Project A: Implementation of Innovative and Sustainable Treatment Technology John Tobiason, Dave Reckhow (UMass) Des Lawler, Lynn Katz, MaryJo

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1 Project A: Implementation of Innovative and Sustainable Treatment Technology John Tobiason, Dave Reckhow (UMass) Des Lawler, Lynn Katz, MaryJo Kirisits (UTexas) Treavor Boyer (U FL), Jane Zhang (USF) Chittaranjan Ray, Bruce Dvorak (UNebraska)

2 Project A Overall Brief Description: Bring well-developed innovative and sustainable technologies to pilot and demonstration stage, and provide treatment implementation guidance A1, A2, A3: further advance technologies developed in prior US EPA funded Innovative Technology for Small Systems research projects A4 Natural filtration impact demonstration A5, A6, A7: Implementation Guidance Anticipated target utility characteristics: - All, depends on specific technology and/or utility (guidance) Continuum of technology development:

3 Program A: Mature Technologies A1: Implementing ferrate treatment of drinking water in the US Reckhow & Tobiason A2: Simultaneous removal of inorganic contaminants, DBP precursors, and particles in alum and ferric coagulation Lawler & Katz A3: Contaminant reduction, life cycle impacts, and life cycle costs of ion exchange treatment and regeneration Boyer & Zhang A4: Natural filtration impacts on post disinfection water quality in small systems Dvorak & Ray Lawler & Tobiason: overall program lead Starting year 2&3 A5: Intermittent treatment plant operation: understanding and minimization of detrimental impacts Tobiason A6: Coagulant selection and dosing control for particle and NOM removal: guidance for small systems and demonstration Tobiason & Lawler A7: Effect of climate change on water treatment practice at small systems Lawler, Kirisits & Tobiason

4 Projects A1-A7 Timing for this morning Start Allotment (min) Topic 9:45 3 Overview Dave 9:48 25 A1: Ferrate John Speaker/Leader 10:13 25 A2 Simultaneous Removal Des, Lynn 10:38 25 A3: Ion Exchange Treavor, Jane 11:03 10 A4: Natural Filtration Bruce 11:13 2 A5-A7 John, Des, Mary Jo 11:15 30 Discussion Dave & John 11:45 End

5 Potential Impacts Mapping of Projects to Health Violations Based on FY 2014 (from sdwis fed) Reason All Sizes Serving < 10K Addressed by Project # # systems population # systems population Lead & Copper 8, M 8, M B3,D Coliform Bacteria 6, M 6, M A1,B3 DBPs M M A1,A2,A4,A6,B3,C1, C3,D Arsenic M M A1,B3 Nitrates M M A3,A4,B3,D Other Inorganics M M A1,A3,B3 Volatile Organics M M C3 Synthetic Orgs M M A1,C1 Radioactive M M A3,B3

6 A1. Implementing Ferrate Treatment of Drinking Water in the U.S. John Tobiason, Dave Reckhow Joseph Goodwill, Yanjun Jiang, Joshua Cunningham University of Massachusetts (Amherst)

7 Funded by US EPA The UMass Ferrate Group Dave Reckhow John Tobiason Yanjun Jiang Joe Goodwill Josh Cunningham RD Xuyen Mai

8 Project A1 Introduction Brief Description: Assess ferrate treatment performance at pilot and demonstration scales, continuous flow Build on USEPA STAR Project, Use of Ferrate in Small Drinking Water Treatment Systems, EPA-G2011-STAR-G1 Address ferrate dosing, bulk water quality impacts Application at pre- versus intermediate- stage in treatment train Role as oxidant, impact on coagulation & particle removal processes, potential disinfection Ct Anticipated target utility characteristics: surface waters (DBPs, T&O, disinfection); groundwaters (Mn(II), As(III), disinfection); any with trace level contaminants Continuum of technology development:

9 Placement of ferrate dosing, typical surface water treatment plant Slide graphic by Dr. Joseph Goodwill

10 Why ferrate? Fe(VI) Strong oxidant Disinfectant Decay in water Role in coagulation No halogenated DBPs Jiang et al 2016 WR evaluate bromate formation; not enough to be a problem Fe( VI) + H O Fe( III)( s) + O + OH 2 2

