Deep-dive into iron-based co-precipitation of arsenic: A review of mechanisms derived from synchrotron techniques and implications for groundwater treatment.

The co-precipitation of Fe(III) (oxyhydr)oxides with arsenic (As) is one of the most widespread approaches to treat As-contaminated groundwater in both low- and high-income settings. Fe-based co-precipitation of As occurs in a variety of conventional and decentralized treatment schemes, including aeration and sand filtration, ferric chloride addition and technologies based on controlled corrosion of Fe(0) (i.e., electrocoagulation). Despite its ease of deployment, Fe-based co-precipitation of As entails a complex series of chemical reactions that often occur simultaneously, including electron-transfer reactions, mineral nucleation, crystal growth, and As sorption. In recent years, the growing use of sophisticated synchrotron-based characterization techniques in water treatment research has generated new detailed and mechanistic insights into the reactions that govern As removal efficiency. The purpose of this critical review is to synthesize the current understanding of the molecular-scale reaction pathways of As co-precipitation with Fe(III), where the source of Fe(III) can be ferric chloride solutions or oxidized Fe(II) sourced from natural Fe(II) in groundwater, ferrous salts or controlled Fe(0) corrosion. We draw primarily on the mechanistic knowledge gained from spectroscopic and nano-scale investigations. We begin by describing the least complex reactions relevant in these conditions (Fe(II) oxidation, Fe(III) polymerization, As sorption in single-solute systems) and build to multi-solute systems containing common groundwater ions that can alter the pathways of As uptake during Fe(III) co-precipitation (Ca, Mg bivalent cations; P, Si oxyanions). We conclude the review by providing a perspective on critical knowledge gaps remaining in this field and new research directions that can further improve the understanding of As removal via Fe(III) co-precipitation.

Heavy metal removal potential of olivine.

Industrial wastewater containing heavy metals, such as Cd and Pb, must be treated prior to discharge to meet increasingly stringent discharge guidelines and to limit the impact of toxic metals on ecosystems and human health. The application of olivine particles is a natural mineral-based solution to treat heavy metal-laden wastewaters, but little is known about the efficiency and mechanism of metal removal by this solid phase. In this work, we investigate the potential of olivine for heavy metal treatment by combining batch metal removal experiments with solid-phase characterization by synchrotron-based X-ray techniques and electron microscopy. We probed the removal behaviour of a variety of metal contaminants (Co, Ni, Cd, Zn, Cu, Pb; initial concentration = 1500 µg/L) and used Zn specifically to identify the metal removal pathway of olivine. We found that olivine in powdered (0.3 g/L) and granulated (0.5 g/L) forms was able to remove up to >90% of the initial metal, depending on the metal identity, with the efficiency increasing in order of Co ≤ Cd ≤ Ni

Molecular-scale characterization of groundwater treatment sludge from around the world: Implications for potential arsenic recovery.

Iron (Fe)-based treatment methods are widely applied to remove carcinogenic arsenic (As) from drinking water, but generate toxic As-laden Fe (oxyhydr)oxide waste that has traditionally been ignored for resource recovery by the water sector. However, the European Commission recently classified As as a Critical Raw Material (CRM), thus providing new incentives to re-think As-laden groundwater treatment sludge. Before As recovery techniques can be developed for groundwater treatment waste, detailed information on its structure and composition is essential. To this end, we comprehensively characterized sludge generated from a variety of As-rich groundwater treatment plants in different geographic regions by combining a suite of macroscopic measurements, such as total digestions, leaching tests and BET surface area with molecular-scale solid-phase analysis by Fe and As K-edge X-ray absorption spectroscopy (XAS). We found that the As mass fraction of all samples ranged from ∼200-1200 mg As/kg (dry weight) and the phosphorous (P) content reached ∼0.5-2 mass%. Notably, our results indicated that the influent As level was a poor predictor of the As sludge content, with the highest As mass fractions (940-1200 mg As/kg) measured in sludge generated from treating low groundwater As levels (1.1-22 µg/L). The Fe K-edge XAS data revealed that all samples consisted of nanoscale Fe(III) precipitates with less structural order than ferrihydrite, which is consistent with their high BET surface area (up to >250 m2/g) and large As and P mass fractions. The As K-edge XAS data indicated As was present in all samples predominantly as As(V) bound to Fe(III) precipitates in the binuclear-corner sharing (2C) geometry. Overall, the similar structure and composition of all samples implies that As recovery methods optimized for one type of Fe-based treatment sludge can be applied to many groundwater treatment sludges. Our work provides a critical foundation for further research to develop resource recovery methods for As-rich waste.

LCA of Disposal Practices for Arsenic-Bearing Iron Oxides Reveals the Need for Advanced Arsenic Recovery.

