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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.

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