11 Proton speciation Ferrate chemistry Monoprotonated and unprotonated anions are dominate at most phs

12 Oxidant, disinfectant MS2 Phage (Hu et al., 2008) Triclosan (Yang et al., 2010) Reduced Sulfur, Nitrogen, Cyanide, etc. (Sharma, 2010)

13 (Goodwill et al., JAWWA, 2016)

14 Ferrate Preoxidation Possibilities!

15 Ferrate in DWT Ferrate Decay Time? Photo Credit: Xuyen Mai

16 Ferrate in DWT Ferrate Decay Solutes play an important role in rate of ferrate decay Fe(III) solids play an key role in rate of ferrate decay ph = 7.5, T = 20 deg C, [Fe(VI)] 0 = 43 µm Buffer = 10 mm (Jiang, Goodwill, Tobiason, and Reckhow, Env. Sci. Technol., 2015)

17 Ferrate in DWT Resulting Particles Differing particle characteristics raises questions about processes

18 Ferric Resultant Particles Ferrate Resultant Particles ph = 6.2, Carbonate Buffer = 1 mm, Total Fe = 3.0 mg/l, Natural TOC = 3.1 mg/l (Goodwill, Jiang, Gikoyno, Reckhow and Tobiason, Environ. Sci. Technol., 2015)

19 Key Questions Does ferrate decay in the same way for all types of waters? Is the mechanism the same? Are the rates similar or predictable? Can we develop models for ferrate decay? This will help to relate laboratory studies (e.g., microbial inactivation tests) to actual performance in different waters at public water treatment plants

20 Ferrate in DWT Oxidation of Mn(II) 1 mm carbonate buffer, Mn(II) i = 4.9 and 9.8 µm (Goodwill, Mai, Jiang, Reckhow and Tobiason., Submitted)

21 Ferrate in DWT Oxidation of Mn(II) Borate Buffer = 0.2 mm, Fe(VI) o = 75 µm, Mn(II) o = 113 µm, ph = 9.2

22 Ferrate in DWT Oxidation of DBP Precursors Natural Water Borate Buffer 1 mm Dose ferrate 20 µm, 50 µm 60 min Rx time Coagulate with FeCl 3 Measure UV254 Determine OFD Chlorinate Measure DBPs THMs and HAAs

23 Ferrate Raw water Coagulation/ Clarification Filtration Cl 2 Finished drinking water Decreased DBPFP Ferrate DBPFP Assessment Raw water Coagulation/ Clarification/ Filtration Cl 2 Finished drinking water DBPFP Assessment DBPFP Assessment Decreased DBPFP Jiang et al., 2016a, accepted, Water Research

24 Ferrate in DWT Batch Preoxidation of DBP Precursors Relative TTHM Formation Slightly better than coagulation alone Ferrate Dose (mg Fe/mg C) Amherst, MA, ph 6.2 Amherst, MA, ph 7.5 Gloucester, MA, ph 6.2 Gloucester, MA, ph 7.5 Holton, KS, ph 6.2 Holton, KS, ph 7.5 Houston, TX, ph 6.2 Houston, TX, ph 7.5 Norwalk, CT (epi), ph 6.2 Norwalk, CT (epi), ph 7.5 Norwalk, CT (meso), ph 6.2 Norwalk, CT (meso), ph 7.5 Norwalk, CT (hypo), ph 6.2 Norwalk, CT (hypo), ph 7.5 Palmer, MA, ph 6.2 Palmer, MA, ph 7.5 Readsboro, MA, ph 6.2 Readsboro, MA, ph 7.5 South Deerfield, MA, ph 6.2 South Deerfield, MA, ph 7.5 Stockbridge, MA, ph 6.2 Stockbridge, MA, ph 7.5 (Jiang et al, 2016a, accepted for Water Research)

25 Atkins and S. Deerfield WTPs

26 Laboratory Pilot Plant (Q = 0.5 L/min)

27 Laboratory Pilot Plant (Q = 0.5 L/min) ph control, coagulant, and ferrate feed solutions

28 Laboratory Pilot Plant (Q = 0.5 L/min) Upflow roughing filter, plastic media.

29 ~20% decrease in turbidity and UV254 abs.

