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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Rapid, high-sensitivity analysis of oxyhalides by non-suppressed ion chromatography-electrospray ionization-mass spectrometry: application to ClO 4 − , ClO 3 − , ClO 2 − , and BrO 3 − quantification during sunlight/chlorine advanced oxidation
A rapid and sensitive method is described for measuring perchlorate (ClO 4 − ), chlorate (ClO 3 − ), chlorite (ClO 2 − ), bromate (BrO 3 − ), and iodate (IO 3 − ) ions in natural and treated waters using non-suppressed ion chromatography with electrospray ionization and tandem mass spectrometry (NS-IC-MS/MS). Major benefits of the NS-IC-MS/MS method include a short analysis time (12 minutes), low limits of quantification for BrO 3 − (0.10 μg L −1 ), ClO 4 − (0.06 μg L −1 ), ClO 3 − (0.80 μg L −1 ), and ClO 2 − (0.40 μg L −1 ), and compatibility with conventional LC-MS/MS instrumentation. Chromatographic separations were generally performed under isocratic conditions with a Thermo Scientific Dionex AS16 column, using a mobile phase of 20% 1 M aqueous methylamine and 80% acetonitrile. The isocratic method can also be optimized for IO 3 − analysis by including a gradient from the isocratic mobile phase to 100% 1 M aqueous methylamine. Four common anions (Cl − , Br − , SO 4 2− , and HCO 3 − /CO 3 2− ), a natural organic matter isolate (Suwannee River NOM), and several real water samples were tested to examine influences of natural water constituents on oxyhalide detection. Only ClO 2 − quantification was significantly affected – by elevated chloride concentrations (>2 mM) and NOM. The method was successfully applied to quantify oxyhalides in natural waters, chlorinated tap water, and waters subjected to advanced oxidation by sunlight-driven photolysis of free available chlorine (sunlight/FAC). Sunlight/FAC treatment of NOM-free waters containing 200 μg L −1 Br − resulted in formation of up to 263 ± 35 μg L −1 and 764 ± 54 μg L −1 ClO 3 − , and up to 20.1 ± 1.0 μg L −1 and 33.8 ± 1.0 μg L −1 BrO 3 − (at pH 6 and 8, respectively). NOM strongly inhibited ClO 3 − and BrO 3 − formation, likely by scavenging reactive oxygen or halogen species. As prior work shows that the greatest benefits in applying the sunlight/FAC process for purposes of improving disinfection of chlorine-resistant microorganisms are realized in waters with lower DOC levels and higher pH, it may therefore be desirable to limit potential applications to waters containing moderate DOC concentrations ( e.g. , ∼1–2 mg C L −1 ), low Br − concentrations ( e.g. , <50 μg L −1 ), and circumneutral to moderately alkaline pH ( e.g. , pH 7–8) to strike a balance between maximizing microbial inactivation while minimizing formation of oxyhalides and other disinfection byproducts.
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- Award ID(s):
- 1236303
- NSF-PAR ID:
- 10296258
- Date Published:
- Journal Name:
- Environmental Science: Water Research & Technology
- Volume:
- 6
- Issue:
- 9
- ISSN:
- 2053-1400
- Page Range / eLocation ID:
- 2580 to 2596
- 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/10.1039/d0ew00429d
