Disinfection Byproducts

The haloacetamides, a class of emerging nitrogenous drinking water disinfection byproduct (DBPs), were analyzed for their chronic cytotoxicity and for the induction of genomic DNA damage in Chinese hamster ovary cells. The rank order for cytotoxicity of 13 haloacetamides was DIAcAm > IAcAm > BAcAm > TBAcAm > BIAcAm > DBCAcAm > CIAcAm > BDCAcAm > DBAcAm > BCAcAm > CAcAm > DCAcAm > TCAcAm. The rank order of their genotoxicity was TBAcAm > DIAcAm approximately equal to IAcAm > BAcAm > DBCAcAm > BIAcAm > BDCAcAm > CIAcAm > BCAcAm > DBAcAm > CAcAm > TCAcAm. DCAcAm was not genotoxic. Cytotoxicity and genotoxicity were primarily determined by the leaving tendency of the halogens and followed the order I > Br > > Cl. With the exception of brominated trihaloacetamides, most of the toxicity rank order was consistent with structure-activity relationship expectations. For di- and trihaloacetamides, the presence of at least one good leaving halogen group (I or Br but not Cl) appears to be critical for significant toxic activity. Log P was not a factor for monohaloacetamides but may play a role in the genotoxicity of trihaloacetamides and possible activation of dihaloacetamides by intracellular GSH and -SH compounds.

Many drinking water utilities that use source waters with significant bromide ion levels are currently seeking disinfection regimes that will minimize the formation of brominated disinfection byproducts while providing adequate disinfection. While ozonation appears to ...

Epidemiologic evidence on the relation between contaminants in drinking water and cancer is reviewed. The reviewed studies cover exposure to: disinfection byproducts; nitrate; arsenic and other metals; volatiles and contaminants from hazardous waste sites; asbestiform fibers; radionuclides; and fluoride. Most investigations are ecologic, with some confirmation of elevated risk from individual-based studies. In the case of waterborne arsenic, and possibly chlorination byproducts, there is a consistent but small body of epidemiologic evidence of an association with one or more types of cancer. Nitrate in groundwater has increased greatly over the years, and the demonstration of endogenous nitrosation among highly exposed subjects raises concern of elevated cancer risk. However, the epidemiologic data are not yet sufficient to draw a conclusion. There is a diversity of studies among populations exposed to water contaminated with pesticides, volatile organics, or mixtures from hazardous...

The effect of Fe2+, Fe3+, H2O2 and the photo-Fenton system (Fe2+ or 3+/H2O2/hv) on solar water disinfection (SODIS) at low temperature and at near neutral pH are discussed in detail. We focus on Escherichia coli K12 suspended in either MilliQ water, water containing mineral ions and in MilliQ water enriched with resorcinol, a model for natural organic matter (NOM).Recently, the photo-Fenton reagent at near neutral pH and at millimolar concentrations (0.6 mg −1 Fe2+ or 3+ and 10 mg L−1 H2O2), was demonstrated to be highly efficient not only for the acceleration of solar disinfection of river water, but also for the elimination of NOM, which is a known precursor for halogenated disinfection byproducts.In this work, these effects were systematically assessed at laboratory scale and in well controlled conditions excluding thermal inactivation. Besides the highly bactericidal properties of the photo-Fenton system at near neutral pH, a bactericidal effect of Fe2+ alone and of Fe3+ under irradiation (Fe3+/hv) were also observed. This was associated with diffusion and intracellular dark Fenton reactions for Fe2+, while the effect of Fe3+/hv was attributed to the adsorption of Fe3+ on the bacterial cell wall and subsequent photosensitization of these iron-bacteria exciplexes, leading to the direct oxidation of the cell membrane and the generation of ROS close to the target microorganism.In MilliQ water, photo-inactivation rates for E. coli were increased by 200% in the presence of Fe2+/hv compared to the basic SODIS system (hv) and up to 250% in the presence of Fe2+/H2O2/hv. When Fe3+ was added, photo-inactivation was enhanced up to 135% for Fe3+/hv and 145% for Fe3+/H2O2/hv.Inorganic ions contained in mineral water did generally inhibit the beneficial effect of Fe2+ or 3+ and H2O2 on bacterial inactivation. In contrast, the systems containing model NOM (resorcinol in MilliQ water, corresponding to 30 mg TOC L−1) resulted in a higher iron-photo-assisted bacterial inactivation. This was associated with the formation of Fe3+-organo bounds, which are stable at near neutral pH and undergo photosensitization under solar radiation leading to the generation of ROS and the oxidation of the organic compounds. Photo-inactivation in the presence of the photo-Fenton reagent was enhanced up to 320% for Fe2+/H2O2/hv and 355% for Fe3+/H2O2/hv, with a simultaneous mineralization of 90% TOC within 4 h.Based on these experimental results and supported by literature, a mechanistic interpretation of iron-catalyzed solar water disinfection is proposed, which illustrates the possible pathways involved in photo-inactivation of E. coli in the presence of Fe2+, Fe3+ and H2O2.

