Sources, Fate and Control of N-Nitrosodimethylamine (NDMA) Precursors

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1 Sources, Fate and Control of N-Nitrosodimethylamine (NDMA) Precursors Eric Dickenson, Ph.D. R&D Project Manager 2015 California-Nevada Section AWWA Fall Conference September 28

2 Acknowledgements o Aleksey Pisarenko, Trussell Technologies o Gwen Woods, University of Toronto o Erica Marti, SNWA, University of Las Vegas o Daniel Gerrity, University of Las Vegas o Teng Zeng and Bill Mitch, Stanford University o SNWA Team: Brett Vanderford, Eric Wert, Beck Trenholm, Oscar Quiñones, Dr. Yue Wang, Janie Zeigler-Holady

3 UCMR2 Nitrosamine Occurrence Woods, G. and Dickenson, E. Journal AWWA, 107 (1), E58, 2015.

4 Woods, G. and Dickenson, Journal AWWA, 107 (1), E58, 2015

5 UCMR2 NDMA: Impact of Source Water Woods, G. and Dickenson, E. Journal AWWA, 107 (1), E58, 2015.

6 UCMR2 NDMA: Impact of Utility Size Woods, G. and Dickenson, E. Journal AWWA, 107 (1), E58, 2015.

7 Chloramine-Reactive Precursor Knowns o Tertiary amines have the potential for significant NDMA yields. (Mitch and Schreiber, 2008) o Tertiary amines containing β-aromatic substituents are particularly highyielding NDMA precursors. (Selbes et al. 2013, Le Roux et al. 2011, Shen and Andrews 2011). o Tertiary amines are common in many pharmaceutical and personal care products and other anthropogenic sources, but are not common functional groups in biomolecules and thus not likely to be prevalent in natural sources in the environment. o Quaternary amines form NDMA, but yields are notably lower. (Kemper et al. 2010, Park et al. 2009) o However, quaternary amine-based compounds are highly prevalent in consumer products but concentrations in wastewater have yet to be estimated owing to the inherent difficulty of measuring quaternary aminecontaining polymers.

8 Entry Routes of Nitrosamine Precursors into a Watershed o NDMA formation is associated with municipal wastewater, with precursor loads found into the 1,000 s ng/l. (Mitch and Sedlak 2004) o Potable Reuse Scenario

9 Potable Reuse Potable reuse: Indirect potable reuse (IPR): Direct potable reuse (DPR): recycled water used to supplement drinking water supplies involves an environmental buffer and possibly additional drinking water treatment involves an engineered storage buffer rather than an environmental buffer Conventional Wastewater Treatment Advanced Water Treatment de facto Environmental or Engineered Buffer Lake, river, spreading basin, aquifer injection Drinking Water Treatment Water Consumer

10 Greywater and Blackwaters Teng and Mitch, Environmental Science and Technology, In review

11 Greywater and Blackwaters Laundry water was the most significant source of precursors, followed by shower water and urine. Teng and Mitch, Environmental Science and Technology, In review

12 Greywater and Blackwaters Loadings of precursors in laundry water were associated more with colored laundry than white laundry. Teng and Mitch, Environmental Science and Technology, In review

13 Potable Reuse Potable reuse: Indirect potable reuse (IPR): Direct potable reuse (DPR): recycled water used to supplement drinking water supplies involves an environmental buffer and possibly additional drinking water treatment involves an engineered storage buffer rather than an environmental buffer Conventional Wastewater Treatment Advanced Water Treatment de facto Environmental or Engineered Buffer Lake, river, spreading basin, aquifer injection Drinking Water Treatment Water Consumer

14 Potable Reuse Conventional Wastewater Treatment Flow Equalization Membrane Filtration (MF/UF) Reverse Osmosis Advanced Oxidation (H 2 O 2 /UV) Engineered Buffer a) Purified Water Conventional Wastewater Treatment Flow Equalization Membrane Filtration (MF/UF) Ozonation Biofiltration GAC- Engineered Buffer b) Purified Water

15 Full- and Pilot-Scale NDMA Results 100 NDMA (ng/l) Ozone influent Ozone effluent Reporting Limit 0

16 Pilot-Scale NDMA Results Gerrity, D., Pisarenko, A. Marti, E., Trenholm, R., Gerringer, F., Reungoat, J., Dickenson, E., Water Research, Volume 72, 2015, Pages , 2015.

