Abiotic formation of organoiodine compounds by manganese dioxide induced iodination of dissolved organic matter

Iodination of dissolved organic matter (DOM) initiated by manganese oxide may represent an important source of organoiodine compounds (OICs) for iodide-containing waters. Here, Suwannee River natural organic matter was selected as model DOM, the OICs formation in simulated freshwater samples from iodinated DOM induced by manganese oxide (δ-MnO2) was investigated at different pHs and concentrations of iodide and δ-MnO2 by using negative ion electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR MS). While no OIC was observed in DOM control samples without δ-MnO2, hundreds of OICs were detected in the presence of δ-MnO2, suggesting the enhanced role of δ-MnO2 played in DOM iodination. The relative abundance was defined as the value of dividing the peak intensity of OICs by the highest m/z peak intensity constantly occurred in each mass spectrum, and selected as a parameter for partly reflecting the real level of OICs. The relative abundance of most OICs were around or greater than 1%, and several OICs with higher relative abundance were identified as diiodo-5-hydroxy-4-cyclopentene-1,3-dione, diiodomethane and diiodoacetic acid. The numbers of the formed OICs increased with the increase concentrations of iodide/δ-MnO2 and the decrease of pH, and nearly all OICs formed at lower levels of iodide/δ-MnO2 and/or higher pH were overlapped by that at higher levels of iodide/δ-MnO2 and/or lower pH, indicating the reliability of FT-ICR MS analysis techniques and data processing method. The OICs were formed mainly from the iodination of typical lignin-like and tannin-like compounds, as well as the precursor compounds with higher relative abundance through substitution reactions. Our findings demonstrate that the OICs formation by δ-MnO2-initiated DOM iodination should receive more attention and the concentration, exact structure and toxicity of the OICs need to be further investigated.