Potential N-nitrosodimethylamine (NDMA) formation from amine-based water treatment polymers in the reactions with chlorine-based oxidants and nitrosifying agents

The NDMA formation potential (NDMA FP) of four commonly used amine-based cationic water treatment polymers was assessed in reactions with chlorine-based oxidants (free chlorine, monochloramine and chlorine dioxide) and nitrosifying agents (nitrite and nitrate). Relatively high dosages of polymers were directly exposed to oxidants for long reaction times in the FP tests to assess the potential to form NDMA and obtain mechanistic insight. Results show that the NDMA FP of the polymers generally follows the trend of aminomethylated polyacrylamide (Mannich polymer)>>poly(epichlorohydrin-dimethylamine) (polyamine) > poly(diallyldimethylammonium chloride) (polyDADMAC) > cationic polyacrylamide copolymer (cationic PAM). The high NDMA FP of Mannich polymer was largely due to the high amount of dimethylamine (DMA) residue in the polymer solution. For the other three polymers, the DMA concentration was increased after oxidation, indicating polymer degradation, and the trend of DMA increase agreed with that of NDMA FP. Among the oxidants, NDMA formation followed the order of monochloramine > free chlorine > chlorine dioxide, despite that the DMA release from the polymers caused by the oxidant followed the opposite order. At equal dosages, nitrite and nitrate generated NDMA from the polymers at levels comparable to those by free chlorine and chlorine dioxide; even so, the nitrosifying agents are unlikely to contribute significantly to NDMA formation due to expected lower concentrations in drinking water treatment systems. Jar tests followed by monochloramination of real water samples using conditions in line with those at potable water treatment plants generally showed relatively small contributions from polyamines and polyDADMACs to the overall NDMA formation.