Fate of Dissolved Nitrogen in a Horizontal Levee: Seasonal Fluctuations in Nitrate Removal Processes.

Horizontal levees are a nature-based approach for removing nitrogen from municipal wastewater effluent while simultaneously providing additional benefits, such as flood control. To assess nitrogen removal mechanisms and the efficacy of a horizontal levee, we monitored an experimental system receiving nitrified municipal wastewater effluent for 2 years. Based on mass balances and microbial gene abundance data, we determined that much of the applied nitrogen was most likely removed by heterotrophic denitrifiers that consumed labile organic carbon from decaying plants and added wood chips. Fe(III) and sulfate reduction driven by decay of labile organic carbon also produced Fe(II) sulfide minerals. During winter months, when heterotrophic activity was lower, strong correlations between sulfate release and nitrogen removal suggested that autotrophic denitrifiers oxidized Fe(II) sulfides using nitrate as an electron acceptor. These trends were seasonal, with Fe(II) sulfide minerals formed during summer fueling denitrification during the subsequent winter. Overall, around 30% of gaseous nitrogen losses in the winter were attributable to autotrophic denitrifiers. To predict long-term nitrogen removal, we developed an electron-transfer model that accounted for the production and consumption of electron donors. The model indicated that the labile organic carbon released from wood chips may be capable of supporting nitrogen removal from wastewater effluent for several decades with sulfide minerals, decaying vegetation, and root exudates likely sustaining nitrogen removal over a longer timescale.

Rapid and Efficient Arsenic Removal by Iron Electrocoagulation Enabled with in Situ Generation of Hydrogen Peroxide.

Millions of people are exposed to toxic levels of dissolved arsenic in groundwater used for drinking. Iron electrocoagulation (FeEC) has been demonstrated as an effective technology to remove arsenic at an affordable price. However, FeEC requires long operating times (∼hours) to remove dissolved arsenic due to inherent kinetics limitations. Air cathode Assisted Iron Electrocoagulation (ACAIE) overcomes this limitation by cathodically generating H2O2 in situ. In ACAIE operation, rapid oxidation of Fe(II) and complete oxidation and removal of As(III) are achieved. We compare FeEC and ACAIE for removing As(III) from an initial concentration of 1464 µg/L, aiming for a final concentration of less than 4 µg/L. We demonstrate that at short electrolysis times (0.5 min), i.e., high charge dosage rates (1200 C/L/min), ACAIE consistently outperformed FeEC in bringing arsenic levels to less than WHO-MCL of 10 µg/L. Using XRD and XAS data, we conclusively show that poor arsenic removal in FeEC arises from incomplete As(III) oxidation, ineffective Fe(II) oxidation and the formation of Fe(II-III) (hydr)oxides at short electrolysis times (<20 min). Finally, we report successful ACAIE performance (retention time 19 s) in removing dissolved arsenic from contaminated groundwater in rural California.

Long-term electrode behavior during treatment of arsenic contaminated groundwater by a pilot-scale iron electrocoagulation system.

Iron electrocoagulation (Fe-EC) is an effective technology to remove arsenic (As) from groundwater used for drinking. A commonly noted limitation of Fe-EC is fouling or passivation of electrode surfaces via rust accumulation over long-term use. In this study, we examined the effect of removing electrode surface layers on the performance of a large-scale (10,000 L/d capacity) Fe-EC plant in West Bengal, India. We also characterized the layers formed on the electrodes in active use for over 2 years at this plant. The electrode surfaces developed three distinct horizontal sections of layers that consisted of different minerals: calcite, Fe(III) precipitates and magnetite near the top, magnetite in the middle, and Fe(III) precipitates and magnetite near the bottom. The interior of all surface layers adjacent to the Fe(0) metal was dominated by magnetite. We determined the impact of surface layer removal by mechanical abrasion on Fe-EC performance by measuring solution composition (As, Fe, P, Si, Mn, Ca, pH, DO) and electrochemical parameters (total cell voltage and electrode interface potentials) during electrolysis. After electrode cleaning, the Fe concentration in the bulk solution increased substantially from 15.2 to 41.5 mg/L. This higher Fe concentration led to increased removal of a number of solutes. For As, the concentration reached below the 10 µg/L WHO MCL more rapidly and with less total Fe consumed (i.e. less electrical energy) after cleaning (128.4 µg/L As removed per kWh) compared to before cleaning (72.9 µg/L As removed per kWh). Similarly, the removal of P and Si improved after cleaning by 0.3 mg/L/kWh and 1.1 mg/L/kWh, respectively. Our results show that mechanically removing the surface layers that accumulate on electrodes over extended periods of Fe-EC operation can restore Fe-EC system efficiency (concentration of solute removed/kWh delivered). Since Fe release into the bulk solution substantially increased upon electrode cleaning, our results also suggest that routine electrode maintenance can ensure robust and reliable Fe-EC performance over year-long timescales.