Iron (Fe)-based groundwater treatment removes carcinogenic arsenic (As) effectively but generates toxic As-rich Fe oxide water treatment residuals (As WTRs) that must be managed appropriately to prevent environmental contamination. In this study, we apply life cycle assessment (LCA) to compare the toxicity impacts of four common As WTR disposal strategies that have different infrastructure requirements and waste control: (i) landfilling, (ii) brick stabilization, (iii) mixture with organic waste, and (iv) open disposal. The As disposal toxicity impacts (functional unit = 1.0 kg As) are compared and benchmarked against impacts of current methods to produce marketable As compounds via As mining and concentrate processing. Landfilling had the lowest non-carcinogen toxicity (2.0 × 10-3 CTUh), carcinogen toxicity (3.8 × 10-5 CTUh), and ecotoxicity (4.6 × 103 CTUe) impacts of the four disposal strategies, with the largest toxicity source being As emission via sewer discharge of treated landfill leachate. Although landfilling had the lowest toxicity impacts, the stored toxicity of this strategy was substantial (ratio of stored toxicity/emitted As = 13), suggesting that landfill disposal simply converts direct As emissions to an impending As toxicity problem for future generations. The remaining disposal strategies, which are frequently practiced in low-income rural As-affected areas, performed poorly. These strategies yielded ∼3-10 times greater human toxicity and ecotoxicity impacts than landfilling. The significant drawbacks of each disposal strategy indicated by the LCA highlight the urgent need for new methods to recover As from WTRs and convert it into valuable As compounds. Such advanced As recovery technologies, which have not been documented previously, would decrease the stored As toxicity and As emissions from both WTR disposal and from mining As ore.

Achieving arsenic concentrations of <1 µg/L by Fe(0) electrolysis: The exceptional performance of magnetite.

Consumption of drinking water containing arsenic at concentrations even below the World Health Organization provisional limit of 10 µg/L can still lead to unacceptable health risks. Consequently, the drinking water sector in the Netherlands has recently agreed to target 1 µg/L of arsenic in treated water. Unfortunately, in many poor, arsenic-affected countries, the costs and complexity of current methods that can achieve <1 µg/L are prohibitive, which highlights the need for innovative methods that can remove arsenic to <1 µg/L without costly support infrastructure and complicated supply chains. In this work, we used Fe(0) electrolysis, a low cost and scalable technology that is also known as Fe(0) electrocoagulation (EC), to achieve <1 µg/L residual dissolved arsenic. We compared the arsenic removal performance of green rust (GR), ferric (oxyhydr)oxides (Fe(III) oxides) and magnetite (Mag) generated by EC at different pH (7.5 and 9) in the presence of As(III) or As(V) (initial concentrations of 200-11,000 µg/L). Although GR and Fe(III) oxides removed up to 99% of initial arsenic, neither Fe phase could reliably meet the 1 µg/L target at both pH values. In contrast, EC-generated Mag consistently achieved <1 µg/L, regardless of the initial As(V) concentration and pH. Only solutions with initial As(III) concentrations ≥2200 µg/L resulted in residual arsenic >1 µg/L. As K-edge X-ray absorption spectroscopy showed that Mag also sorbed arsenic in a unique mode, consistent with partial arsenic incorporation near the particle surface. This sorption mode contrasts with the binuclear, corner sharing surface complex for GR and Fe(III) oxides, which could explain the difference in arsenic removal efficiency among the three Fe phases. Our results suggest that EC-generated Mag is an attractive method for achieving <1 µg/L particularly in decentralized water treatment.

Emerging investigator series: interdependency of green rust transformation and the partitioning and binding mode of arsenic.

We investigated the impact of aging-induced structural modifications of carbonate green rust (GR), a mixed valent Fe(ii,iii) (hydr)oxide with a high oxyanion sorption affinity, on the partitioning and binding mode of arsenic (As). Suspensions of carbonate GR were produced in the presence of As(v) or As(iii) (i.e. co-precipitated with As(iii) or As(v)) and aged in anoxic and oxic conditions for up to a year. We tracked aqueous As over time and characterized the solid phase by X-ray absorption spectroscopy (XAS). In experiments with initial As(v) (4500 µg L-1, As/Fe = 2 mol%), the fresh GR suspension sorbed >99% of the initial As, resulting in approximately 14 ± 8 µg L-1 residual dissolved As. Anoxic aging of the As(v)-laden GR for a month increased aqueous As to >60 µg L-1, which was coupled to an increase in GR structural order revealed by Fe K-edge XAS. Further anoxic aging up to a year transformed As(v)-laden GR into magnetite and decreased significantly the aqueous As to <2 µg L-1. The As binding mode was also modified during GR transformation to magnetite from sorption to GR particle edges to As substitution for tetrahedral Fe in the magnetite structure. These GR structural modifications altered the ratio of As partitioning to the solid (µg As/mg Fe) and liquid (µg As per L) phase from 2.0 to 0.4 to 14 L mg-1 for the fresh, month, and year aged suspensions, respectively. Similar trends in GR transformation and As partitioning during anoxic aging were observed for As(iii)-laden suspensions, but occurred on more rapid timescales: As(iii)-laden GR transformed to magnetite after a day of anoxic aging. In oxic aging experiments, rapid GR oxidation by dissolved oxygen to Fe(iii) precipitates required only an hour for both As(v) and As(iii) experiments, with lepidocrocite favored in As(v) experiments and hydrous ferric oxide favored in As(iii) experiments. Aqueous As during GR oxidation decreased to <10 µg L-1 for both As(v) and As(iii) series. Knowledge of this interdependence between GR aging products and oxyanion fate improves biogeochemical models of contaminant and nutrient dynamics during Fe cycling and can be used to design more effective arsenic remediation strategies that rely on arsenic sorption to GR.