We apply Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy and pair distribution function (PDF) analysis of high-energy X-ray scattering to investigate the effects of bivalent cation-oxyanion pairs on the structure of Fe(III) precipitates formed from the oxidation of Fe(II) generated by the electrolytic dissolution of Fe(0) electrodes. We found that Fe(II) oxidation in the presence of weakly adsorbing electrolytes (NaCl, CaCl2, MgCl2) leads to pseudo-lepidocrocite (Lp; γ-FeOOH), a poorly crystalline version of Lp with low sheet-stacking coherence. In the absence of bivalent cations, P and As(V) have similar uptake behavior, but different effects on the average Fe(III) precipitate structure: pseudo-Lp dominates in the presence of P, whereas a disordered ferrihydrite-like precipitate akin to hydrous ferric oxide (HFO) is the dominant phase that forms in the presence of As(V). Despite its lower affinity for Fe(III) precipitates, Si leads to Si-HFO in all conditions tested. The presence of 1mM Ca2+ or Mg2+ enhances oxyanion uptake, destabilizes the colloidally stable oxyanion-bearing particle suspensions and, in some P and As(V) electrolytes, results in more crystalline precipitates. The trends in oxyanion uptake and Fe(III) precipitate structure in the presence of Ca2+/Mg2+ suggest a systematic decrease in the strength of bivalent cation:oxyanion interaction in the order of Ca2+>Mg2+ and P>As(V)≫Si. Using the PDF technique, we identify the polyhedral linkages that contribute to the intermediate structures (>6Å) of disordered, nanoscale oxyanion-bearing Fe(III) precipitate samples. Our results suggest that oxyanions present during Fe(III) polymerization bind to corner-sharing Fe surface sites leading to a precipitate surface deficient in corner-sharing Fe, whereas the edge- and corner-sharing Fe sites in the precipitate core likely remain intact. © 2013 Elsevier Ltd.

Iron electrocoagulation (Fe-EC) is a low-cost process in which Fe(II) generated from an Fe(0) anode reacts with dissolved O2 to form (1) Fe(III) precipitates with an affinity for bacterial cell walls and (2) bactericidal reactive oxidants. Previous work suggests that Fe-EC is a promising treatment option for groundwater containing arsenic and bacterial contamination. However, the mechanisms of bacteria attenuation and the impact of major groundwater ions are not well understood. In this work, using the model indicator Escherichia coli (E. coli), we show that physical removal via enmeshment in EC precipitate flocs is the primary process of bacteria attenuation in the presence of HCO3(-), which significantly inhibits inactivation, possibly due to a reduction in the lifetime of reactive oxidants. We demonstrate that the adhesion of EC precipitates to cell walls, which results in bacteria encapsulation in flocs, is driven primarily by interactions between EC precipitates and phosphate functional groups on bacteria surfaces. In single solute electrolytes, both P (0.4 mM) and Ca/Mg (1-13 mM) inhibited the adhesion of EC precipitates to bacterial cell walls, whereas Si (0.4 mM) and ionic strength (2-200 mM) did not impact E. coli attenuation. Interestingly, P (0.4 mM) did not affect E. coli attenuation in electrolytes containing Ca/Mg, consistent with bivalent cation bridging between bacterial phosphate groups and inorganic P sorbed to EC precipitates. Finally, we found that EC precipitate adhesion is largely independent of cell wall composition, consistent with comparable densities of phosphate functional groups on Gram-positive and Gram-negative cells. Our results are critical to predict the performance of Fe-EC to eliminate bacterial contaminants from waters with diverse chemical compositions.

