Use of Advanced Oxidation Processes for Resource Recovery. Wednesday, July 13 th, :00 PM 3:00 PM Eastern Time

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1 Use of Advanced Oxidation Processes for Resource Recovery Wednesday, July 13 th, :00 PM 3:00 PM Eastern Time 1 Introduction Water is limited! Objectives of today s webcast: To present an overview of the use of advanced oxidation processes (AOP) to achieve a higher level of wastewater treatment in order to recover the most valuable resource on earth To demonstrate AOP s effectiveness as a means for resource (water) recovery 2 1

2 Agenda Three speakers discussing municipal and industrial wastewater applications of using AOP Advances in High Level Disinfection Processes Hunter Recent Advances in AOP for Treatment of Microconstituents Cleary Finding the Optimal Solution for EDC and Pathogen Destruction - Salveson 3 Advances in High Level Disinfection Processes Gary Hunter, P.E., BCEE Senior Wastewater Process Specialist Black & Veatch Responsible for design, operation, maintenance and troubleshooting of wastewater disinfection projects Former Chair of the WEF Disinfection Committee 4 2

3 High Level Disinfection Regulatory differs from State to State General Trends Filtered effluent Less than 2.2 MPN/100 ml total coliform 4 of 7 samples Non detectable concentrations for Fecal coliform 5 Title 22 Requirements Filtered wastewater has been disinfected by either a. Chlorine Chlorination To Reuse b. Other Disinfection Process Min CT = 450 mg-min/l Min Contact time = 90 min 5-log removal of poliovirus Process X To Reuse 6 3

4 Conditional Acceptance Process for evaluation of technologies in California Chlorine 450 mg-min/l based on 90 minute modal contact time and 5 mg/l residual Other disinfection technologies tested to validate performance for 5 log removal of polio-virus 7 Factors that Impact Disinfection Process Mechanical Electrical I&C Flow Effluent quality: Solids Amount, size, type Ammonia Impact Chlorine and a UV absorber Residual COD pass through Non-biodegradable fraction Color additional chlorine demand/uv absorber Iron additional requirements/o&m/replacement of feed lines Hardness O&M/replacement of feed lines Transmittance UV spectra 8 4

5 What Disinfectant Do I choose for High Level Disinfection? Chemical Chlorine Gas Hypochlorite Liquid On-site Generation Chlorine Dioxide Chloramines UV Emerging Ozone, Pulsed UV PAA, Ferrate Peroxide, BDCMH 9 CONDITIONALLY APPROVED TECHNOLOGIES 10 5

6 Chlorine Disinfection Alternatives Chlorine Gas Sodium Hypochlorite (liquid) On-site generation of Hypochlorite On-site generation of Chlorine Gas Chlorine dioxide 11 Most common approach for reuse applications 1 pound of chlorine = 1 gallon of Hypochlorite at 12.5% solution. Storage Tank, Pump, and Contact Basin 450 mg-min/l based on 90 minute modal contact time and 5 mg/l residual. Requirements vary from State to State. Work being completed by Soroushian etal is indicating that ct might be able to be decreased to 100 mg-min/l using free chlorine Hypochlorite 12 6

7 On-site Generation of Hypochlorite Raw Materials Salt Electricity Water Generates 0.8% - 15% hypochlorite solution Survey of Facilities Few WW facilities All primary disinfection Other applications include Filament control Odor control Limited use in reuse applications interest increasing 13 CHEMISTRY AND MIXING ARE CRITICAL TO EFFECTIVE DISINFECTION Limited Detention Time (30 to 90 minute modal) = Ct approach Chlorine chemistry Free chlorine possible Multiple application locations Good Mixing Natural Energy Mechanical Energy Control Approach response time Control system need to respond to detention time 14 7

8 UV Design Dose For Reuse Reuse Media Filtration Membrane Filtration (MF and UF) Reverse Osmosis Minimum UV Design Dose (mj/cm 2 ) %T Turbidity Requirements Avg 2 NTU Peak 5 NTU Avg 2 NTU Peak 5 NTU Avg 2 NTU Peak 5 NTU 15 UV LIGHT Lamps wattage range from 250 to Low Pressure, Low Pressure high Output and medium pressure received conditional acceptance Validation and Performance testing (SCB) Mixing and flow distribution Cleaning critical Good distribution of UV Method of disposal/retreatment of off spec water Successfully used at numerous locations 16 8

