Spontaneous Reduction of Transition Metal Ions by One Electron in Water Microdroplets and the Atmospheric Implications

Freshman chemistry teaches that Fe³⁺ and Cu²⁺ ions are stable in water solutions, but their reduced forms, Fe²⁺ and Cu⁺, cannot exist in water as the major oxidation state due to the fast oxidation by O₂ and/or disproportionation. Contrary to these well-known facts, significant fractions of dissolved Fe and Cu species exist in their reduced oxidation states in atmospheric water such as deliquesced aerosols, clouds, and fog droplets. Current knowledge attributes these phenomena to the stabilization of the lower oxidation states by the complexation of ligands and the various photochemical or thermal pathways that can reduce the higher oxidation states. In this study, by spraying the water solutions of transition metal ions into microdroplets, we show the results of the spontaneous reduction of ligated Fe(III) and Cu(II) species into Fe(II) and Cu(I) species, presenting a previously unknown source of reduced transition metal ions in atmospheric water. It is the spontaneously generated electrons in water microdroplets that are responsible for the reduction. Control experiments in the atmosphere and in a glove box filled with precisely controlled gaseous contents reveal that O₂, CO₂, and NO₂ are the major competitors for the electrons, forming O₂^-, HCO₂^-, and NO₂^-, respectively. Taking these findings together, we opine that microdroplet chemistry might play significant but previously underestimated roles in atmospheric redox chemistry.