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NDMA formation from 4,4′-hexamethylenebis (HDMS) during ozonation: influencing factors and mechanisms

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Abstract

N-nitrosodimethylamine (NDMA), a toxic disinfection byproduct commonly associated with chloramination, has recently been found to form from an anti-yellowing agent (4,4′-hexamethylenebis (1,1-dimethylsemicarbazide) (HDMS)) during ozonation but the mechanisms are unclear. In this paper, the potential roles of molecular ozone (O3) and hydroxyl radical (∙OH) on NDMA formation from HDMS were investigated under various oxidation conditions (ozone dosages, pH) and different components in water (bromide ion (Br−), bicarbonate ion (HCO3−), sulfate ion (SO42−), and humic acid (HA), as well as natural organic matter (NOM) from a lake). Moreover, HDMS transformation pathways by ozonation were determined. The results indicated that the formation of NDMA was enhanced through the combined effect of O3 and ∙OH compared to that by O3 alone (addition of tert-butyl alcohol (tBA) as ∙OH scavenger). ∙OH itself cannot generate NDMA directly; however, it can transform HDMS to intermediates with higher NDMA yield than parent compound. The NDMA generation was affected (small dosages promoted but high dosages inhibited) by HA or Br− no matter with or without tBA. The presence of SO42− and HCO3− ions lowered NDMA formation through ∙OH scavenging effect. Increasing pH not only increased degradation rate constant by enhancing ∙OH generation but also affected HDMS dissociation ratio, reaching the maximum NDMA formation at pH 7–8. Natural constituents in selected water matrix inhibited NDMA formation. Impacts of these influencing factors on NDMA formation by only O3 however were significantly less pronounced over that by the joint roles of O3 and ∙OH. Based on the result of Q-TOF, LC/MS/MS, and GC/MS, the possible transformation pathways of HDMS by ozonation were proposed. The NDMA enhancement mechanism by the combined effect of O3 and ∙OH can be attributed to greater amounts of intermediates with higher NDMA yield (such as unsymmetrical dimethylhydrazine (UDMH)) produced. These findings provide new understanding of NDMA formation upon ozonation of typical amine-based compounds.

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References

  • Andrzejewski P, Kasprzyk-Hordern B, Nawrocki J (2008) Nnitrosodimethylamine (NDMA) formation during ozonation of dimethylamine containing waters. Water Res 42:863–870

    Article  CAS  Google Scholar 

  • Acero JL, Gunten V (1998) Influence of carbonate on advanced oxidation process for drinking water treatment. France: poitiers 13:1–9

    Google Scholar 

  • Bickelhaupt FM, Nibbering NMM, Wezenbeek EMV, Baerends EJ (1992) Central bond in the three CN” dimers NC-CN, CN-CN, and CN-NC: electron pair bonding and Pauli repulsion effects. J Phys Chem 96(12):4864–4873

    Article  CAS  Google Scholar 

  • Chen WH, Huang TH, Wang CY (2018) Impact of pre-oxidation on nitrosamine formation from a source to drinking water: a perspective on cancer risk assessment. Process Saf Environ 113:424–434

    Article  CAS  Google Scholar 

  • Elovitz MS, von Gunten U, Kaiser HP (1999) Hydroxyl radical/ozone ratios during ozonation processes. I the Rct concept. Ozone Sci Eng 21(3):239–260

    Article  CAS  Google Scholar 

  • Elovitz MS, von Gunten U, Kaiser HP (2000) Hydroxyl radical/ozone ratios during ozonation processes. II. The effect of temperature, pH, alkalinity, and DOM properties, ozone. Sci Eng 22(2):123–150

    CAS  Google Scholar 

  • Gamage S, Gerrity D, Pisarenko AN, Wert EC, Snyder SA (2013) Evaluation of process control alternatives for the inactivation of Escherichia coli, MS2 bacteriophage, and Bacillus subtilis spores during wastewater ozonation. Ozone Sci Eng 35(6):501–513

    Article  CAS  Google Scholar 

  • Gerrity D, Pisarenko AN, Marti E, Trenholm RA, Gerringer F, Reungoat J, Dickenson E (2015) Nitrosamines in pilot-scale and full-scale wastewater treatment plants with ozonation. Water Res 72:251–261

    Article  CAS  Google Scholar 

  • Health Canada, Guidelines for Canadian drinking water quality. Guideline technical document. N-Nitrosodimethylamine (NDMA). 2011, Ottawa, ON

  • Hoigné J, Bader H (1985) Rate constants of reactions of ozone with organic and inorganic compounds in water-III. Inorganic compounds and radicals. Water Res 19(8):993–1004

    Article  Google Scholar 

  • Hoigné J, Bader H (1994) Characterization of water quality criteria for ozonation processes. Part II: lifetime of added ozone. Ozone Sci. Eng 16(2):121–134

    Article  Google Scholar 

  • Hu JL, Chu WH, Sui MH, Xu B, Gao NY, Ding SK (2018) Comparison of drinking water treatment processes combinations for the minimization of subsequent disinfection by-products formation during chlorination and chloramination. Chem Eng J 335:352–361