9 How is Pasteurization Energy Efficient? Raw Water 70 F 73 F Pasteurized Water Preheater Module 220 F Exhaust 175 F 180 F Waste Heat Recovery Module Fuel (gas or liquid) 950 F Air Gas Turbine Generator Power 17 Total Coliform Dose Response Determined 4 Log Reduction in Total Coliform Temperature (deg F) 18 9

10 Ozone Not typically used for WW disinfection. Past History in US with Pure Oxygen Activated Sludge plants. Receiving new interest to THM/EDC Ozone will oxidize remaining COD before bacteria Becoming cost competative Received conditional accceptance 19 WRF and Other Studies Prove that Ozone Simultaneously Disinfects and Destroys EDCs Log Reduction of Seeded MS Ozone Only, Sand 0.6 Molar Ratio, Sand 2.3 Molar Ratio, Sand Ozone Only, MF Molar Ratio, MF 2.6 Molar Ratio, MF Applied Ozone Dose, mg/l Coliform Concentration, pfu/100 ml Total Coliform, Ozone Only Total Coliform, 0.6 Peroxide to Ozone Molar Ratio Fecal Coliform, Ozone Only Fecal Coliform, 0.6 Peroxide to Ozone Molar Ratio Applied Ozone Dose, mg/l 20 10

11 NON CONDITIONALLY APPROVED TECHNOLOGIES 21 Offers power efficiency of LPHI with lower number of lamps 800 W LPHO lamp Others such as WEDECO introducing new lamp technologies New Validation studies for Conditional Acceptance New LPHO Lamp 22 11

12 Chlorine Dioxide Must be generated on-site Requires Chlorine gas as feed (does not eliminate RMP) Research indicates less THM formation Variety of methods for generation Will need bench study to establish demand Limited success with application - City of San Luis Obispo 2 to 4 mg/l could achieve ND - Murray Peracetic Acid PAA appears to be effective disinfectant based on limit pilot data in US/Full scale in Europe. Decompose to Acetic Acid, Hydrogen Peroxide, Oxygen BOD and Side reactions. First Full scale facility WEFTEC 2008 NY State Recent application in St. Augustine, FL showed a dose of 1.5 mg/l of PAA yielded similar disinfection results to 7 mg/l chlorine 24 12

13 Ferrate Ferrate (Fe +6 ) is a strong oxidant, which can be utilized in reacting with refractory organics, inactivate pathogens and assist the coagulation process. By producing the ferrate in a liquid form the cost of the ferrate drops to around 2 to 4 dollars per pound or less. This liquid form can produced on site. On going testing Use with other Disinfectants UV/H 2 O 2 Ozone/H 2 O 2 Generally for Advanced Oxidation of Organic Compounds side reaction Disinfection Peroxide 26 13

14 BCDMH BCDMH 1-Bromo-3-chloro-5,5- dimethylhydantoin Effective Component 96% effective halogen decomposes into HOCl, HOBr, and Cl in water Full scale demonstration for CSO disinfection in Japan. 6 mg/l BCDMH 6 minutes contact time Initial testing showing less toxic and less generation of DBP s 27 FUTURE REUSE DISINFECTION CONCEPTS 28 14

15 Future Disinfection Alternatives Dual Disinfection Systems UV/Hypochlorite LA County doing research that appears to be promising. UV/On-site used when chemical limitation UV/PAA Multiple Barrier Approach 29 Dual/Multi-Barrier Used by Potable Water Industry Required for NDMA/perchlorate (UV/Peroxide) Take advantage of best of all systems UV for basic and Hypo for Reuse 30 15

16 Make Decision on What System is to be Used Economic Analysis Construction Cost O&M PW Analysis (10 years vs 20 years?) Non-Economic Analysis Decision mapping Public Acceptance Local Support Type of Technology Technology Support Parts/Pieces Availability Emerging Contaminants 31 Advantages of Technology All conditionally approved technologies have successfully been used at numerous locations Disinfection alternatives can be easily be modified to provide both disinfection and emerging contaminant removal 32 16

17 Challenges of Technologies Operation and maintenance of process Hydraulics Water quality improvements Conditional acceptance by new and improved processes 33 CONCLUSION Selection of disinfection technology is not as easy as it looks Future applications may influence selection of disinfection Disinfection is Fun!!! 34 17

