No abstract

Natural organic matter (NOM) from five water sources was fractionated using XAD resins and ultrafiltration membranes into different groups based on hydrophobicity and molecular weight (MW), respectively. The disinfection byproduct formation from each fraction during chlorination and chloramination was studied. In tests using chlorination, hydrophobic and high MW (e.g., >0.5 kDa) precursors produced more unknown total organic halogen (UTOX) than corresponding hydrophilic and low MW (e.g., <0.5 kDa) precursors. Trihaloacetic acid (THAA) precursors were more hydrophobic than trihalomethane (THM) precursors. The formation of THM and THAA was similar among different fractions for a water with low humic content. Hydrophilic and low MW (<0.5 kDa) NOM fractions gave the highest dihaloacetic acid (DHAA) yields. No significant difference was found for DHAA formation among different NOM fractions during chloramination. Increasing pH from 6 to 9 led to lower TOX formation for hydrophobic and high MW NOM fractions but had little impact on TOX yields from hydrophilic and low MW fractions. Bromine and iodine were more reactive with hydrophilic and low MW precursors as measured by THM or HAA formation than their corresponding hydrophobic and high MW precursors. However, hydrophobic and high MW precursors produced more UTOX when reacting with bromine and iodine.

Two natural waters were fortified with various levels of bromide or iodide ions (0-30 microM) and chlorinated in the laboratory to study the impact of bromide and iodide ions on the formation and speciation of disinfection byproducts. Trihalomethanes (THMs), haloacetic acids (HAAs), total organic halogen (TOX), and its halogen-specific fractions total organic chlorine (TOCl), bromine (TOBr), and iodine (TOI), were measured in this work. The molar yields of THMs and HAAs increased as the initial bromide concentration increased. No significant change in TOX concentration was found for varying bromide concentrations. However, TOX concentrations decreased substantially with increasing initial iodide concentrations. At higher levels of bromide, there was a decreasing level of unknown TOX and unknown TOCl but an increasing level of unknown TOBr. The extent of iodine substitution was much lower than that of bromine substitution when comparing identical initial concentrations because a substantial amount of iodide was oxidized to iodate by chlorine. The tendency toward iodate formation resulted in the unusual situation where higher chlorine doses actually caused reduced levels of iodinated organic byproducts. Quantitative assessment of the results of this study showed a good agreement with kinetic data in the literature.

Despite extensive efforts in the identification of new disinfection by‐products (DBPs) by environmental scientists, a significant fraction of the total organic halogen (TOX) in drinking water still cannot be accounted for by known specific DBPs. The formation and control of these unknown DBPs have not been well established. The primary aim of this study was to evaluate the effect of reaction time, pH, dosage, and temperature on the formation of unknown TOX (UTOX) during chlorination and chloramination. Results showed that greater conversion of UTOX to measurable by‐products occurred with increasing reaction time, pH, dose, and temperature during chlorination. The UTOX‐to‐TOX ratio increased with reaction time but decreased with pH and dose during chloramination. The formation of unknown brominated and iodinated DBPs decreased as chlorination or chloramination pH increased. TOX formation was significantly reduced at high pH values during chloramination. For best control of DBPs, the authors recommend that water utilities using chloramines perform chloramination under alkaline conditions. Given that dihaloacetic acids and trihaloacetic acids exhibited distinct responses to the evaluated parameters, the authors also recommend that these be considered different classes of DBPs in future studies.