    Article  CAS  Google Scholar 

  • Kosaka K., Asami M., Konno Y., Oya M., Kunikane S. Identification of antiyellowing agents as precursors of N-nitrosodimethylamine production on ozonation from sewage treatment plant influent Environ. Sci Technol 2009, 43(14), 5236–5241

  • Kosaka K, Asami M, Ohkubo K, Iwamoto T, Tanaka Y, Koshino H, Echigo S, Akiba M (2014) Identification of a new N-nitrosodimethylamine precursor in sewage containing industrial effluents. Environ. Sci. Technol. 48(19):11243–11250

    Article  CAS  Google Scholar 

  • Krasner SW, Mitch WA, McCurry DL, Hanigan D, Westerhoff P (2013) Formation, precursors, control, and occurrence of nitrosamines in drinking water: a review. Water Res 47(13):4433–4450

  • Langlais B., Reckhow D.A., Brink D. R. Ozone in water treatment: application and engineering AWWA Research Foundation and lewis Publisher.1991.18–19

  • Lee C, Choi W, Kim YG, UV YJ (2005) Photolytic mechanism of N-nitrosodimethylamine in water: dual pathways to methylamine versus dimethylamine. Environ. Sci Technol 39:2101–2106

    Article  CAS  Google Scholar 

  • Lee C, Yoon J, Schmidt C, Von Gunten U (2007) Oxidative degradation of N-nitrosodimethylamine by conventional ozonation and the advanced oxidation process ozone/hydrogen peroxide. Water Res 41(3):581–590

    Article  CAS  Google Scholar 

  • Lim MK, Zoh KD (2013) Effects of natural water constituents on the photo-decomposition of methylmercury and the role of hydroxyl radical. Sci Total Environ 449:95–101

    Article  CAS  Google Scholar 

  • Lim S.G., Lee W.G., Na S.Y., Shin J.D., Lee Y.H. N-nitrosodimethylamine (NDMA) formation during ozonation of N, N-dimethylhydrazine compounds: reaction kinetics, mechanisms, and implications for NDMA formation control. Water Res2016, 105:119–128

  • Liu JJ, Liao XB, Zhou ZM, Li F, Yuan BL (2015) Determination of seven N-nitrosamines in eutrophic drinking water after chlorination by high performance liquid chromatography-tandem mass spectrometry. Chinese J Anal Chem 4:502–506

    Google Scholar 

  • Lv J, Li YM, Song Y (2013) Reinvestigation on the ozonation of N-nitrosodimethylamine: Influencing factors and degradation mechanism. Water Res 47:4993–5002

    Article  CAS  Google Scholar 

  • Ma J, Graham NJD (2000) Degradation of atrazine by mangaese catalysed ozonation-influence of radical scavengers. Water Res 34:3822–3828

    Article  CAS  Google Scholar 

  • Marti EJ, Pisarenko AN, Peller JR, Dickenson ERV (2015) N-Nitrosodimethylamine (NDMA) formation from the ozonation of model compounds. Water Res 72:262–270

    Article  CAS  Google Scholar 

  • McCurry DL, Krasner SW, von Gunten U, Mitch WA (2015) Determinants of disinfectant pretreatment efficacy for nitrosamine control in chloraminated drinking water. Water Res 84:161–170

    Article  CAS  Google Scholar 

  • Mitch WA, Sharp JO, Trussell RR, Valentine RL, Alvarez-Cohen L, Sedlak DL (2003) N-Nitrosodimethylamine (NDMA) as a drinking water contaminant: a review. Environ Eng Sci 20:389–404

    Article  CAS  Google Scholar 

  • Oya M, Kosaka K, Asami M, Kunikane S (2008) Formation of N-nitrosodimethylamine (NDMA) by ozonation of dyes and related compounds. Chemosphere 73(11):1724–1730

    Article  CAS  Google Scholar 

  • Padhye L, Luzinova YL, Cho M, Mizaikoff B, Kim JH, PolyDADMAC HCH (2011) Dimethylamine as precursors of N-Nitrosodimethylamine during ozonation: reaction kinetics and mechanisms. Environ. Sci. Technol. 45:4353–4359

    Article  CAS  Google Scholar 

  • Park SH, Padhye LP, Wang P, Cho M, Kim JH (2015) Huang C.H. N-nitrosodimethylamine (NDMA) formation potential of amine-based water treatment polymers: effects of in situ chloramination, breakpoint chlorination, and pre-oxidation. J Hazard Mater 282:133–140

    Article  CAS  Google Scholar 

  • Pisarenko AN, Stanford BD, Yan D, Gerrity D, Snyder SA (2012) Effects of ozone and ozone/peroxide on trace organic contaminants and NDMA in drinking water and water reuse applications. Water Res 46(2):316–326

    Article  CAS  Google Scholar 

  • Pisarenko AN, Marti EJ, Gerrity D, Peller JR, Dickenson ERV (2015) Effects of molecular ozone and hydroxyl radical on formation of N-nitrosamines and perfluoroalkyl acids during ozonation of treated wastewaters. Environ Sci: Water Res Technol 1(5):668–678

