Abstract

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.

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