Chlorine
dioxide (ClO2) is commonly used as an alternative
disinfectant to chlorine in drinking water treatment because it produces
limited concentrations of halogenated organic disinfection byproducts.
During drinking water treatment, the primary ClO2 byproducts
are the chlorite (50–70%) and the chlorate ions (0–30%).
However, a significant portion of the ClO2 remains unaccounted
for. This study demonstrates that when ClO2 was reacting
with phenol, one mole of free available chlorine (FAC) was produced
per two moles of consumed ClO2. The in situ formed FAC completed the mass balance on Cl for inorganic ClO2 byproducts (FAC + ClO2
+ ClO3
). When reacting with organic matter extracts
at near neutral conditions (pH 6.5–8.1), ClO2 also
yielded a significant amount of FAC (up to 25%). Up to 27% of this in situ formed FAC was incorporated in organic matter forming
adsorbable organic chlorine, which accounted for up to 7% of the initial
ClO2 dose. Only low concentrations of regulated trihalomethanes
were produced because of an efficient mitigation of their precursors
by ClO2 oxidation. Conversely, dichloroacetonitrile formation
from ClO2-induced generation of FAC was higher than from
addition of FAC in absence of ClO2. Overall, these findings
provide important information on the formation of FAC and disinfection
byproducts during drinking water treatment with ClO2.
Soil-air partition coefficient (Ksoil-air) values are often employed to investigate the fate of organic contaminants in soils; however, these values have not been measured for many compounds of interest, including semivolatile current-use pesticides. Moreover, predictive equations for estimating Ksoil-air values for pesticides (other than the organochlorine pesticides) have not been robustly developed, due to a lack of measured data. In this work, a solid-phase fugacity meter was used to measure the Ksoil-air values of 22 semivolatile current- and historic-use pesticides and their degradation products. Ksoil-air values were determined for two soils (semiarid and volcanic) under a range of environmentally relevant temperature (10-30 °C) and relative humidity (30-100%) conditions, such that 943 Ksoil-air measurements were made. Measured values were used to derive a predictive equation for pesticide Ksoil-air values based on temperature, relative humidity, soil organic carbon content, and pesticide-specific octanol-air partition coefficients. Pesticide volatilization losses from soil, calculated with the newly derived Ksoil-air predictive equation and a previously described pesticide volatilization model, were compared to previous results and showed that the choice of Ksoil-air predictive equation mainly affected the more-volatile pesticides and that the way in which relative humidity was accounted for was the most critical difference.
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