Parabens and salicylates were examined as disinfection byproduct (DBP) precursors to explore the possible influence of ipso substitution (i.e., halogen exchange) on the yield and speciation of trihalomethanes (THMs) formed during water chlorination. Substoichiometric conversion of C–Br bonds into C–Cl bonds was confirmed for several parabens and salicylates. The co-occurrence of (mono)brominated and nonhalogenated precursors in the presence of free chlorine (but in the absence of added Br–) generated polybrominated THMs, implicating ipso substitution. The THM molar yield, bromine incorporation, and bromine recovery from brominated and nonhalogenated precursor mixtures were commensurate with those observed from equimolar additions of NaBr, indicating efficient displacement of aromatic bromine by free chlorine followed by reincorporation of liberated HOBr into DBP precursors. The THM molar yield from brominated precursors was enhanced by a factor of ≤20 relative to that from nonhalogenated precursors. Trends in THM molar yields and bromine incorporation differed between brominated parabens and brominated salicylates, suggesting that the influence of ipso substitution on THM formation varies with the structure of the organic precursor. Collectively, these results provide new evidence of the often-overlooked role ipso substitution can play in promoting halogen exchange and bromine enrichment among DBPs in chlorinated waters.
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Spatial and Seasonal Variations of Disinfection Byproduct (DBP) Precursors in Relation with Total Organic Carbon (TOC)
Disinfection is an essential process for both potable water and wastewater treatment plants. However, disinfection byproducts (DBPs) like trihalomethanes (THMs), haloacetonitriles (HANs), and nitrosamines (NOAs) are formed when organic matter precursors react with disinfectants such as chlorine, chloramine, and ozone. Formation of DBPs is strongly associated with the type of water source, type of disinfectant, and organic matter concentration, which can have seasonal variation. In this study, water samples were collected from 20 different intra-watershed locations, which included urban runoff (with and without the influence of unsheltered homeless populations), wastewater effluent discharges, and a large, terminal reservoir that serves as the local drinking water source. Samples were collected on dry and rainy days, which represent seasonal samples. DBP formation potential (FP) tests were conducted at consistent pH, contact time, and temperature. THMs, NOAs, and HANs were analyzed by gas chromatography-mass spectrometry (GC-MS). The FP tests performed on these water samples revealed that chlorine formed the highest THM concentrations, while THM concentrations were low for the ozone FP test as expected. Chloramine produced the greatest HAN concentrations, with dichloroacetonitrile representing the highest concentration. With respect to sample type, more DBPs were formed at the non-wastewater-impacted runoff sites as compared to the wastewater effluent discharge sites. With respect to TOC levels, rain event samples for all locations had higher TOC concentrations compared to dry sampling days. Similarly, rain event samples showed increased DBP formation; a significant amount of precursors for THMs was found in runoff waters that were influenced by wastewater effluent discharges and unsheltered homeless locations (concentration of total THMs for chlorine FP test was >200 μg/L). Therefore, urban runoff waters should be considered as potential sources of DBP precursors to drinking water source waters, and runoff water is prone to seasonal variation.
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- Award ID(s):
- 1832713
- NSF-PAR ID:
- 10341126
- Date Published:
- Journal Name:
- World Environmental and Water Resources Congress 2021
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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null (Ed.)Previous studies have shown that algal-derived dissolved organic matter (DOM) has a strong influence on the formation of disinfection byproducts (DBPs) during the treatment of drinking water. In the summer of 2010, we evaluated the role of nitrogen and phosphorus loading and phytoplankton abundance as drivers of the concentrations and quality of DOM and the associated DBP formation in 30 reservoirs in the mountains and plains of the State of Colorado. Optical properties such as Specific Ultraviolet Absorbance at 254 nm (SUVA 254 ) and fluorescence spectroscopy were used to characterize DOM quality. Nutrient concentrations such as total nitrogen were also assessed and were associated with high concentrations of chlorophyll a (Chl-a). In turn, high total organic carbon (TOC) concentrations were associated with high concentrations of Chl-a, and the DOM in these reservoirs had a fluorescence signature indicative of contributions from phytoplankton growth. The reservoirs with TOC concentrations above 4 mgC/L were predominantly located in the plains and many are impacted by agricultural runoff and wastewater discharges, rather than in the mountains and are characterized by warm water conditions and shallow depths. For a subset of fourteen reservoirs, we characterized the composition of the phytoplankton using a rapid imaging microscopy technique and observed a dominance by filamentous Cyanobacteria in reservoirs with TOC concentrations above 4 mgC/L. The combination of high TOC concentrations with microbial characteristics resulted in high potential for production of two major classes of regulated DBPs, trihalomethanes and haloacetic acids. While fluorescence spectroscopy was useful in confirming the contribution of phytoplankton growth to high TOC concentrations, evaluation of predictive models for DBP yields found that all equally predictive models included SUVA 254 and some of these models also included fluorescence indices or logTOC. These findings provide a limnological context in support of the recent guidelines that have been implemented for protection of high-quality drinking water supplies in the State of Colorado.more » « less
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Abstract Drinking water disinfection by‐products (DBPs), including the ubiquitous trihalomethanes (THMs), are formed during the treatment of water with disinfectants (e.g., chlorine, chloramines) to produce and distribute potable water. Brominated THMs (Br‐THMs) are activated to mutagens via glutathione
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Conference Paper:
- https://doi.org/10.1061/9780784483466.058
