Nitrite-Induced Activation of Iodate into Molecular Iodine in Frozen Solution.

A new mechanism for the abiotic production of molecular iodine (I2) from iodate (IO3-), which is the most abundant iodine species, in dark conditions was identified and investigated. The production of I2 in aqueous solution containing IO3- and nitrite (NO2-) at 25 °C was negligible. However, the redox chemical reaction between IO3- and NO2- rapidly proceeded in frozen solution at -20 °C, which resulted in the production of I2, I-, and NO3-. The rapid redox chemical reaction between IO3- and NO2- in frozen solution is ascribed to the accumulation of IO3-, NO2-, and protons in the liquid regions between ice crystals during freezing (freeze concentration effect). This freeze concentration effect was verified by confocal Raman microscopy for the solute concentration and UV-visible absorption spectroscopy with cresol red (acid-base indicator) for the proton concentration. The freezing-induced production of I2 in the presence of IO3- and NO2- was observed under various conditions, which suggests this abiotic process for I2 production is not restricted to a specific region and occurs in many cold regions. NO2--induced activation of IO3- to I2 in frozen solution may help explain why the measured values of iodine are larger than the modeled values in some polar areas.