Electrochemical degradation of PFOA and its common alternatives: Assessment of key parameters, roles of active species, and transformation pathway.

This study investigates an electrochemical approach for the treatment of water polluted with per- and poly-fluoroalkyl substances (PFAS), looking at the impact of different variables, contributions from generated radicals, and degradability of different structures of PFAS. Results obtained from a central composite design (CCD) showed the importance of mass transfer, related to the stirring speed, and the amount of charge passed through the electrodes, related to the current density on decomposition rate of PFOA. The CCD informed optimized operating conditions which we then used to study the impact of solution conditions. Acidic condition, high temperature, and low initial concentration of PFOA accelerated the degradation kinetic, while DO had a negligible effect. The impact of electrolyte concentration depended on the initial concentration of PFOA. At low initial PFOA dosage (0.2 mg L-1), the rate constant increased considerably from 0.079 ± 0.001 to 0.259 ± 0.019 min-1 when sulfate increased from 0.1% to 10%, likely due to the production of SO4•-. However, at higher initial PFOA dosage (20 mg L-1), the rate constant decreased slightly from 0.019 ± 0.001 to 0.015 ± 0.000 min-1, possibly due to the occupation of active anode sites by excess amount of sulfate. SO4•- and •OH played important roles in decomposition and defluorination of PFOA, respectively. PFOA oxidation was initiated by one electron transfer to the anode or SO4•-, undergoing Kolbe decarboxylation where yielded perfluoroalkyl radical followed three reaction pathways with •OH, O2 and/or H2O. PFAS electrooxidation depended on the chemical structures where the decomposition rate constants (min-1) were in the order of 6:2 FTCA (0.031) > PFOA (0.019) > GenX (0.013) > PFBA (0.008). PFBA with a shorter chain length and GenX with -CF3 branching had slower decomposition than PFOA. While presence of C-H bonds makes 6:2 FTCA susceptible to the attack of •OH accelerating its decomposition kinetic. Conducting experiments in mixed solution of all studied PFAS and in natural water showed that the co-presence of PFAS and other water constituents (organic and inorganic matters) had adverse effects on PFAS decomposition efficiency.

In Vivo Polymerization ("Hard-Wiring") of Bioanodes Enables Rapid Start-Up and Order-of-Magnitude Higher Power Density in a Microbial Battery.

For microbial electrochemical technologies to be successful in the decentralized treatment of wastewater, steady-state power density must be improved and cost must be decreased. Here, we demonstrate in vivo polymerization ("hard-wiring") of a microbial community to a growing layer of conductive polypyrrole on a sponge bioanode of a microbial battery, showing rapid biocatalytic current development (∼10 times higher than a sponge control after 4 h). Moreover, bioanodes with the polymerized inoculant maintain higher steady-state power density (∼2 times greater than the control after 28 days). We then evaluate the same hard-wired bioanodes in both a two-chamber microbial fuel cell and microbial battery with a solid-state NaFeIIFeIII(CN)6 (Prussian Blue) cathode, showing approximately an order-of-magnitude greater volumetric power density with the microbial battery. The result is a rapid start-up, low-cost (no membrane or platinum catalyst), and high volumetric power density system (independent of atmospheric oxygen) for harvesting energy and carbon from dilute organics in wastewater.

Charge-Free Mixing Entropy Battery Enabled by Low-Cost Electrode Materials.

Salinity gradients are a vast and untapped energy resource. For every cubic meter of freshwater that mixes with seawater, approximately 0.65 kW h of theoretically recoverable energy is lost. For coastal wastewater treatment plants that discharge to the ocean, this energy, if recovered, could power the plant. The mixing entropy battery (MEB) uses battery electrodes to convert salinity gradient energy into electricity in a four-step process: (1) freshwater exchange; (2) charging in freshwater; (3) seawater exchange; and (4) discharging in seawater. Previously, we demonstrated a proof of concept, but with electrode materials that required an energy investment during the charging step. Here, we introduce a charge-free MEB with low-cost electrodes: Prussian Blue (PB) and polypyrrole (PPy). Importantly, this MEB requires no energy investment, and the electrode materials are stable with repeated cycling. The MEB equipped with PB and PPy achieved high voltage ratios (actual voltages obtained divided by the theoretical voltages) of 89.5% in wastewater effluent and 97.6% in seawater, with over 93% capacity retention after 50 cycles of operation and 97-99% over 150 cycles with a polyvinyl alcohol/sulfosuccinic acid (PVA/SSA) coating on the PB electrode.