    CAS  Google Scholar 

  • Roux LJ, Gallard H, Croué J (2012) Formation of NDMA and halogenated DBPs by Chloramination of tertiary amines: the influence of bromide ion. Environ Sci Technol 46(3):1581–1589

    Article  CAS  Google Scholar 

  • Schmidt CK, Brauch HJN (2008) N-dimethosulfamide as precursor for N-nitrosodimethylamine (NDMA) formation upon ozonation and its fate during drinking water treatment. Environ. Sci. Technol. 42:6340–6346

    Article  CAS  Google Scholar 

  • Selbes M, Kim D, Karanfil T (2014) The effect of pre-oxidation on NDMA formation and the influence of pH. Water Res 66:169–179

    Article  CAS  Google Scholar 

  • Sgroi M, Roccaro P, Oelker GL, Snyder SA (2014) N-Nitrosodimethylamine formation upon ozonation and identification of precursors source in a municipal wastewater treatment plant. Environ Sci Technol 48(17):10308–10315

    Article  CAS  Google Scholar 

  • Sgroi M, Roccaro P, Oelker G, Snyder SA (2016) N-nitrosodimethylamine (NDMA) formation during ozonation of wastewater and water treatment polymers. Chemosphere 144:1618–1623

    Article  CAS  Google Scholar 

  • Staehelin J, Hoigné J (1985) Decomposition of ozone in water in the presence of organic solutes acting as promoters and inhibitors of radical chain reactions. Environ Sci Technol 19(12):1206–1213

    Article  CAS  Google Scholar 

  • Trogolo D, Mishra BK, Heeb MB, von Gunten U, Arey JS (2015) Molecular mechanism of NDMA formation from N,N-dimethylsulfamide during ozonation: quantum chemical insights into a bromide-catalyzed pathway. Environ. Sci. Technol 49:4163–4175

    Article  CAS  Google Scholar 

  • Vione D., Falletti G., Maurino V., Minero C., Pelizzetti E., Malandrino M., Ajassa R., Iulian Olariu R., Arsene.C. Sources and sinks of hydroxyl radicals upon irradiation of natural water samples. Environ. Sci. Technol. 2006, 40:3775–3781

  • von Gunten U, Hoigné J (1994) Bromate formation during ozonation of bromide-containing waters: interaction of ozone and hydroxyl radical reactions. Environ. SciTechnol 28:1234–1242

    Article  Google Scholar 

  • von Gunten U (2003) Ozonation of drinking water: part I. oxidation kinetics and product formation. Water Res 37(7):1443–1467

    Article  CAS  Google Scholar 

  • von Gunten U, Salhi E, Schmidt CK, Arnold WA (2010) Kinetics and mechanisms of N-nitrosodimethylamine formation upon ozonation of N,N-dimethylsulfamide containing waters: bromide catalysis. Environ. Sci. Technol. 44(15):5762–5768

    Article  CAS  Google Scholar 

  • Wang WC, Gan J, Liu WP, Greem R (2005) Degradation of N-Nitrosodimethylamine (NDMA) in landscape soils. J Environ Qual 34(1):336–341

    Article  Google Scholar 

  • Zhang T, Chen WP, Ma J, Qiang Z (2008) Minimizing bromate formation with cerium dioxide during ozonation of bromide-containing water. Water Res 42(14):3651–3658

    Article  CAS  Google Scholar 

  • Zou RS, Liao XB, Zhao L, Yuan BL (2018) Reduction of N-nitrosodimethylamine formation from ranitidine by ozonation preceding chloramination: influencing factors and mechanisms. Environ Sci Pollut Res 25(14):13489–13498

    Article  CAS  Google Scholar 

Download references

Funding

This work was financially supported by National Natural Science Foundation of China (No. 51878301; No. 51678255; No. 51508209), Key projects of Quanzhou science and technology plan (No. 2018Z004), and it was also supported by Promotion Program for Young and Middle-aged Teacher in Science and Technology Research of Huaqiao University (ZQN-PY413).

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Authors and Affiliations

  1. Institute of Municipal and Environmental Engineering, College of Civil Engineering, Huaqiao University, Xiamen, 361021, Fujian, China

    Linlu Shen, Xiaobin Liao, Lei Zhao, Fei Li & Baoling Yuan

  2. College of Textiles and Appearl, Quanzhou Normal University, Quanzhou, 362002, Fujian, China

    Huan Qi

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  1. Linlu Shen
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  2. Xiaobin Liao
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  3. Huan Qi
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  4. Lei Zhao
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  6. Baoling Yuan
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Correspondence to Xiaobin Liao.

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Responsible editor: Vítor Pais Vilar

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Shen, L., Liao, X., Qi, H. et al. NDMA formation from 4,4′-hexamethylenebis (HDMS) during ozonation: influencing factors and mechanisms. Environ Sci Pollut Res 26, 1584–1594 (2019). https://doi.org/10.1007/s11356-018-3684-5

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  • DOI: https://doi.org/10.1007/s11356-018-3684-5

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