Polyoxometalate-enhanced oxidation of organic compounds by nanoparticulate zero-valent iron and ferrous ion in the presence of oxygen

Abstract

The oxidation of N-nitrosodimethylamine (NDMA) precursors during water treatment was investigated using ozone and chlorine dioxide (CIO2). Second-order rate constants for the reactions of model NDMA precursors (dimethylamine (DMA) and 7 tertiary amines) with ozone (kapp at pH 7 = 2.4 × 10-1 to 2.3 × 109 M-1 s-1), CIO2 (kapp at pH 7 = 6.7 × 10 -3 to 3.0 × 107 M-1 s-1), and hydroxyl radical (̇OH) (kapp at pH 7 = 6.2 × 107 to 1.4 × 1010 M-1 s-1) were determined, which showed that the selected NDMA precursors, with the exception of dimethylformamide (DMFA) can be completely transformed via their direct reaction with ozone. During ozonation, DMFA may be partially transformed through oxidation by the secondary oxidant ̇OH. CIO2 was also shown to effectively transform most of the precursors, with the exceptions of DMA and DMFA. In the second part of the study, the NDMA formation potentials (NDMA-FP) in synthetic and natural waters were measured with and without pre-oxidation with ozone and CIO2. A significant reduction in the NDMA-FPs was observed after complete transformation of the model NDMA precursors. Ozonation generally led to more effective reduction of the NDMA-FP than CIO2. For most of the precursors, the formation of DMA could account for the NDMA-FPs remaining after complete transformation of the model NDMA precursors. In contrast, dimethylethanolamine and dimethyldithio-carbamate yielded other NDMA precursors (not DMA) as their oxidation products. Pre-oxidation by ozone and CIO2 of several natural waters showed behavior similar to that of the oxidation of model NDMA precursors with a reduction of the NDMA-FP by 32-94% for various natural water sources.