While natural organic matter (NOM) surrogates are established in disinfection byproduct (DBP) research, their use in fractionation studies is rare. To understand how surrogates relate to drinking waters, a range of NOM surrogates were fractionated with XAD resins. Their trihalomethane (THM), haloacetic acid (HAA), haloacetaldehyde, haloacetonitrile, and haloketone formations after chlorination were recorded. While compounds with higher log K(ow) values behaved as hydrophobic acids, fractionation of the more hydrophilic compounds did not clearly correlate to the log K(ow). High HAA formation from ferulic and aspartic acids and 1,1,1-trichloropropanone (1,1,1-TCP) formation from 3-oxopropanoic acid were notable. Three amino acids, asparagine, aspartic acid, and tryptophan, formed significant levels of dichloroacetonitrile (DCAN) and trichloroacetaldehyde (TCA). Formation of DBPs did not correlate to any compound physical property; however, there were several correlations between DBP groups. The most significant were between dichloroacetic acid (DCAA) and dichloroacetonitrile (DCAN), DCAN and TCA, and dichloroacetaldehyde (DCA) and trichloroacetaldehyde, indicating the possibility of similar relationships in natural waters.

The HIWATE (Health Impacts of long-term exposure to disinfection byproducts in drinking WATEr) project was a systematic analysis that combined the epidemiology on adverse pregnancy outcomes and other health effects with long term exposure to low levels of drinking water disinfection byproducts (DBPs) in the European Union. The present study focused on the relationship of the occurrence and concentration of DBPs with in vitro mammalian cell toxicity. Eleven drinking water samples were collected from 5 European countries. Each sampling location corresponded with an epidemiological study for the HIWATE program. Over 90 DBPs were identified; the range in the number of DBPs and their levels reflected the diverse collection sites, different disinfection processes, and the different characteristics of the source waters. For each sampling site, chronic mammalian cell cytotoxicity correlated highly with the numbers of DBPs identified and the levels of DBP chemical classes. Although there was a clear difference in the genotoxic responses among the drinking waters, these data did not correlate as well with the chemical analyses. Thus, the agents responsible for the genomic DNA damage observed in the HIWATE samples may be due to unresolved associations of combinations of identified DBPs, unknown emerging DBPs that were not identified, or other toxic water contaminants. This study represents the first to integrate quantitative in vitro toxicological data with analytical chemistry and human epidemiologic outcomes for drinking water DBPs.

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Disinfection by-products (DBPs) in drinking water, including trihalomethanes (THMs) and haloacetic acids (HAAs), arise from reactions of natural organic matter (NOM) with chlorine and other disinfectants. The objective of this review was to investigate relationships between the molecular properties of NOM surrogates and DBP formation using data collated for 185 compounds. While formation of THMs correlated strongly with chlorine substitution, no meaningful relationships existed between compound physicochemical properties and DBP formation. Thus non-empirical predictors of DBP formation are unlikely in natural waters. Activated aromatic compounds are well known to be reactive precursors; in addition DBP formation from β-dicarbonyl, amino acid and carbohydrate precursors can be significant. Therefore effective DBP control strategies need to encompass both hydrophobic and hydrophilic NOM components, as well as consider data from NOM surrogates in the context of knowledge from representative treatment scenarios. In future experiments, employing surrogates of NOM is likely to remain a powerful tool in the search for unknown precursors and in understanding their response to various disinfection conditions

The formation of disinfection by-products (DBPs) from chlorination and monochloramination of treated drinking waters was determined. Samples were collected after treatment at 11 water treatment works but before exposure to chlorine or monochloramine. Formation potential tests were carried out to determine the DBPs formed by chlorination and monochloramination. DBPs measured were trihalomethanes (THMs), haloacetic acids (HAAs), halonitromethanes (HNMs), haloacetonitriles (HANs), haloaldehydes (HAs), haloketones (HKs) and iodo-THMs (i-THMs). All waters had the potential to form significant levels of all the DBPs measured. Compared to chlorine, monochloramination generally resulted in lower concentrations of DBPs with the exception of 1,1-dichloropropanone. The concentrations of THMs correlated well with the HAAs formed. The impact of bromine on the speciation of the DBPs was determined. The literature findings that higher bromide levels lead to higher concentrations of brominated DBPS were confirmed.

Formation of harmful disinfection by-products (DBPs), of which trihalomethanes (THMs) and haloacetic acids (HAAs) are the major groups, can be controlled by removal of natural organic matter (NOM) before disinfection. In the literature, removal of precursors is variable, even with the same treatment. The treatment of DBP precursors and NOM was examined with the intention of outlining precursor removal strategies for various water types. Freundlich adsorption parameters and hydroxyl rate constants were collated from the literature to link treatability by activated carbon and advanced oxidation processes (AOPs), respectively, to physico-chemical properties. Whereas hydroxyl rate constants did not correlate meaningfully with any property, a moderate correlation was found between Freundlich parameters and log K(ow), indicating activated carbon will preferentially adsorb hydrophobic NOM. Humic components of NOM are effectively removed by coagulation, and, where they are the principal precursor source, coagulation may be sufficient to control DBPs. Where humic species remaining post-coagulation retain significant DBP formation potential (DBPFP), activated carbon is deemed a suitable process selection. Anion exchange is an effective treatment for transphilic species, known for high carboxylic acid functionality, and consequently is recommended for carboxylic acid precursors. Amino acids have been linked to HAA formation and are important constituents of algal organic matter. Amino acids are predicted to be effectively removed by biotreatment and nanofiltration. Carbohydrates have been found to reach 50% of NOM in river waters. If the carbohydrates were to pose a barrier to successful DBP control, additional treatment stages such as nanofiltration are likely to be required to reduce their occurrence.

Biodegradation is a potentially important loss process for haloacetic acids (HAAs), a class of chlorination byproducts, in water treatment and distribution systems, but little is known about the organisms involved (i.e., identity, substrate range, biodegradation kinetics). In this research, 10 biomass samples (i.e., tap water, distribution system biofilms, and prechlorinated granular activated carbon filters) from nine drinking water systems were used to inoculate a total of thirty enrichment cultures fed monochloroacetic acid (MCAA), dichloroacetic acid (DCAA), or trichloroacetic (TCAA) as sole carbon and energy source. HAA degraders were successfully enriched from the biofilm samples (GAC and distribution system) but rarely from tap water. Half of the MCAA and DCAA enrichment cultures were positive, whereas only one TCAA culture was positive (two were inconclusive). Eight unique HAA-degrading isolates were obtained including several Afipia spp. and a Methylobacterium sp.; all isolates were members of the phylum Proteobacteria. MCAA, monobromoacetic acid (MBAA), and monoiodoacetic acid (MIAA) were rapidly degraded by all isolates, and DCAA and tribromoacetic (TBAA) were also relatively labile. TCAA and dibromoacetic acid (DBAA)were degraded by only three isolates and degradation lagged behind the other HAAs. Detailed DCAA biodegradation kinetics were obtained for two selected isolates and two enrichment cultures. The maximum biomass-normalized degradation rates (Vm) were 0.27 and 0.97 microg DCAA/ microg protein/h for Methylobacterium fujisawaense strain PAWDI and Afipia felis strain EMD2, respectively, which were comparable to the values obtained for the enrichment cultures from which those organisms were isolated (0.39 and 1.37 microg DCAN/microg protein/h, respectively). The half-saturation constant (Km) values ranged from 4.38 to 77.91 microg DCAA/L and the cell yields ranged from 14.4 to 36.1 mg protein/g DCAA.

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