Impact of pH on Iron Redox Transformations in Simulated Freshwaters Containing Natural Organic Matter

The impact of the pH of natural waters on the various pathways contributing to the formation and decay of Fe(II) in the presence of Suwannee River Fulvic Acid (SRFA) is investigated in this study. Our results show that thermal Fe(III) reduction occurs as a result of the presence of hydroquinone-like moieties in SRFA with the rate of Fe(III) reduction by these entities relatively invariant with change in pH in the range 6.8-8.7. The Fe(II) oxidation rate in the dark is controlled by its interaction with O₂ and increases with increase in pH with the overall outcome that the steady-state Fe(II) concentration in the dark is strongly affected by solution pH. On irradiation, a portion of the hydroquinone-like moieties present are oxidized to form semiquinones that are capable of reducing Fe(III) and/or oxidizing Fe(II) under circumneutral pH conditions. The extent of photogeneration of semiquinones on irradiation of SRFA and the persistence of these radicals increases significantly with decrease in pH. Due to the higher concentration and longevity of these organic moieties under low pH conditions, the impact of pH on steady-state Fe(II) concentration is less pronounced in previously irradiated SRFA solution compared to that observed in dark SRFA solution. Under irradiated conditions, the rates of Fe transformation (including both Fe(II) oxidation and Fe(III) reduction) are nearly independent of pH. While ligand-to-metal charge transfer (LMCT) is the dominant pathway for photochemical Fe(III) reduction, Fe(II) oxidation under irradiated conditions mainly occurs as a result of interaction with O₂, semiquinones and other short-lived oxidants. Overall, our data supports the conclusion that, as a result of the contribution from photogenerated organic moieties to Fe redox transformations, the steady-state Fe(II) concentration in irradiated surface waters containing natural organic matter may not be impacted significantly by changes in pH.