbon released to surface environments per year, where it can be rapidly degraded. These findings highlight the importance of considering groundwater DOM in global carbon budgets.

Elucidating degradation mechanisms for a range of per- and polyfluoroalkyl substances (PFAS) via controlled irradiation studies.

Per- and polyfluoroalkyl substances (PFAS) are a challenging class of environmental pollutants due to a lack of available destructive remediation technologies. Understanding the fundamental mechanisms for degradation of PFAS is key for the development of field scalable and in-situ destructive based remediation technologies. This study aimed to elucidate and refine the current understanding of PFAS degradation mechanisms in water through a series of controlled gamma irradiation studies. Gamma irradiation of PFAS was performed using a cobalt-60 source in a batch irradiation up to 80 kGy at the Australian Nuclear Science and Technology Organisation. Perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), 6:2 fluorotelomer sulfonate (6:2 FTS), and a suite of thirteen different PFAS (including C4-C12 PFCAs, C4, C6, C8 PFSAs, and FOSA) were irradiated to investigate degradation, influence of pH, chain length, and transformation. High resolution mass spectrometry was used to identify more than 80 fluorinated transformation products throughout the degradation experiments. These included the -F/+H, -F/+OH, -F/CH2OH exchanged PFAS and n - 1 PFCA, amongst others. Given the reactive species present (hydroxyl radicals (·OH), hydrogen radicals (·H) and aqueous electrons (e-aq)), and the degradation products formed it was shown that aqueous electrons were the key reactive species responsible for initial PFAS degradation. Most importantly, based on degradation product formation, we found that the initial -F/+H does not have to occur at the α-fluoride (nearest the functional head group), rather occurring throughout the chain length leading to more complex degradation pathways than previously postulated. While our results support some of the reaction steps postulated in the literature, we have developed a unified 16 step and 3 pathway schematic of degradation supported by experimental observations.

Aerobic biotransformation of 6:2 fluorotelomer sulfonate by Dietzia aurantiaca J3 under sulfur-limiting conditions.

The polyfluorinated alkyl substance 6:2 fluorotelomer sulfonate (6:2 FTS) has been detected in diverse environments impacted by aqueous film-forming foams used for firefighting. In this study, a bacterial strain (J3) using 6:2 FTS as a sulfur source was isolated from landfill leachate previously exposed to polyfluoroalkyl substances in New South Wales, Australia. Strain J3 shares 99.9% similarity with the 16S rRNA gene of Dietzia aurantiaca CCUG 35676T. Genome sequencing yielded a draft genome sequence of 37 contigs with a G + C content of 69.7%. A gene cluster related to organic sulfur utilisation and assimilation was identified, that included an alkanesulfonate monooxygenase component B (ssuD), an alkanesulfonate permease protein (ssuC), an ABC transporter (ssuB), and an alkanesulfonate-binding protein (ssuA). Proteomic analyses comparing strain J3 cultures using sulfate and 6:2 FTS as sulfur source indicated that the ssu gene cluster was involved in 6:2 FTS biodegradation. Upregulated proteins included the SsuD monooxygenase, the SsuB transporter, the ABC transporter permease (SsuC), an alkanesulfonate-binding protein (SsuA), and a nitrilotriacetate monooxygenase component B. 6:2 Fluorotelomer carboxylic acid (6:2 FTCA) and 6:2 fluorotelomer unsaturated acid (6:2 FTUA) were detected as early degradation products in cultures (after 72 h) while 5:3 fluorotelomer acid (5:3 FTCA), perfluorohexanoic acid (PFHxA) and perfluoropentanoic acid (PFPeA) were detected as later degradation products (after 168 h). This work provides biochemical and metabolic insights into 6:2 FTS biodegradation by the Actinobacterium D. aurantiaca J3, informing the fate of PFAS in the environment.

Predicting the impact of salt mixtures on the air-water interfacial behavior of PFAS.

