Nitrosamines, including N-nitrosodimethylamine (NDMA), are disinfection by-products of concern for drinking water utilities that use chloramines as a disinfectant. In this study, batch experiments were performed to investigate the effectiveness of preoxidation with ozone, free chlorine, or both on removal of NDMA precursors in raw, lime-softened, and recarbonated water from a full-scale water treatment plant treating primarily Mississippi River water and in a tributary water sample before and after bench-scale lime softening. NDMA “precursor” concentrations were assessed indirectly by quantifying NDMA formed after addition of preformed chloramines using the uniform formation conditions (UFC) protocol. NDMA concentrations (NDMAUFC) in the raw plant water were 8 ng/L in summer and 10 ng/L in winter and increased to 13–26 ng/L in lime-softened and recarbonated waters. NDMAUFC in the raw tributary water was 33.7 ng/L. Preoxidation by ozone at doses of up to 5 mg/L effectively decreased NDMAUFC concentrations in all water samples with and without hydrogen peroxide addition (hydrogen peroxide:ozone mass ratio of 0.5:1). The effectiveness of ozone at destroying ambient NDMA precursors was independent of water temperature and ozone dose. NDMA precursor destruction, however, increased with increasing ozone dose for a recarbonated water sample spiked with ranitidine (initial NDMAUFC = 358 ng/L). Free chlorine at a dose of 5 mg/L as Cl2 for 20 min of contact time (i.e., Ct ∼70 mg-min/L) was most effective at destroying ambient NDMA precursors in recarbonated water, and similarly, free chlorine treatment following ozone (2 mg/L) was more effective at destroying NDMA precursors in the ranitidine-spiked water than ozone alone. Preoxidation with ozone, free chlorine, or both proved to be an effective strategy for limiting NDMA formation upon subsequent chloramination for surface waters impacted by agricultural activities and municipal wastewater discharges.
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References
1.
American Public Health Association, American Water Works Association and Water Environment Federation. Standard Methods for the Examination of Water and Wastewater. In: 24th ed. (Lipps WC, Braun-Howland EB, Baxter TE. eds.) APHA Press: Washington DC; 2023.
2.
AndrzejewskiP, Kasprzyk-HordernB, NawrockiJ. N-Nitrosodimethylamine (NDMA) formation during ozonation of dimethylamine-containing waters. Water Res, 2008; 42(4–5):863–870; doi: 10.1016/j.watres.2007.08.032
3.
AydinE, YamanFB, Ates GenceliE, et al.Occurrence of THM and NDMA precursors in a watershed: Effect of seasons and anthropogenic pollution. J Haz Mater, 2012; 221–222:86–91; doi: 10.1016/j.jhazmat.2012.04.012
4.
BaderH, HoignéJ. Determination of ozone in water by the indigo method. Water Res, 1981; 15(4):449–456; doi: 10.1016/0043-1354(81)90054-3
5.
BuxtonGV, GreenstockCL, HelmanWP, et al.Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (•OH/•O−) in aqueous solution. J Phys Chem Ref Data, 1988; 17(2):513–886; doi: 10.1063/1.555805
ChenZ, ValentineRL. The influence of the pre-oxidation of natural organic matter on the formation of N-nitrosodimethylamine (NDMA). Environ Sci Technol, 2008; 42(14):5062–5067; doi: 10.1021/es8006673
8.
DebordeM, von GuntenU. Reactions of chlorine with inorganic and organic compounds during water treatment-kinetics and mechanisms: A critical review. Water Res, 2007; 42:13–51; doi: 10.1016/j.watres.2007.07.025
9.
ElovitzMS, von GuntenU. Hydroxyl radical ozone ratios during ozonation processes. I-The Rct concept. Ozone Sci Eng, 1999; 21(3):239–260; doi: 10.1080/01919519908547239
10.
ElovitzMS, von GuntenU, KaiserHP. Hydroxyl radical/ozone ratios during ozonation processes. II. The effect of temperature, pH, alkalinity, and DOM properties. Ozone Sci Eng, 2000; 22(2):123–150; doi: 10.1080/01919510008547216
11.
GerrityD, PisarenkoAN, MartiE, et al.Nitrosamines in pilot-scale and full-scale wastewater treatment plants with ozonation. Water Res, 2014; 72:251–261; doi: 10.1016/j.watres.2014.06.025
12.
GilcaAF, TeodosiuC, FioreS, et al.Emerging disinfection byproducts: A review on their occurrence and control in drinking water treatment processes. Chemosphere, 2020; 259:1–17; doi: 10.1016/j.chemosphere.2020.127476
13.
