Controls on the redox potential of rainwater.

Hydrogen peroxide acting as a reductant affects the redox potential of rainwater collected at the Bermuda Atlantic Time Series Station, the South Island of New Zealand, the contiguous USA, and the primary study site in Wilmington, NC. Analytical measurements of both halves of redox couples for dissolved iron, mercury, and the nitrate-nitrite-ammonium system can predict the rainwater redox potential measured directly by a platinum electrode. Measurements of these redox couples along with the pH in rain yields pe⁻ between 8 and 11; the half reaction for hydrogen peroxide acting as a reductant using typical rainwater conditions of 15 μM H₂O₂ at pH 4.7 gives pe⁻ = 9.12, where pe⁻ = negative log of the activity of hydrated electrons. Of the six rainwater redox systems investigated, only manganese speciation appeared to be controlled by molecular oxygen (pe⁻ = 15.90). Copper redox speciation was consistent with superoxide acting as a reductant (pe⁻ = 2.7). The concentration of H₂O₂ in precipitation has more than doubled over the preceding decade due to a decrease in SO₂ emissions, which suggests the redox chemistry of rainwater is dynamic and changing, potentially altering the speciation of many organic compounds and trace metals in atmospheric waters.