Salts are known to have strong impacts on environmental behavior of per- and polyfluoroalkyl substances (PFAS) including air-water interfacial adsorption. Multivalent salts impact interfacial adsorption to a greater extent than monovalent salts. Models to make a priori predictions of PFAS interfacial adsorption in the presence of multiple salts with different ionic charges are needed given the need to predict PFAS environmental fate. This study further develops a mass-action model to predict the interfacial behavior of PFAS as a function of both salt valency and concentration. The model is validated using surface tension data for a series of monovalent and divalent salt mixtures over a wide range of ionic strengths (i.e., from no added salt to 0.5 M) as well as comparison to data from literature. This model highlights the disproportionate impact of multivalent salts on interfacial adsorption and the practical utility of the model for predicting interfacial adsorption in the presence of multiple monovalent and multivalent inorganic salts. Results suggest that failure to account for divalent salt, even when concentrations are much smaller than monovalent salt, under most environmentally relevant aqueous phase conditions will result in significant underpredictions of PFAS interfacial adsorption. Simple examples of PFAS distribution in a range of salt conditions in the vadose zone and in aerated-water treatment reactors highlight the predictive utility of the model.

Silver nanomaterials released from commercial textiles have minimal impacts on soil microbial communities at environmentally relevant concentrations.

Silver nanomaterials (Ag NMs) have been used in a variety of commercial products to take advantage of their antimicrobial properties. However, there are concerns that these AgNMs can be released during/after use and enter wastewater streams, potentially impacting aquatic systems or accumulating in wastewater biosolids. Biosolids, which are a residual of wastewater treatment processes, have been found to contain AgNMs and are frequently used as agricultural fertilizer. Since the function of soil microbial communities is imperative to nutrient cycling and agricultural productivity, it is important to characterize and assess the effects that silver nanomaterials could have in agricultural soils. In this study agricultural soil was amended with pristine engineered (PVP-coated or uncoated AgNMs), aged silver (sulphidized or released from textiles) nanomaterials, and ionic silver to determine the fate and toxicity over the course of three months. Exposures were carried out at various environmentally relevant concentrations (1 and 10 mg Ag/kg soil) representing between 30 to over 800 years of equivalent biosolid loadings. Over thirteen different methodologies and measures were used throughout this study to assess for potential effects of the silver nanomaterials on soil, including microbial community composition, average well colour development (AWCD) and enzymatic activity. Overall, the AgNM exposures did not exhibit significant toxic effects to the soil microbial communities in terms of density, activity, function and diversity. However, the positive ionic silver treatment (100 mg Ag/kg soil) resulted in suppression to microbial activity while also resulting in significantly higher populations of Frankia alni (nitrogen-fixer) and Arenimonas malthae (phytopathogen) as compared to the negative control (p < 0.05, Tukey HSD) which warrants further investigation.

The role of microbial ecology in improving the performance of anaerobic digestion of sewage sludge.

The use of next-generation diagnostic tools to optimise the anaerobic digestion of municipal sewage sludge has the potential to increase renewable natural gas recovery, improve the reuse of biosolid fertilisers and help operators expand circular economies globally. This review aims to provide perspectives on the role of microbial ecology in improving digester performance in wastewater treatment plants, highlighting that a systems biology approach is fundamental for monitoring mesophilic anaerobic sewage sludge in continuously stirred reactor tanks. We further highlight the potential applications arising from investigations into sludge ecology. The principal limitation for improvements in methane recoveries or in process stability of anaerobic digestion, especially after pre-treatment or during co-digestion, are ecological knowledge gaps related to the front-end metabolism (hydrolysis and fermentation). Operational problems such as stable biological foaming are a key problem, for which ecological markers are a suitable approach. However, no biomarkers exist yet to assist in monitoring and management of clade-specific foaming potentials along with other risks, such as pollutants and pathogens. Fundamental ecological principles apply to anaerobic digestion, which presents opportunities to predict and manipulate reactor functions. The path ahead for mapping ecological markers on process endpoints and risk factors of anaerobic digestion will involve numerical ecology, an expanding field that employs metrics derived from alpha, beta, phylogenetic, taxonomic, and functional diversity, as well as from phenotypes or life strategies derived from genetic potentials. In contrast to addressing operational issues (as noted above), which are effectively addressed by whole population or individual biomarkers, broad improvement and optimisation of function will require enhancement of hydrolysis and acidogenic processes. This will require a discovery-based approach, which will involve integrative research involving the proteome and metabolome. This will utilise, but overcome current limitations of DNA-centric approaches, and likely have broad application outside the specific field of anaerobic digestion.

Factors controlling phosphorus mobility in nearshore aquifers adjacent to large lakes.

