CH₃NCl₂ Formation from Chlorination of Carbamate Insecticides

Carbamate insecticides, which are common micropollutants in surface waters, were found to generate dichloromethlyamine (DCMA) during chlorination. DCMA formation from other precursors has been reported previously; it is part of the emerging class of nitrogen-based disinfection byproducts (N-DBPs) of health concern in chlorinated water. However, there is a limited understanding about its formation, stability, and toxicity. Four carbamate insecticides (methomyl, carbofuran, carbaryl, and thiodicarb) were examined as DCMA precursors over a range of reaction conditions, based on variables of chlorine/precursor (Cl/P) molar ratio, pH, time, and temperature. DCMA was found to be the dominant volatile DBP to result from chlorination of all four carbamate insecticides, with molar yields ranging from 12% to 150% at a Cl/P molar ratio of 20. Further experiments indicated CH₃NCl₂ to be relatively stable, with a half-life of up to 35 h in water. The toxicity of CH₃NCl₂ was investigated using a bacterial bioluminescence inhibition test and survival of human lung tumor cells. The results of these toxicity assays indicated that CH₃NCl₂ is about 3 orders of magnitude more toxic than CHCl₃. CH₃NCl₂ concentrations in the ppb range were observed to result from chlorination of surface water or tap water samples collected from several different locations in China. The results suggest that precursors to CH₃NCl₂ formation are ubiquitous and that CH₃NCl₂ poses a hazard to public health and the environment and should be considered in disinfection chemistry and water treatment.