Abstract

In studies on the formation of disinfection byproducts (DBPs), it is necessary to scavenge residual active (oxidizing) chlorine in order to fix the chlorination byproducts (such as haloethanoates) at a point in time. Such research projects often have distinct needs from requirements for regulatory compliance monitoring. Thus, methods designed for compliance monitoring are not always directly applicable, but must be adapted. This research describes an adaptation of EPA Method 552 in which ascorbic acid treatment is shown to be a satisfactory means for reducing residual oxidizing chlorine, i.e., HOCl, ClO⁻, and Cl₂, prior to determining concentrations of halocarboxylates. Ascorbic acid rapidly reduces oxidizing chlorine compounds, and it has the advantage of producing inorganic halides and dehydroascorbic acid as opposed to halogenated organic molecules as byproducts. In deionized water and a sample of chlorinated tap water, systematic biases relative to strict adherence to Method 552 were precise and could be corrected for using similarly treated standards and analyte-fortified (spiked) samples. This was demonstrated for the quantitation of chloroethanoate, bromoethanoate, 2,2-dichloropropanoate (dalapon), trichloroethanoate, bromochloroethanoate, and bromodichloroethanoate when extracted, as the acids, into tert-butyl methyl ether (MTBE) and esterified with diazomethane prior to gas chromatography with electron capture detection (GC-ECD). Recoveries for chloroethanoate, bromoethanoate, dalapon, dichloroethanoate, trichloroethanoate, bromochloroethanoate, bromodichloroethanoate, dibromoethanoate, and 2-bromopropanoate at concentrations near the lower limit of detection were acceptable. Ascorbic acid reduction appears to be the best option presently available when there is a need to quench residual oxidants fast in a DBP formation study without generating other halospecies but must be implemented cautiously to ensure no untoward interactions in the matrix.