Internal P stores in offshore lakebed sediments play an important role in lake nutrient dynamics. While P stores in nearshore aquifer sediments may also be important for nutrient dynamics, it is unclear whether P accumulates in these sediments, and if so, what factors control P accumulation and its potential later release from the sediments to nearshore waters. This knowledge gap was addressed by conducting field investigations at seven nearshore sites located along the shores of Lake Erie, Lake Huron and Lake Ontario, Canada, with more detailed dissolved and sediment phase characterization completed for two nearshore sites. PO4 concentrations were observed to be higher (>50 µg/L) in the more reducing nearshore aquifers compared to more oxidizing nearshore aquifers (<20 µg/L), despite similar total solid phase P concentrations at the sites. PO4 mobility in the nearshore aquifers was found to be closely linked to redox-driven Fe cycling. In the more reducing aquifers, dissolved PO4 was highest near the redox boundary present in the shallow sediments where oxic infiltrating surface water mixes with reducing groundwater. In the more oxidizing aquifers, solid phase characterization indicated that PO4 is sequestered to Fe oxide mineral phases throughout the nearshore aquifer which explains the low dissolved PO4. While pH was not found to be important for PO4 mobility at the study sites, batch laboratory experiments indicate that increased infiltration of more alkaline surface water into nearshore aquifers may promote PO4 release from the sediments. The study findings demonstrate that while internal P storage mechanisms in nearshore aquifer sediments may currently be limiting P loads to lakes, it is possible that P stores that build up over time may result in increased P loads to lakes in the future.

A new framework for modeling the effect of salt on interfacial adsorption of PFAS in environmental systems.

Per- and polyfluoroalkyl substances (PFAS) are surface active contaminants of great environmental concern, due to their widespread historical use and their environmental persistence. Salts are known to have a profound influence on the interfacial behaviors of all ionic surfactants, including some of the most commonly detected PFAS. This work describes a new mass-action model for predicting the interfacial behavior of surfactants as a function of salt concentration. The three-parameter model is fit to interfacial tension data over a range of salt concentrations, and is then able to predict interfacial adsorption isotherms for the entire range from no added salt, up to 0.5 M added salt. The phenomenological nature of the model means that it is likely to provide more robust predictions for new systems and conditions than some of the existing empirical approaches, and the minimal number of adjustable parameters ensures that unique calibrations are possible with limited data. The model is found to be consistent with experimental data, and is bracketed by experimental values at low PFAS concentrations. Of particular interest, the model predicts the existence of sigmoidal adsorption isotherms at low salt concentrations, a deviation from isotherms calculated the commonly-used Szyszkowski equation; the observation is supported by a maximum in measured interfacial adsorption coefficient calculated from low-concentration surface tension measurements. Because adsorption affinities can vary by orders of magnitude with changing salt concentration, the ability to predict the effects of salt on adsorption is of critical importance for quantitative prediction of PFAS behavior in the environment.

Predicting the relationship between PFAS component signatures in water and non-water phases through mathematical transformation: Application to machine learning classification.

Per- and polyfluoroalkyl substances (PFAS) are widespread in the environment, as a result of decades of use across a range of applications. While PFAS contamination often enters the environment in the aqueous phase, PFAS is regularly detected in a range of different phases, including soils, sediments and biota. Although PFAS at a given site may originate from the same sources, the compositions observed in different phases are nearly always different, a fact that can complicate source allocation efforts. This paper presents a quantitative method for prediction of the relative composition of PFAS in different phases for components for which differences in behavior are primarily driven by hydrophobicity. The derived equations suggest that under these conditions, the relative compositions in different phases in contact with water should be independent of overall affinity for the phase, and as such should be the same for all non-water phases. This result is illustrated with data from individual samples, as well as from site-wide evaluations for a range of different phases. The results of the work provide a useful tool to reconcile PFAS composition differences in different phases, and provide a baseline for recognizing cases where hydrophobicity is not the primary driver of differences in distribution between phases. Furthermore, the results may be useful in forensic applications for classification of PFAS across different phases. The use of the resulting equations to transform water data to train a supervised learning algorithm for forensic analysis of PFAS in non-water phases is illustrated.

Recent Advances in Sulfidated Zerovalent Iron for Contaminant Transformation.