Corrosion of carbon steel and the passivating properties of corrosion films formed under high-PT geothermal conditions.

Corrosion is a major obstacle to a safe implementation of geotechnical applications. Using a novel approach that includes vertical scanning interferometry (VSI) and electrochemical impedance spectroscopy (EIS) we discuss time-dependent carbon steel corrosion and film formation at geothermally relevant temperatures (80-160 °C) in CO2-saturated mildly acidic NaCl brine. Iron dissolution kinetics follows a logarithmic rate at 80 and 160 °C and a linear rate at 120 °C. At 80 °C, high initial corrosion rates (first 24 h) generate H2 at a minimum rate of 12 µmol h-1 cm-2 and lead to the formation of a continuous ~100 µm thick porous corrosion film. It exhibits a duplex structure with a crystalline outer FeCO3 layer and an inner layer composed of a skeletal network of Fe3C impregnated with FeCO3. Being an electrical conductor we hypothesize the Fe3C to strongly enhance corrosion rates by providing additional cathodic sites. Pseudo-passivity due to an anodic film-forming reaction (presumably Fe-oxide) was observed at 120 and 160 °C, soon followed by the initiation of pitting at 120 °C. Steady-state corrosion rates at 160 °C are at least one order of magnitude lower than for 120 °C. Our experimental approach demonstrated potential for general applicability in studying corrosion-related phenomena.

Formation of macroscopic surface layers on Fe(0) electrocoagulation electrodes during an extended field trial of arsenic treatment.

Extended field trials to remove arsenic (As) via Fe(0) electrocoagulation (EC) have demonstrated consistent As removal from groundwater to concentrations below 10 µg L(-1). However, the coulombic performance of long-term EC field operation is lower than that of laboratory-based systems. Although EC electrodes used over prolonged periods show distinct passivation layers, which have been linked to decreased treatment efficiency, the spatial distribution and mineralogy of such surface layers have not been investigated. In this work, we combine wet chemical measurements with sub-micron-scale chemical maps and selected area electron diffraction (SAED) to determine the chemical composition and mineral phase of surface layers formed during long-term Fe(0) EC treatment. We analyzed Fe(0) EC electrodes used for 3.5 months of daily treatment of As-contaminated groundwater in rural West Bengal, India. We found that the several mm thick layer that formed on cathodes and anodes consisted of primarily magnetite, with minor fractions of goethite. Spatially-resolved SAED patterns also revealed small quantities of CaCO3, Mn oxides, and SiO2, the source of which was the groundwater electrolyte. We propose that the formation of the surface layer contributes to decreased treatment performance by preventing the migration of EC-generated Fe(II) to the bulk electrolyte, where As removal occurs. The trapped Fe(II) subsequently increases the surface layer size at the expense of treatment efficiency. Based on these findings, we discuss several simple and affordable methods to prevent the efficiency loss due to the surface layer, including alternating polarity cycles and cleaning the Fe(0) surface mechanically or via electrolyte scouring.

Electro-chemical arsenic remediation: field trials in West Bengal.

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.