18 Recent Advances in AOP for Treatment of Microconstituents Joseph G. Cleary, P.E., BCEE Senior Vice President and Section Manager at HDR HydroQual Expertise in pharmaceutical, chemical and food and beverage industries; focused on fate and transport of microconstituents through treatment plants Current Chair of WEF Industrial Wastewater Committee and Microconstitutents Community of Practice 35 Acknowledgements Ed Helmig Consultant Gary Grey HDR HydroQual Barbara Schilling - Ozonia 36 18

19 Presentation Outline Background on Microconstituents and APIs Ozone Treatment Fundamentals Industrial Wastewater Treatability Studies Industrial Full Scale Case Studies Summary 37 Background 38 19

20 APIs in the Environment Background Information Active Pharmaceutical Ingredients (APIs) are among the emerging contaminants of concern that can be classified into three potentially harmful categories: API s Endocrine Disrupting Compounds (EDCs) Toxic Compounds Antibiotic/Antimicrobial Agents Endocrine Effects Antibiotic Effects Toxic Effects 39 APIs in the Environment Background Information Endocrine Disrupting Compounds (EDCs) Manifest themselves as defects to reproduction, development and behavior of an organism Can affect the endocrine systems at parts per trillion levels Other Common Sources of EDCs Detergents, pesticides, plasticizers, flame retardants, agriculture products, natural hormones from plants, humans and animals Toxic Compounds (Acute & Chronic Effects) Adversely affect living species & ecosystems Effects are dose-dependent Antibiotic/Antimicrobial Agents May play a role in proliferation of resistant strains of bacteria 40 20

21 APIs in the Environment Background Information Pathways of APIs to the ecosystem*: Discharges from manufacturing facilities (<5%) Typically result in the highest localized concentrations found in the environment Disposal of unused dosages prescribed to patients (<10%) Excretion of un-metabolized API s by humans and livestock (<90%) * % contribution is based on average dispersion of API s in the environment, contributions local to major sources (manufacturing facilities, hospitals, CAFO etc.) could be very different. * EPA Active Pharmaceutical Ingredients (APIs) Regulatory & Treatment Challenges Lack of information on fate and long-term effects Ongoing challenge to identify the extent of the contamination in the water supply Due to varied physicochemical properties, there is no universal treatment technology Certain technologies appear to be effective for a broad range of compounds such as: Biological Treatment Activated Carbon Adsorption Ozone Oxidation 42 21

22 Ozone Treatment Basics 43 AOP Ozone Oxidation O 3 Feed Gas Preparation Ozone Generation Influent Ozone Contacting Effluent Vent Ozone Destruction 44 22

23 Ozone Oxidation - O 3 Virtually colorless gas Produced either from air or from oxygen Triatomic oxygen molecule (O 3 ) Unstable molecule must be generated on site which degrades to O 2 Extremely strong oxidizing agent Breaks down into hydroxyl radicals ( OH) Leaves a dissolved residual which ultimately converts back to oxygen Short half-life Atomic oxygen Ozone Molecular oxygen 45 Properties of Ozone - How it works: Oxidant: Breaks double carbon bonds Creates OH radicals which break higher carbon bonds Increased temp. and ph accelerates O 3 decomposition to OH Disinfectant: Kills by cell lysing or causing the cell wall to rupture Attacks all bacteria virus, cysts and spores in varying degrees 46 23

24 Properties of Ozone Relative Strength of Ozone Oxidizing Agent EOP (volt) EOP vs C12 Fluorine Hydroxyl radical Oxygen (atomic) OZONE Hydrogen peroxide Hypochlorite Chlorine Chlorine dioxide Oxygen (molecular) Ozone Treatment HOOC H N Cl Cl Diclofenac H 2 N O S O H N Sulfamethoxazole N O N O NH 2 Carbamazepine CH 3 OH R 1 C CH HO OR 2 HO O OH HO O O N Huber et al., 2003, Env.Sci.Technol. O O OCH Ethinylestradiol O OH Roxithromycin 48 24

25 Treatability Studies and Process Modeling 49 Chemical Oxidation Technology Evaluation Run Number Treatment Process Compound Reduction Toxicity Reduction 1 UV, hydrogen peroxide 99.5% 58% 2 Catalyzed UV, hydrogen 99.8% 88.2% peroxide 3 UV, ozone 99.4% 99.1% 4 UV, ozone, hydrogen peroxide 99.5% 95% 50 25

26 Pharmaceutical Facility, Netherlands AOP Treatment of Estrogens MBR Effluent COD ~1500 mg/l Characterize the MBR effluent for the estrogen compounds Evaluate AOP and GAC treatment technologies Estimate AOP chemical dosage and hydraulic detention time Characterize the impact of AOP on estrogenicity Removal (%) Percent Removals of Estrogens During ScreeningTests 99.8% 100.0% 100.0% 99.2% 98.9% 99.7% 100.0% 100% 95.5% 90.9% 90.9% 88.2% 88.2% 90% 81.8% 80% 70% 60% 50% 41.2% 40% 30% 18.2% 20% 10% 0% Ozone UV Ozone Peroxide UV Peroxide Chemical Oxidation Treatment Estrone 17A-Ethynyl Estradiol 17B-Estradiol 17A-Estradiol Figure 6: Percent Removals for Ozone Treatment at Different Dosages Removal, % 100% 80% 60% 40% 20% 0% Ozone Dosage, g/l 51 Bench Top Pilot Plant Ozone Removal of Target Compounds from Reuse Water (Snyder et al. 2007) 52 26

27 Full Scale Case Study 53 Case Study Pharmaceutical plants in Ireland and France (four plants). Each plant has one or two APIs. Concern was fate of APIs in the existing treatment plants. How does removal in plant correlate to treatment plant design and operating parameters? Alternatives to reduce APIs from plant? 54 27

28 Conclusions (Example Mass Balance) Plant 1 Plant 2 Influent API (ug/l) Effluent API (ug/l) Sludge API (ug/l) % Effluent 34 < 1 % Adsorbed to Sludge < 1 < 1 % Volatilized (assumption) 0 0 % Biodegraded Sludge Age (days) Aeration Basin Temperature ( C) Proposed Treatment Alternatives Alternative 1 Higher Sludge Age Alternative 2 Convert to Membrane Bioreactor (MBR) Alternative 3 Moving Bed Bioreactor (MBBR) Alternative 4 Membrane Bioreactor and Ozone Alternative 5 Membrane Bioreactor and Reverse Osmosis Alternative 6 Ozone and Activated Sludge Alternative 7 Ozone and Activated Sludge and Filtration Alternative 8 PACT System Alternative 9 Higher Sludge Age and Ozone 56 28

29 APIs Evaluated & Targeted by this Project Includes free and conjugated forms of the following types of APIs: Hormone Replacement Therapy (HRT): Medroxy Progesterone Acetate (MPA),Trimegestone,17-α-estradiol,17-βestradiol,17-α-dihydroequilin and Estrone Oral Contraceptives (OC): 17-α-ethinyl estradiol, Norgestrel, Gestodene, Estriol, Medrogestone and Estradiol Valerate Tranquilizers: Oxazepam, Lorazepam and Lormatazepam Selective Serotonin Reuptake Inhibitor (SSRI) 57 Process Selection for API Treatment - Robust Multi-Barrier Approach Ozone Oxidation Preceded by MBR Treatment Membrane Bioreactor (MBR) System Provides: High Quality Effluent Devoid of Suspended Solids (re-usable) Oxidation of Bulk Organic Competition for Ozone Biodegradation of Susceptible APIs Removal of Solids-Associated APIs Sorption of APIs to Biomass Ozone Oxidation Provides: Chemical Oxidation of Recalcitrant APIs Assits with disinfection of WW Oxygenation of WW 58 29

30 Selection Rationale for Ozone Oxidation Technology Proven Effective for APIs in Bench-Scale Tests One of the Most Powerful Chemical Oxidants Available High Turn-Up/Turn Down - Rapid Response No Solid Residual for Disposal Full-Scale Experience with High Performance Ozone Systems at Other Plant Locations 59 Process Flow Diagram for Full Scale System Process Vents Atmosphere Influent Drum Screens RAS (5Q) Odor Scrubber Recirculation (5Q) Ozone Destruct Injector Biology Ozone Contact Tank Effluent Discharge Equalization Tanks Aeration Tanks WAS Membrane Tanks Ozone Generators Degas Tank Flash Tank Utility Make-Up Solids Disposal Centrifuge Disk Thickener Vaporizers Liquid O 2 Tank