2021 marks 10 years since controlled abiotic synthesis of sulfidated nanoscale zerovalent iron (S-nZVI) for use in site remediation and water treatment emerged as an area of active research. It was then expanded to sulfidated microscale ZVI (S-mZVI) and together with S-nZVI, they are collectively referred to as S-(n)ZVI. Heightened interest in S-(n)ZVI stemmed from its significantly higher reactivity to chlorinated solvents and heavy metals. The extremely promising research outcomes during the initial period (2011-2017) led to renewed interest in (n)ZVI-based technologies for water treatment, with an explosion in new research in the last four years (2018-2021) that is building an understanding of the novel and complex role of iron sulfides in enhancing reactivity of (n)ZVI. Numerous studies have focused on exploring different S-(n)ZVI synthesis approaches, and its colloidal, surface, and reactivity (electrochemistry, contaminant selectivity, and corrosion) properties. This review provides a critical overview of the recent milestones in S-(n)ZVI technology development: (i) clear insights into the role of iron sulfides in contaminant transformation and long-term aging, (ii) impact of sulfidation methods and particle characteristics on reactivity, (iii) broader range of treatable contaminants, (iv) synthesis for complete decontamination, (v) ecotoxicity, and (vi) field implementation. In addition, this review discusses major knowledge gaps and future avenues for research opportunities.

Electrokinetically-enhanced emplacement of lactate in a chlorinated solvent contaminated clay site to promote bioremediation.

Bioremediation through the injection of electron donors and bacterial cultures is effective at treating chlorinated solvent contamination. However, it has had limited application in low permeability zones where amendments cannot be delivered successfully. This field-scale study investigated the application of electrokinetics to enhance the delivery of lactate at a clay site contaminated with chlorinated solvents. Groundwater and soil samples were collected before, during and for 1 year after the 71-day field test and analyzed for a wide suite of chemical and biological parameters. Lactate was successfully delivered to all monitoring locations. Lactate emplacement resulted in the stimulation of bacterial populations, specifically within the phylum Firmicutes, which contains fermenters and strict anaerobes. This likely led to biodegradation, as the field trial resulted in significant decreases in both soil and aqueous phase chlorinated solvent concentrations. Contaminant decreases were also partially attributable to dilution, given evidence of some advective lactate flux. This research provides evidence that electrokinetically-enhanced bioremediation has potential as a treatment strategy for contaminated low permeability strata.

Development and validation of a method for the weathering and detachment of representative nanomaterials from conventional silver-containing textiles.

Nanotoxicology research commonly utilizes pristine nanomaterials for toxicity assessment, which may not be perfectly representative of what is released into environmental systems. The goal of the present study was to develop a method to simulate human weathering of silver-containing textiles. To achieve this goal the roles of physical and chemical stress on X-Static® containing athletic textiles were investigated and compared to data collected from human weathering experiments and literature. Chemical weathering methods (artificial sweat) were used independently and alongside physical weathering methods (3D printed stretching and abrasion instruments). Non-weathered control textiles were found to release 29 ± 11 mg Ag/kg of textile into wash water effluent (ICP-MS), with 16% being released as ionic silver (ICP-MS) and the rest as metallic nanomaterials, nanosheets, and particulates of varying size (SEM/XANES). Real and simulated human weathered textiles released similar amounts of total silver (67 ± 11 mg Ag/kg, 84 ± 13 mg Ag/kg respectively) with the silver released being composed of ionic (1.5%, 2%) and a mixture of metallic and chlorinated nanomaterials, nanosheets, and particulates. The method was shown to effectively detach environmentally representative silver materials from silver-containing textiles and can provide such materials for future studies on the assessment of their fate, transport, and toxicity.

Occurrence of Arsenic in Nearshore Aquifers Adjacent to Large Inland Lakes.

Metal oxides that form near sediment-water interfaces in marine and riverine settings are known to act as a sediment trap for pollutants of environmental concern (e.g., arsenic and mercury). The occurrence of these pollutant traps near sediment-water interfaces in nearshore lake environments is unclear yet important to understand because they may accumulate pollutants that may be later released as environmental conditions change. This study evaluates the prevalence of pollutant sediment traps in nearshore aquifers adjacent to large lakes and the factors that affect the accumulation and release of pollutants, specifically arsenic. Field data from six sites along the Laurentian Great Lakes indicate widespread enrichment of arsenic in nearshore aquifers with arsenic sequestered to iron oxide phases. Arsenic enrichment at all sites (solid-phase arsenic >2 µg/g) suggests that this is a naturally occurring phenomenon. Arsenic was more mobile in reducing aquifers with elevated dissolved arsenic (up to 60 µg/L) observed, where reducing groundwater mixes with infiltrating oxic lake water. Dissolved arsenic was low (<3 µg/L) in all oxic nearshore aquifers studied despite high solid-phase arsenic concentrations. The findings have broad implications for understanding the widespread accumulation of reactive pollutants in nearshore aquifers and factors that affect their release to large lakes.