HozalskiRM, MaB, EvansAN, et al.Production of N-nitrosodimethylamine precursors by biofilters is highly dynamic and affected by filter media type and backwashing conditions. ACS Environ Sci Technol Water, 2021; 1(3):661–671; doi: 10.1021/acsestwater.0c00166
14.
KrasnerSW, MitchWA, McCurryDL, et al.Formation, precursors, control, and occurrence of nitrosamines in drinking water: A review. Water Res, 2013; 47:4433–4450; doi: 10.1016/j.watres.2013.04.050
15.
LeeC, LeeY, SchmidtC, et al.Oxidation of suspected N-nitrosodimethylamine (NDMA) precursors by ferrate (VI): Kinetics and effect on the NDMA formation potential of natural waters. Water Res, 2008; 42(1–2):433–441; doi: 10.1016/j.watres.2007.07.035
16.
LeeC, SchmidtC, YoonJ, et al.Oxidation of N-nitrosodimethylamine (NDMA) precursors with ozone and chlorine dioxide: Kinetics and effect on NDMA formation potential. Environ Sci Technol, 2007a;41(6):2056–2063; doi: 10.1021/es062484q
17.
LeeC, YoonJ, von GuntenU. Oxidative degradation of N-nitrosodimethylamine by conventional ozonation and the advanced oxidation process ozone/hydrogen peroxide. Water Res, 2007b;41(3):581–590; doi: 10.1016/j.watres.2006.10.033
18.
LiaoX, ShenL, JiangZ, et al.NDMA formation during ozonation of metformin: Roles of ozone and hydroxyl radicals. Sci Total Environ, 2021; 796:149010; doi: 10.1016/j.scitotenv.2021.149010
19.
LimS, ShiJL, von GuntenU, et al.Ozonation of organic compounds in water and wastewater: A critical review. Water Res, 2022; 213; 118053; doi: 10.1016/j.watres.2022.118053
20.
MartiEJ, PisarenkoAN, PellerJR, et al.N-Nitrosodimethylamine (NDMA) formation from the ozonation of model compounds. Water Res, 2014; 72:262–270; doi: 10.1016/j.watres.2014.08.047
21.
MillerJW, UdenPC. Characterization of nonvolatile aqueous chlorination products off humic substances. Environ Sci Technol, 1983; 17(3):150–157; doi: 10.1021/es00109a006
MunchJW, BassettMV. Method 521: Determination of Nitrosamines in Drinking Water by Solid-Phase Extraction and Capillary Column Gas Chromatography with Large Volume Injection and Chemical Ionization Tandem Mass Spectrometry (MS/MS). EPA Document #: EPA/600/R-05/054, 2004; 47.
24.
OyaM, KosakaK, AsamiM, et al.Formation of N-nitrosodimethylamine (NDMA) by ozonation of dyes and related compounds. Chemosphere, 2008; 73:1724–1730; doi: 10.1016/j.chemosphere.2008.09.026
25.
PadhyeL, LuzinovaY, ChoM, et al.PolyDADMAC and dimethylamine as precursors of N-nitrosodimethylamine during ozonation: Reaction kinetics and mechanisms. Environ Sci Technol, 2011; 45(10):4353–4359; doi: 10.1021/es104255e
26.
PinkernellU, NowackB, GallardH, et al.Methods for the photometric determination of reactive bromine and chlorine species with ABTS. Water Res, 2000; 34(18):4343–4350; doi: 10.1016/S0043-1354(00)00216-5
27.
PisarenkoAN, StanfordBD, YanD, et al.Effects of ozone and ozone/peroxide on trace organic contaminants and NDMA in drinking water and water reuse applications. Water Res, 2012; 46(2):316–326; doi: 10.1016/j.watres.2011.10.021
28.
R Core Team. R: A Language and Environment for Statistical Computing, Vienna, Austria; 2021. Available from: https://www.R-project.org
29.
RookJJ. Formation of haloforms during chlorination of natural waters. Water Treat Exam, 1974; 234–243.
30.
SchmidtCK, BrauchH-J. N,N-dimethylsulfamide as precursor for N-nitrosodimethylamine (NDMA) formation upon ozonation and its fate during drinking water treatment. Environ Sci Technol, 2008; 42(17):6340–6346; doi: 10.1021/es7030467
31.
SchreiberIM, MitchWA. Influence of the order of reagent addition on NDMA formation during chloramination. Environ Sci Technol, 2005; 39(10):3811–3818; doi: 10.1021/es0483286
32.
