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)

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:

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 • 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

Starting year 2&3

Lawler & Tobiason: overall program lead

Projects A1-A7 • Timing for this morning

Start Allotment

(min) Topic Speaker/Leader

9:45 3 Overview Dave

9:48 25 A1: Ferrate John

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

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 8,542 17.94 M 8,193 6.05 M B3,D

Coliform Bacteria 6,179 9.89 M 6,000 2.64 M A1,B3

DBPs 789 9.54 M 689 1.24 M A1,A2,A4,A6,B3,C1, C3,D

Arsenic 550 0.69 M 538 0.30 M A1,B3

Nitrates 555 0.37 M 552 0.13 M A3,A4,B3,D

Other Inorganics 98 0.29 M 92 0.06 M A1,A3,B3

Volatile Organics 21 0.06 M 20 0.01 M C3

Synthetic Orgs. 12 0.05 M 10 0.003 M A1,C1

Radioactive 288 0.49 M 278 0.019 M A3,B3

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)

The UMass Ferrate Group

Dave Reckhow John Tobiason

Yanjun Jiang Joe Goodwill

Josh Cunningham Xuyen Mai

Funded by US EPA

RD 83560201-0

Project A1 Introduction • Brief Description: Assess ferrate treatment performance at pilot

and demonstration scales, continuous flow • Build on 2011-2015 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:

Slide graphic by Dr. Joseph Goodwill

Placement of ferrate dosing, typical surface water treatment plant

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

−++→+ OHOsIIIFeOHVIFe 22 ))(()(

Ferrate chemistry • Proton speciation

– Monoprotonated and unprotonated anions are dominate at most pHs

Oxidant, disinfectant

Triclosan (Yang et al., 2010)

MS2 Phage (Hu et al., 2008)

Reduced Sulfur, Nitrogen, Cyanide, etc. (Sharma, 2010)

(Goodwill et al., JAWWA, 2016)

Ferrate Preoxidation Possibilities!

Ferrate in DWT – Ferrate Decay

Time?

Photo Credit: Xuyen Mai

Ferrate in DWT – 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)

Solutes play an important role in rate of ferrate decay

Fe(III) solids play an key role in rate of ferrate decay

Ferrate in DWT – Resulting Particles

Differing particle characteristics raises questions about processes

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)

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

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)

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

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 FeCl3

Measure UV254 • Determine ‘OFD’

Chlorinate Measure DBPs

• THMs and HAAs

Coagulation/ Clarification/ Filtration

Cl2

Ferrate

Raw water

Coagulation/ Clarification

Finished drinking

water

Ferrate

Raw water

Decreased DBPFP

Filtration

DBPFP Assessment DBPFP Assessment

Finished drinking

water

Decreased DBPFP

DBPFP Assessment

Cl2

Jiang et al., 2016a, accepted, Water Research

Ferrate in DWT – Batch Preoxidation of DBP Precursors

(Jiang et al, 2016a, accepted for Water Research)

Ferrate Dose (mg Fe/mg C)

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

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HM

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0.0

0.2

0.4

0.6

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1.0

1.2

Amherst, MA, pH 6.2Amherst, MA, pH 7.5Gloucester, MA, pH 6.2Gloucester, MA, pH 7.5Holton, KS, pH 6.2Holton, KS, pH 7.5Houston, TX, pH 6.2Houston, TX, pH 7.5Norwalk, CT (epi), pH 6.2Norwalk, CT (epi), pH 7.5Norwalk, CT (meso), pH 6.2Norwalk, CT (meso), pH 7.5Norwalk, CT (hypo), pH 6.2Norwalk, CT (hypo), pH 7.5Palmer, MA, pH 6.2Palmer, MA, pH 7.5Readsboro, MA, pH 6.2Readsboro, MA, pH 7.5South Deerfield, MA, pH 6.2South Deerfield, MA, pH 7.5Stockbridge, MA, pH 6.2Stockbridge, MA, pH 7.5

Slightly better than coagulation alone

Atkins and S. Deerfield WTPs

Laboratory Pilot Plant (Q = 0.5 L/min)

Laboratory Pilot Plant (Q = 0.5 L/min)

pH control, coagulant, and ferrate feed solutions

Laboratory Pilot Plant (Q = 0.5 L/min)

Upflow roughing filter, plastic media.

~20% decrease in turbidity and UV254 abs.

• d

Ferrate Dose (M)

0 10 20 30 40 50

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0.4

0.6

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Houston, pH 6.2Houston, pH 7.5Palmer, pH 6.2Palmer, pH 7.5Readsboro, pH 6.2Readsboro, pH 7.5Atkins, pH 6.2Atkins, pH 7.5Amherst, pH 6.2Amherst, pH 7.5Stockbridge, pH 6.2Stockbridge, pH 7.5

Ferrate Dose (M)

0 10 20 30 40 50 60

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South DeerfieldNorwalkNorwalk_50 ftBabsonNorwalk_5 ft

Batch Intermediate Fe(VI) and THMs

Intermediate Fe(VI)

Compare with Pre-Fe(VI)

Project A1: Next Steps & Challenges • Next:

– 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

Project A1 Ferrate: Outputs and Outreach-1 Completed: 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. 4955-4962, March 2015. DOI: 10.1021/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, 2016. doi:http://dx.doi.org/10.5942/jawwa.2016.108.0029

• 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 2016.

• 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. 2841-2848, Mar 2015, DOI 10.1021/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 2016.

• 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.

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, 2016.

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.