17 Impact of O 3 :TOC on NDMA: Bench-Scale Pisarenko, A., Marti, E., Gerrity, D., Peller, J., Dickenson, E. Environmental Science: Water Research & Technology. 2015, 1,

18 Biological Activated Carbon Treatment Dickenson, E., Pisarenko, A., Marti, E., Gerrity, D., Vanderford, B. Formation of Nitrosamines and Perfluoroalkyl Acids During Ozonation in Water Reuse Applications, WateReuse Foundation, Alexandria, VA, 2015.

19 Ozone Reactive Precursors Already Established Name Structure Yield Ref. 1,1-Dimethylhydrazine 80% 1 (UDMH) Potential NDMA Precursors Group Ex. Structure Similarity Dimethylhydrazone UDMH Daminozide 55% 1 TMDS 27% 2 Dimethyl- Semicarbazide Dimethylthiosemicarbazide TMDS Dimethylsulfamide 52% 1 (DMS) Methylene blue 8.3 x 10-3 % 3 (and other dyes) Dimethylcarbamate 1. Schmidt and Brauch, Kosaka et al., Oya et al., 2008 DMS Marti, Pisarenko, Peller, Dickenson (2015). Water Research, 72,

20 Entry Routes of Nitrosamine Precursors into a Watershed

21 Natural Attenuation of NDMA Precursors in an Urban, Wastewater-Dominated Wash Lake Las Vegas LW1 BR Lake Mead CCWRD LW9 LW3 DC LW7 LW5 0 5 Kilometers

22 NDMA FP Levels Along the Wash: Field Data NDMA (ng/l) (B) 0 LW9 LW7 LW5 LW3 LW1 BR Sampling site NDMA-FP Ambient NDMA Woods, G. and Dickenson, E. Water Research, In Review

23 Photolysis Experiment

24 Photolysis Experiment NDMA-FP (ng/l) Hours of sunlight exposure Photolysis Dark control Woods, G. and Dickenson, E. Water Research, In Review

25 Bench-Scale Microcosm Experiment WQTC Presentation! 500 NDMA-FP (ng/l) Time (days) Sorp (wat + sed) Microb (wat) Microb (wat + sed) Sorp (wat) Sorp (DI + sed) Microb (DI) Microb (DI + sed) Woods, G. and Dickenson, E. Water Research, In Review

26 Entry Routes of Nitrosamine Precursors into a Watershed

27 Nitrification in Distribution Systems Teng and Mitch, Environmental Science and Technology, In review

28 Nitrification in Distribution Systems NDMA increases likely due to release of precursors by nitrifying biofilms. Teng and Mitch, Environmental Science and Technology, In review

29 Nitrification in Distribution Systems Breakpoint chlorination suppressed nitrification and reduced precursor levels Teng and Mitch, Environmental Science and Technology, In review

30 Summary Precursor sources in raw water: wastewater effluent Colored laundry wastewater Both chloramine and ozone can react with precursors to form NDMA NDMA can be mitigated by biological filtration treatment NDMA precursors can be potentially attenuated in receiving waters, i.e., the environmental buffer Nitrifying biofilms can potentially release NDMA precursors within a distribution system mitigated by breakpoint chlorination

31 Water Research Foundation #4591: Major Sources of Nitrosamine Precursors from Raw Waters and Principal Investigators: Eric Dickenson Southern Nevada Water Authority Tanju Karanfil, Clemson University William Mitch, Stanford University Distribution Systems 31

32 Wednesday Session 11B Recycled Water RM: COHIBA 1 4:30 Removing Trace Organic Contaminants Using Biofiltration in Potable Reuse Marco Velarde, University of Nevada, Las Vegas 5:00 A Hazardous Ozone Disinfection Byproduct: NDMA Formation and Implications for Water Reuse Erica Marti, University of Nevada, Las Vegas

33 Questions or Thoughts? Contact: