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Interactions of 1,4-hydroquinone with soluble iron species over a pH range of 3-5 in the air-saturated and partially deoxygenated solution are examined here. Our results show that 1,4-hydroquinone reduces Fe(III) in acidic conditions, generating semiquinone radicals (Q(•-)) that can oxidize Fe(II) back to Fe(III). The oxidation rate of Fe(II) by Q(•-)increases with increase in pH due to the speciation change of Q(•-) with its deprotonated form (Q(•-)) oxidizing Fe(II) more rapidly than the protonated form (HQ(•)). Although the oxygenation of Fe(II) is negligible at pH < 5, O2 still plays an important role in iron redox transformation by rapidly oxidizing Q(•-) to form benzoquinone (Q). A kinetic model is developed to describe the transformation of quinone and iron under all experimental conditions. The results obtained here are compared with those obtained in our previous studies of iron-Suwannee River fulvic acid (SRFA) interactions in acidic solutions and support the hypothesis that hydroquinone moieties can reduce Fe(III) in natural waters. However, the semiquinone radicals generated in pure hydroquinone solution are rapidly oxidized by dioxygen, while the semiquinone radicals generated in SRFA solution are resistant to oxidation by dioxygen, with the result that steady-state semiquinone concentrations in SRFA solutions are 2-3 orders of magnitude greater than in solutions of 1,4-hydroquinone. As a result, semiquinone moieties in SRFA play a much more important role in iron redox transformations than is the case in solutions of simple quinones such as 1,4-hydroquinone. This difference in the steady-state concentration of semiquinone species has a dramatic effect on the cycling of iron between the +II and +III oxidation states, with iron turnover frequencies in solutions containing SRFA being 10-20 times higher than those observed in solutions of 1,4-hydroquinone.

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 O 2 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 O 2 , 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.