SchurterLM, BachelorPP, MargerumDW. Nonmetal redox kinetics: Mono-, di-, and trichloramine reactions with cyanide ion trichloramine reacts with excess CN-in a stepwise series of Cl+ transfer reactions to give ClCN and to generate in sequence dichloramine, monochloramine, and ammonia: NCl3. Environ Sci Technol, 1995; 29:1127–1134.
33.
SelbesM, Beita-SandíW, KimD, et al.The role of chloramine species in NDMA formation. Water Res, 2018; 140:100–109; doi: 10.1016/j.watres.2018.04.033
34.
SelbesM, KimD, AtesN, et al.The roles of tertiary amine structure, background organic matter and chloramine species on NDMA formation. Water Res, 2012; 47(2):945–953; doi: 10.1016/j.watres.2012.11.014
35.
SelbesM, KimD, KaranfilT. The effect of pre-oxidation on NDMA formation and the influence of PH. Water Res, 2014; 66:169–179; doi: 10.1016/j.watres.2014.08.015
36.
SgroiM, VagliasindiFGA, SnyderSA, et al.N-Nitrosodimethylamine (NDMA) and its precursors in water and wastewater: A review on formation and removal. Chemosphere, 2018; 191:685–703; doi: 10.1016/j.chemosphere.2017.10.089
37.
ShahAD, KrasnerSW, FenC, et al.Trade-offs in disinfection byproduct formation associated with precursor preoxidation for control of N-nitrosodimethylamine formation. Environ Sci Technol, 2012; 46:4809–4818; doi: 10.1021/es204717j
38.
ShenR, AndrewsSA. Demonstration of 20 pharmaceuticals and personal care products (PPCPs) as nitrosamine precursors during chloramine disinfection. Water Res, 2010; 45:944–952; doi: 10.1016/j.watres.2010.09.036
39.
SoltermannF, LeeM, CanonicaS, et al.Enhanced N-nitrosamine formation in pool water by UV irradiation of chlorinated secondary amines in the presence of monochloramine. Water Res, 2013; 47:79–90; doi: 10.1016/j.watres.2012.09.034
40.
SongY, FengS, QinW, et al.Formation mechanism and control strategies of N-nitrosodimethylamine (NDMA) formation during ozonation. Sci Total Environ, 2022; 823:153679; doi: 10.1016/j.scitotenv.2022.153679
41.
TrogoloD, MishraBK, MichèII, et al.Molecular mechanism of NDMA formation from N,N-dimethylsulfamide during ozonation: Quantum chemical insights into a bromide-catalyzed pathway. Environ Sci Technol, 2015; 49:4163–4175; doi: 10.1021/es504407h
USEPA. Integrated Risk Information System; 2022b. Available from: https://www.epa.gov/iris [Last accessed: May20, 2022].
45.
von GuntenU. Ozonation of drinking water: Part I. Oxidation kinetics and product formation. Water Res, 2003; 37:1443–1467.
46.
von GuntenU, SalhiE, SchmidtCK, et al.Kinetics and mechanisms of N-nitrosodimethylamine formation upon ozonation of N,N-dimethylsulfamide-containing waters: Bromide catalysis. Environ Sci Technol, 2010; 44(15):5762–5768; doi: 10.1021/es1011862
47.
WangX, YangH, ZhouB, et al.Effect of oxidation on amine-based pharmaceutical degradation and N-nitrosodimethylamine formation. Water Res, 2015; 87:403–411; doi: 10.1016/j.watres.2015.07.045
WoodsGC, Dickenson ERV. Evaluation of the final UCMR2 database: Nationwide trends in NDMA. J Am Water Works Assoc, 2015; 107(1):58–68; doi: 10.2307/jamewatworass.107.1.e58
50.
YangL, ChenZ, ShenJ, et al.Reinvestigation of the nitrosamine-formation mechanism during ozonation. Environ Sci Technol, 2009; 43(14):5481–5487; doi: 10.1021/es900319f
51.
ZengT, GloverCM, MartiEJ, et al.Relative importance of different water categories as sources of N-nitrosamine precursors. Environ Sci Technol, 2016; 50:13239–13248; doi: 10.1021/acs.est.6b04650
52.
ZengT, MitchWA. Contribution of N-nitrosamines and their precursors to domestic sewage by greywaters and blackwaters. Environ Sci Technol, 2015; 49(22):13158–13167; doi: 10.1021/acs.est.5b04254
53.
ZouR, LiaoX, ZhaoL, et al.Reduction of N-nitrosodimethylamine formation from ranitidine by ozonation preceding chloramination: Influencing factors and mechanisms. Environ Sci Poll Res, 2018; 25(14):13489–13498; doi: 10.1007/s11356-018-1470-z
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