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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Removal of Haloacetic Acids via Adsorption and Biodegradation in a Bench-Scale Filtration System
Brominated disinfection byproducts (DBPs) are a concern to drinking water utilities due to their toxicity and increasing prevalence in water systems. Haloacetic acids (HAAs) are a class of DBPs that are partially regulated by the United States Environmental Protection Agency (USEPA), but regulations are likely to increase as evidenced by the brominated HAAs listed on the USEPA Fourth Unregulated Contaminant Monitoring Rule and Fifth Contaminant Candidate List. Utilities often use a pre-oxidant to assist in their treatment training, but this can lead to increased HAA formation during treatment. In this study, tap water was spiked with bromine (Br2) at varying concentrations to simulate bromine-to-chlorine ratios found in the natural environment and the DBPs that may be formed from those waters. The water was fed through a bench-scale biological filter (biofilter) with a small layer of fresh granular activated carbon (GAC) media followed by acclimated anthracite media. The HAA species studied were found to be removable by an average of 89.5% through combined GAC filtration and biofiltration. Biodegradation occurred predominantly in the first five minutes for the acclimated anthracite, with minimal additional removal observed at longer empty bed contact times (15 and 30 min EBCT). This study provides recommendations on biofilter parameters for utilities to reduce the formation of both regulated and unregulated HAAs during the drinking water treatment process.
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- Award ID(s):
- 2019561
- PAR ID:
- 10429394
- Date Published:
- Journal Name:
- Water
- Volume:
- 15
- Issue:
- 8
- ISSN:
- 2073-4441
- Page Range / eLocation ID:
- 1445
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/w15081445
