Formation of N-nitrosodimethylamine (NDMA) from humic substances in natural water

N-nitrosodimethylamine (NDMA)formation in chloraminated Iowa River water (IRW) is primarily attributed to reactions with natural organic matter (NOM) generally classified as humic substances. Experiments were conducted to determine the contribution of various NOM humic fractions to the NOMA formation potential (NDMA FP) in this drinking water source. NOM was concentrated by reverse osmosis (RO) and humic fractions were obtained by a series of resin elution procedures. Mass balances showed that nearly 90% of the NOMA formation potential could be recovered in the NOM concentrate and in water reconstituted using additions of the various humic fractions. Generally, the hydrophilic fractions tended to form more NOMA than hydrophobic fractions, and basic fractions tend to form more NDMA than acid fractions when normalized to a carbon basis. Overall, the hydrophobic acid fraction was the dominant source of NOMA when both formation efficiency and water composition were considered. The amount of NOMA formed in a sample was found to correlate linearly with an oxidation-induced decrease in specific UV absorbance (SUVA) value at 272 nm. This is consistent with a mechanism in which precursors are formed as the direct consequence of the oxidation of NOM. The NDMA FP estimated using the slope of this relationship and the initial SUVA value compared closely to the value obtained by measuring the NDMA formed in solutions dosed with excess concentrations of monochloramine that presumably exhaust all potential precursor sources. However, the NDMA FP could not be correlated to the SUVA value of the individual humic fractions indicating that the relationship of the NOMA FP to SUVA value is probably a water-specific parameter dependent on the exact composition of humic fractions. It is hypothesized that either specific NOMA precursors are distributed among the various humic fractions or that the humic material itself represents a "generic" nonspecific precursor source that requires some degree of oxidation to eventually produce NOMA. The non-monotonic behavior of NOM fluorescence spectra during chloramination and lack of correlation between NOM fluorescence characteristics and NOMA formation limited the usage of fluorescence spectra into probing NOMA formation.