Applying polarity rapid assessment method and ultrafiltration to characterize NDMA precursors in wastewater effluents.

Certain nitrosamines in water are disinfection byproducts that are probable human carcinogens. Nitrosamines have diverse and complex precursors that include effluent organic matter, some anthropogenic chemicals, and natural (likely non-humic) substances. An easy and selective tool was first developed to characterize nitrosamine precursors in treated wastewaters, including different process effluents. This tool takes advantages of the polarity rapid assessment method (PRAM) and ultrafiltration (UF) (molecular weight distribution) to locate the fractions with the strongest contributions to the nitrosamine precursor pool in the effluent organic matter. Strong cation exchange (SCX) and C18 solid-phase extraction cartridges were used for their high selectivity for nitrosamine precursors. The details of PRAM operation, such as cartridge clean-up, capacity, pH influence, and quality control were included in this paper, as well as the main parameters of UF operation. Preliminary testing of the PRAM/UF method with effluents from one wastewater treatment plant gave very informative results. SCX retained 45-90% of the N-nitrosodimethylamine (NDMA) formation potential (FP)-a measure of the precursors-in secondary and tertiary wastewater effluents. These results are consistent with NDMA precursors likely having a positively charged amine group. C18 adsorbed 30-45% of the NDMAFP, which indicates that a substantial portion of these precursors were non-polar. The small molecular weight (MW) (<1 kDa) and large MW (>10 kDa) fractions obtained from UF were the primary contributors to NDMAFP. The combination of PRAM and UF brings important information on the characteristics of nitrosamine precursors in water with easy operation.

Reactions of thiocarbamate, triazine and urea herbicides, RDX and benzenes on EPA Contaminant Candidate List with ozone and with hydroxyl radicals.

Second-order rate constants of the direct ozone reactions [formula: see text] and the indirect OH radical reactions [formula: see text] for nine chemicals on the US EPA's Drinking Water Contaminant Candidate List (CCL) were studied during the ozonation and ozone/hydrogen peroxide advanced oxidation process (O(3)/H(2)O(2) AOP) using batch reactors. Except for the thiocarbamate herbicides (molinate and EPTC), all other CCL chemicals (linuron, diuron, prometon, RDX, 2,4-dinitrotoluene, 2,6-dinitrotoluene and nitrobenzene) show low reactivity toward ozone. The general magnitude of ozone reactivity of the CCL chemicals can be explained by their structures and the electrophilic nature of ozone reactions. The CCL chemicals (except RDX) are highly reactive toward OH radicals as demonstrated by their high [formula: see text] values. Ozonation at low pH, which involves mainly the direct ozone reaction, is only efficient for the removal of the thiocarbamates. Ozonation at high pH and O(3)/H(2)O(2) AOP will be highly efficient for the treatment of all chemicals in this study except RDX, which shows the lowest OH radical reactivity. Removal of a contaminant does not mean complete mineralization and reaction byproducts may be a problem if they are recalcitrant and are likely to cause health concerns.

Nitrogen-phosphorus detection and nitrogen chemiluminescence detection of volatile nitrosamines in water matrices: optimization and performance comparison.

Two nitrogen-specific detection methods, nitrogen-phosphorus detection (NPD) and nitrogen chemiluminescence detection (NCD), were investigated as low cost alternatives to mass spectrometry (MS) with chemical ionization (CI) for analysis of nitrosamines in aqueous samples. NCD showed greater sensitivity to N-nitrosodimethylamine (NDMA) and seven other volatile nitrosamines than did NPD. Instrument detection levels for NDMA were established at 2.6 microg/L and 4.0 microg/L in solvent with 3 microL splitless gas chromatograph (GC) injection for NCD and NPD, respectively. Using a dual-column confirmation method, both NCD and NPD compared favorably with CI-MS results for NDMA analysis in a variety of water sample types. For seven other nitrosamines, both detectors showed excellent accuracy in analyzing high concentrations (greater than 300 ng/L) in complex wastewater matrices, while the accuracy of spike recoveries of very low levels (less than 15 ng/L) in clean matrices varied for each nitrosamine and detection method.