Freeze–Thaw Cycle-Enhanced Transformation of Iodide to Organoiodine Compounds in the Presence of Natural Organic Matter and Fe(III)

The formation of organoiodine compounds (OICs) is of great interest in the natural iodine cycle as well as water treatment processes. Herein, we report a pathway of OIC formation that reactive iodine (RI) and OICs are produced from iodide oxidation in the presence of Fe(III) and natural organic matter (NOM) in frozen solution, whereas their production is insignificant in aqueous solution. Moreover, thawing the frozen solution induces the further production of OICs. A total of 352 OICs are detected by Fourier transform ion cyclotron resonance mass spectrometry in the freeze-thaw cycled reactions of Fe(III)/I-/humic acid solution, which are five times as many as OICs in aqueous reactions. Using model organic compounds instead of NOM, aromatic compounds (e.g., phenol, aniline, o-cresol, and guaiacol) induce higher OIC formation yields (10.4-18.6%) in the freeze-thaw Fe(III)/I- system than those in aqueous (1.1-2.1%) or frozen (2.7-7.6%) solutions. In the frozen solution, the formation of RI is enhanced, but its further reaction with NOM is hindered. Therefore, the freeze-thaw cycle in which RI is formed in the frozen media and the resulting RI is consumed by reaction with NOM in the subsequently thawed solution is more efficient in producing OICs than the continuous reaction in frozen solution.