Production and transformation of mixed-valent nanoparticles generated by Fe(0) electrocoagulation.

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.

In-situ identification of iron electrocoagulation speciation and application for natural organic matter (NOM) removal.

In this work, iron speciation in electrocoagulation (EC) was studied to determine the impact of operating parameters on natural organic matter (NOM) removal from natural water. Two electrochemical EC parameters, current density (i) and charge loading rate (CLR), were investigated. Variation of these parameters led to a near unity current efficiency (φ = 0.957 ± 0.03), at any combination of i in a range of 1-25 mA/cm(2) and CLR in a range of 12-300 C/L/min. Higher i and CLR led to a higher bulk pH and limited the amount of dissolved oxygen (DO) reduced at the cathode surface due to mass transfer limitations. A low i (1 mA/cm(2)) and intermediate CLR (60 C/L/min) resulted in low bulk DO (<2.5 mg/L), where green rust (GR) was identified by in-situ Raman spectroscopy as the primary crystalline electrochemical product. Longer electrolysis times at higher i led to magnetite (Fe3O4) formation. Both higher (300 C/L/min) and lower (12 C/L/min) CLR values led to increased DO and/or increased pH, with lepidocrocite (γ-FeOOH) as the only crystalline species observed. The NOM removal of the three identified species was compared, with conditions leading to GR formation showing the greatest dissolved organic carbon removal, and highest removal of the low apparent molecular weight (<550 Da) chromophoric NOM fraction, determined by high performance size exclusion chromatography.

Standardizing electrocoagulation reactor design: iron electrodes for NOM removal.

A novel systematic approach for reactor design was described for iron electrocoagulation (EC) and applied to drinking water treatment. Suwannee NOM was used as a model compound; performance was quantified by UV-abs-254 and DOC removal. Significant EC design variables were identified and examined: current density (i) (2.43-26.8 mA cm(-2)), coagulant or charge loading rate (CLR) (100-1000 CL(-1) min(-1)), and flocculation methodology ("fast" and "slow"). A correlation was found between increased i and decreased current efficiency (φ), optimum NOM removal was found at i ~10 mA cm(-2). A lower CLR showed greater total DOC removal, while a higher CLR led to less reactor residence time and required either longer flocculation times or greater coagulant dose for similar NOM removal. This paper defines and describes the four general EC "classes" of operation that have implications on several important measures of success: coagulant dose, electrical consumption, process speed, volumetric footprint, and post-EC flocculation requirements. Two classes were further examined with or without pH adjustment for DOC removal, showing that a "fast" EC mode without flocculation is more appropriate for smaller applications, while a "slow" EC mode is more effective for large permanent applications, where flocculation and settling can reduce coagulant and electrical consumption. The effect of pH adjustment showed greater impact with the "fast" dosing mode than with the "slow" mode, adjustment to pH 6 with the "fast" mode gave 13.8% and 29.1% greater DOC and UV-abs-254 removal, respectively, compared to the baseline without pH adjustment.

Metal type and natural organic matter source for direct filtration electrocoagulation of drinking water.

Electrocoagulation (EC) was combined with immediate microfiltration as direct filtration electrocoagulation (DFEC) for dissolved organic carbon (DOC) removal in drinking water from synthetic and natural highly natural organic matter (NOM) impacted waters from three different sources: Suwannee River (Georgia, USA DOC(0)=13.79 mg/L), Nordic Reservoir (Vallsjøen, Norway DOC(0)=9.03 mg/L), and a natural source (Lost Lagoon, Vancouver, Canada DOC(0)=13.31 mg/L). Three anode materials were investigated: iron, aluminum, and zinc, in a batch EC process without rapid mixing, flocculation, or settling. Fifteen seconds of process time with the iron electrode (36 mg Fe/L) led to DOC removal of 44%. After 1 min of process time, DOC reduction was 65% (zinc)-73 (iron)%, with ~ 85% reduction (all metals) in UV-abs-254 (UV-abs-254 final=0.06 cm(-1)) for Suwannee NOM. Specific UV absorbance (SUVA-L/mgm) values decreased from 3.1 to 4.2 to under 2.0, indicating removal of high MW fractions of NOM. High performance size exclusion chromatography (HPSEC) fractionation supported SUVA results, showing reductions from 76% of DOC>1450 Da to approximately 40% after EC for all metals and Suwannee NOM. EC performed equally well for two different initial DOC concentrations of 13.79 and 21.59 mg/L DOC, showing 75% DOC and 89% UV-abs-254 reductions.