30 Batch Intermediate Fe(VI) and THMs 1.2 Relative TTHM Formation d 1.1 Houston, ph 6.2 Houston, ph 7.5 Palmer, ph 6.2 Palmer, ph 7.5 Readsboro, ph 6.2 Readsboro, ph 7.5 Atkins, ph 6.2 Atkins, ph 7.5 Amherst, ph 6.2 Amherst, ph 7.5 Stockbridge, ph 6.2 Stockbridge, ph 7.5 Compare with Pre-Fe(VI) Ferrate Dose ( M) Intermediate Fe(VI) Relative TTHM Formation South Deerfield Norwalk Norwalk_50 ft Babson Norwalk_5 ft Ferrate Dose ( M)

31 Next: Project A1: Next Steps & Challenges Lab-scale pilot of intermediate ferrate (surface waters) DBPFP impact, taste & odor (?)), algal toxin(?) Evaluate ferrate exposure (Ct) Assess subsequent particle removal, ferrate impact on ph Lab-scale pilot of groundwater (Mn, As, direct media filtration) Desired: mobile pilot-scale demonstration Challenges: Ferrate supply/availability No current US commercial manufacture of K-ferrate salt. We are in contact with Batelle (license holder). Need kg s for larger scale pilot testing. Available on-site liquid product not generally appropriate for drinking water treatment Documentation of ferrate disinfection effectiveness: regulatory Ct Lab studies needed Challenges of ferrate species, measurement

32 Completed: Project A1 Ferrate: Outputs and Outreach-1 Journal articles, mostly based on prior EPA STAR project Goodwill, J.G., Jiang, Y., Reckhow, D.A., Gikonyo, J.G, and Tobiason, J.E. (2015) Characterization of Particles from Ferrate Pre-oxidation, Environmental Science & Technology, Vol. 49, pp , March DOI: /acs.est.5b00225 Goodwill, J.G., Jiang, Y., Reckhow, D.A., and Tobiason, J.E. (2016a) Laboratory assessment of ferrate for drinking water treatment, Journal American Water Works Association, Vol. 108, doi: Goodwill, J.G., Mai, X., Jiang, Y., Reckhow, D.A., and Tobiason, J.E. (2016b) Evaluation of manganese(ii) oxidation by ferrate for drinking water treatment, submitted to Chemosphere, March Jiang, Y., Goodwill, J.G., Tobiason, J.E, and Reckhow, D.A. (2015) Effect of Different Solutes, Natural Organic Matter, and Particulate Fe(III) on Ferrate(VI) Decomposition in Aqueous Solutions, Environmental Science & Technology, Vol. 49, pp , Mar 2015, DOI /es505516w. Jiang, Y., Goodwill, J.G., Tobiason, J.E, and Reckhow, D.A. (2016a) Impacts of ferrate oxidation on natural organic matter and disinfection byproduct precursors, accepted by Water Research, March Jiang, Y., Goodwill, J.G., Tobiason, J.E, and Reckhow, D.A. (2016b) Bromide Oxidation by Ferrate(VI): The Formation of Active Bromine and Bromate, accepted subject to minor revision, Water Research, February 2016.

33 Project A1 Ferrate: Outputs and Outreach-2 Completed (cont.): Implementation of Ferrate Treatment Technology, National Centers for Innovation in Small Drinking Water Systems (DeRisk, WINSSS, RE SEAU) Newsletter, Feb, Scheduled: Presentations: AWWA ACE Chicago, June, 2016; Goodwill et al., Evaluation of Ferrate For Drinking Water Treatment IWA Particle Separation Conference, Oslo, Norway, June 2016; Tobiason et al., Ferrate Induced Particles in Drinking Water Treatment Anticipated: Manuscript on intermediate ferrate treatment for submission to a technical Journal, Fall 2016.