Enhanced Chlorine Dioxide Decay in the Presence of
Metal Oxides: Relevance to Drinking Water Distribution Systems
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Abstract
Chlorine dioxide (ClO<sub>2</sub>) decay in the presence of typical
metal oxides occurring in distribution systems was investigated. Metal
oxides generally enhanced ClO<sub>2</sub> decay in a second-order
process via three pathways: (1) catalytic disproportionation with
equimolar formation of chlorite and chlorate, (2) reaction to chlorite
and oxygen, and (3) oxidation of a metal in a reduced form (e.g.,
cuprous oxide) to a higher oxidation state. Cupric oxide (CuO) and
nickel oxide (NiO) showed significantly stronger abilities than goethite
(α-FeOOH) to catalyze the ClO<sub>2</sub> disproportionation
(pathway 1), which predominated at higher initial ClO<sub>2</sub> concentrations
(56–81 μM). At lower initial ClO<sub>2</sub> concentrations
(13–31 μM), pathway 2 also contributed. The CuO-enhanced
ClO<sub>2</sub> decay is a base-assisted reaction with a third-order
rate constant of 1.5 × 10<sup>6</sup> M<sup>–2</sup> s<sup>–1</sup> in the presence of 0.1 g L<sup>–1</sup> CuO
at 21 ± 1 °C, which is 4–5 orders of magnitude higher
than in the absence of CuO. The presence of natural organic matter
(NOM) significantly enhanced the formation of chlorite and decreased
the ClO<sub>2</sub> disproportionation in the CuO–ClO<sub>2</sub> system, probably because of a higher reactivity of CuO-activated
ClO<sub>2</sub> with NOM. Furthermore, a kinetic model was developed
to simulate CuO-enhanced ClO<sub>2</sub> decay at various pH values.
Model simulations that agree well with the experimental data include
a pre-equilibrium step with the rapid formation of a complex, namely,
CuO-activated Cl<sub>2</sub>O<sub>4</sub>. The reaction of this complex
with OH<sup>–</sup> is the rate-limiting and pH-dependent step
for the overall reaction, producing chlorite and an intermediate that
further forms chlorate and oxygen in parallel. These novel findings
suggest that the possible ClO<sub>2</sub> loss and the formation of
chlorite/chlorate should be carefully considered in drinking water
distribution systems containing copper pipes