Technologies addressing both arsenic and microbial contamination of Bengal groundwater are needed. Fe electrocoagulation (Fe-EC), a simple process relying on the dissolution of an Fe(0) anode to produce Fe(III) precipitates, has been shown to efficiently remove arsenic from groundwater at low cost. We investigated Escherichia coli (E. coli) attenuation by Fe-EC in synthetic Bengal groundwater as a function of Fe dosage rate, total Fe dosed, pH, and presence of natural organic matter (NOM). A 2.5 mM Fe dosage simultaneously achieved over 4-log E. coli attenuation and arsenic removal from 450 to below 10 μg/L. E. coli reduction was significantly enhanced at pH 6.6 compared to pH 7.5, which we linked to the decreased rate of Fe(II) oxidation at lower pH. 3 mg/L-C of NOM (Suwanee River fulvic acid) did not significantly affect E. coli attenuation. Live-dead staining and comparisons of Fe-EC with chemical coagulation controls showed that the primary mechanism of E. coli attenuation is physical removal with Fe(III) precipitates, with inactivation likely contributing as well at lower pH. Transmission electron microscopy showed that EC precipitates adhere to and bridge individual E. coli cells, resulting in large bacteria-Fe aggregates that can be removed by gravitational settling. Our results point to the promising ability of Fe-EC to treat arsenic and bacterial contamination simultaneously at low cost.

Mixed-valent iron nanoparticles (NP) generated electrochemically by Fe(0) electrocoagulation (EC) show promise for on-demand industrial and drinking water treatment in engineered systems. This work applies multiple characterization techniques (in situ Raman spectroscopy, XRD, SEM, and cryo-TEM) to investigate the formation and persistence of magnetite and green rust (GR) NP phases produced via the Fe(0) EC process. Current density and background electrolyte composition were examined in a controlled anaerobic system to determine the initial Fe phases generated as well as transformation products with aging. Fe phases were characterized in an aerobic EC system with both simple model electrolytes and real groundwater to investigate the formation and aging of Fe phases produced in a system representing treatment of arsenic-contaminated ground waters in South Asia. Two central pathways for magnetite production via Fe(0) EC were identified: (i) as a primary product (formation within seconds when DO absent, no intermediates detected) and (ii) as a transformation product of GR (from minutes to days depending on pH, electrolyte composition, and aging conditions). This study provides a better understanding of the formation conditions of magnetite, GR, and ferric (oxyhydr)oxides in Fe EC, which is essential for process optimization for varying source waters.

Millions of people in rural South Asia are exposed to high levels of arsenic through groundwater used for drinking. Many deployed arsenic remediation technologies quickly fail because they are not maintained, repaired, accepted, or affordable. It is therefore imperative that arsenic remediation technologies be evaluated for their ability to perform within a sustainable and scalable business model that addresses these challenges. We present field trial results of a 600 L Electro-Chemical Arsenic Remediation (ECAR) reactor operating over 3.5 months in West Bengal. These results are evaluated through the lens of a community scale micro-utility business model as a potential sustainable and scalable safe water solution for rural communities in South Asia. We demonstrate ECAR's ability to consistently reduce arsenic concentrations of ~266 μg/L to <5 μg/L in real groundwater, simultaneously meeting the international standards for iron and aluminum in drinking water. ECAR operating costs (amortized capital plus consumables) are estimated as $0.83-$1.04/m(3) under realistic conditions. We discuss the implications of these results against the constraints of a sustainable and scalable business model to argue that ECAR is a promising technology to help provide a clean water solution in arsenic-affected areas of South Asia.

Preservatives deter microbial growth, providing crucial functions of safety and durability in composite materials, formulated products, and food packaging. Concern for human health and the environmental impact of some preservatives has led to regulatory restrictions and public pressure to remove individual classes of compounds, such as parabens and chromated copper arsenate, from consumer products. Bans do not address the need for safe, effective alternative preservatives, which are critical for both product performance (including lifespan and therefore life cycle metrics) and consumer safety. In this work, we studied both the safety and efficacy of a series of phenolic preservatives and compared them to common preservatives found in personal care products and building materials. We quantified antimicrobial activity against Aspergillus brasiliensis (mold) and Pseudomonas aeruginosa (Gram negative bacteria), and we conducted a hazard assessment, complemented by computational modeling, to evaluate the human and environmental health impacts of these chemicals. We found that octyl gallate demonstrates better antimicrobial activity and comparable or lower hazards, compared to current-use preservatives. Therefore, octyl gallate may serve as a viable small-molecule preservative, particularly in conjunction with low concentrations of other preservatives that act through complementary mechanisms.