The formation potential of four trihalomethanes (THMFP) and seven haloacetic acids (HAA7FP) in 13 source waters taken from four major water basin areas in China was evaluated using the simulated distribution system (SDS) chlorination method. The specific ...

Water samples from a local water treatment plant were analyzed, using gas chromatography Fourier transform ion cyclotron resonance mass spectrometry (GC/FT-ICR MS), to identify potential disinfection byproducts (DBPs). Both liquid-liquid extraction (LLE) and solid-phase microextraction (SPME) techniques were used for sample preparation prior to GC/MS analyses. Based on the averaged mass measurement accuracy (MMA) of better than five parts-per-million (<5 ppm), multiple solvent artifacts were identified. It is shown that solventless SPME can be utilized to reduce potential interferences from solvent stabilizers. Six DBPs were detected and their molecular compositions were assigned at a high level of confidence. At the ppb concentration ranges and in the broadband mass spectral detection mode, internally calibrated mass spectra provided concurrent high resolution (resolving power M/deltaM50% > 30,000 at m/z values -110) and MMA of better than one part-per-million (MMA < 1 ppm). The use of thermochemical data, such as proton affinities, as a complementary tool to enhance analytical resolution is also demonstrated.

Halonitromethanes are drinking water disinfection byproducts that have recently received a high priority for health effects research from the U.S. Environmental Protection Agency (EPA). Our purpose was to identify and synthesize where necessary the mixed halonitromethanes and to determine the chronic cytotoxicity and the acute genotoxicity of these agents in mammalian cells. The halonitromethanes included bromonitromethane (BNM), dibromonitromethane (DBNM), tribromonitromethane (TBNM), bromochloronitromethane (BCNM), dibromochloronitromethane (DBCNM), bromodichloronitromethane (BDCNM), chloronitromethane (CNM), dichloronitromethane (DCNM), and trichloronitromethane (TCNM). Low- and high-resolution gas chromatography/mass spectrometry (GC/MS) was used to identify the mixed chloro-bromonitromethanes in finished drinking waters, and analytical standards that were not commercially available were synthesized (BDCNM, DBCNM, TBNM, CNM, DCNM, BCNM). The rank order of their chronic cytotoxicity (72 h exposure) to Chinese hamster ovary (CHO) cells was DBNM > DBCNM > BNM > TBNM > BDCNM > BCNM > DCNM > CNM > TCNM. The rank order to induce genomic DNA damage in CHO cells was DBNM > BDCNM > TBNM > TCNM > BNM > DBCNM > BCNM > DCNM > CNM. The brominated nitromethanes were more cytotoxic and genotoxic than their chlorinated analogues. This research demonstrated the integration of the procedures for the analytical chemistry and analytical biology when working with limited amounts of sample. The halonitromethanes are potent mammalian cell cytotoxins and genotoxins and may pose a hazard to the public health and the environment.

... Although health effects data on many of these compounds are not available, there is ... of 1 mg/L. Three rounds of treatment included the effect of added ... These include bromoform, dibromoacetonitrile, bromoacetic acid, dibromoacetic acid, cyanogen bromide, bromopicrin, 1, ...

Halonitromethanes are drinking water disinfection byproducts that have recently received a high priority for health effects research from the U.S. Environmental Protection Agency (EPA). Our purpose was to identify and synthesize where necessary the mixed halonitromethanes and to determine the chronic cytotoxicity and the acute genotoxicity of these agents in mammalian cells. The halonitromethanes included bromonitromethane (BNM), dibromonitromethane (DBNM), tribromonitromethane (TBNM), bromochloronitromethane (BCNM), dibromochloronitromethane (DBCNM), bromodichloronitromethane (BDCNM), chloronitromethane (CNM), dichloronitromethane (DCNM), and trichloronitromethane (TCNM). Low- and high-resolution gas chromatography/mass spectrometry (GC/MS) was used to identify the mixed chloro-bromonitromethanes in finished drinking waters, and analytical standards that were not commercially available were synthesized (BDCNM, DBCNM, TBNM, CNM, DCNM, BCNM). The rank order of their chronic cytotoxicity (72 h exposure) to Chinese hamster ovary (CHO) cells was DBNM > DBCNM > BNM > TBNM > BDCNM > BCNM > DCNM > CNM > TCNM. The rank order to induce genomic DNA damage in CHO cells was DBNM > BDCNM > TBNM > TCNM > BNM > DBCNM > BCNM > DCNM > CNM. The brominated nitromethanes were more cytotoxic and genotoxic than their chlorinated analogues. This research demonstrated the integration of the procedures for the analytical chemistry and analytical biology when working with limited amounts of sample. The halonitromethanes are potent mammalian cell cytotoxins and genotoxins and may pose a hazard to the public health and the environment.