31 Full Scale Treatment System 61 Bioreactor & Membrane Tanks 2 GE/Zenon Z-500 C cassettes (0.04/0.1 micron pore size) with filtration area of 2,241 m 2 per cassette and header for 1 additional cassette per tank. There are 88 modules per cassette. RAS is 6Q

32 Ozone Generators and Catalytic Ozone Destruct System 2 x 300 kg/d Wedeco PDO 2000 Variable Frequency Ozone Generators complete with PSUs, LOx feed, dedicated chillers, gas monitoring systems and individual containers outfitted with O 2 /O 3 sensors, alarms and 12 Air Changes per hour exhaust fans. 63 Performance Verification Sampling Locations Concentrated API Waste IBC s Sampling Locations Influent wet well Balance Tank MBR System Permeate Ozone System Treated Effluent Screenings Waste Activated Sludge 64 32

33 Treated Effluent Analytical Testing Three Different Types of Testing Conducted: APIs GC/MS Estrogenicity Yeast Estrogen Screen (YES) Assay Toxicity Microtox Acute Toxicity Test 65 Full Scale Results APIs and Gross Organics Measured values EQ Permeate Effluent COD mg/l BOD mg/l Sum of APIs (g/d)

34 Yeast Estrogen Screen (YES) Results 1,000, , ,000 ng/l as 17-B estradiol equivalent 10,000 1,000 4,100 1, First Rinse EQ Tank/MBR Influent Ozone Influent/MBR Effluent Ozone Effluent 67 Summary Ozone is a proven technology for APIs in Pharmaceutical Industry Ozone is typically a polishing step after biological treatment Treatability studies are needed to develop design criteria Process modeling tools are also helpful for fate through treatment 68 34

35 Finding the Optimal Solution for EDC and Pathogen Destruction Andrew Salveson, P.E. Associate Vice President at Carollo Engineers Oversees advanced treatment of wastewater and wastewater disinfection projects 2007 WateReuse Association Person of the Year 69 WateReuse Foundation Project (02-009)-Innovative Treatment Technologies for Reclaimed Water Funding Agencies Project Team Duke University United States Department of Agriculture Carollo Engineers 70 35

36 We Have New Drivers for Alternative Treatment Public Concern Environmental Concern New Regulatory Investigations 71 WRF is Tasked with Finding Cost Efficient Advanced Treatment $10,000,000 $9,000,000 $8,000,000 $7,000,000 $6,000,000 $5,000,000 $4,000,000 $3,000,000 $2,000,000 $1,000,000 $0 1 mgd construction cost (estimate) UF/RO/AOP Sand and Chlorine WRF Findings??? Project Goal: Find relatively low-cost technologies that result in substantial pathogen and microconstituent reductions 72 36

37 WRF Project Bench top Studies Chlorine Chloramine Medium pressure (MP) UV MP UV with H Ozone Ozone with H PAA PAA with UV 73 Pilot Testing Refines Full-Scale Implementation Costs UV UV/PAA Pilot in Florida OH TiO 2 /UV Pilot in North Carolina H 2 O 2 O 3 Ozone Pilot in California UV/Peroxide Pilot in Florida 74 37

38 Memcor Microfilter at DSRSD Memcor Microfiltration System 9010 MC pressurized MF 0.2 micron pore size 75 Andritz Sand Filter at DSRSD Andritz Sand Filter Continuous backwash upflow filter Media depth of 80-inches with nominal sand media of millimeters 76 38

39 The HiPOx TM Pilot Reactor 77 Filtration Performance Comparison - PSD Number of particles per size channel, counts/ml Pre sand filter (2.99 NTU, 68% UVT) Post sand filter (2.13 NTU, 71% UVT) Pre microfilter (3.51 NTU, 70% UVT Post microfilter (0.19 NTU, 73% UVT) Particle diameter, m 78 39

40 Does Particulate Removal Equate to Microbe Removal? Larger percentage of smaller particulates removed with microfilters Particulate Size Turbidity TSS 1 m 5 m 10 m 25 m 50 m NTU mg/l Sand Filtration 20% 85% 85% 95% 75% 35% 51% Microfiltration 90% 99% 99% >99% >99% 95% 99% 79 MF Provides a Measurable Microbiological Barrier While No Substantial Removal is Seen with Sand Filters 80 40

41 MF/UF Membranes Do Reduce Some TOrCs 81 Ozone Pilot at DSRSD 82 41

42 Virus Correlation Tests Showed That 6.5-Log Reduction of MS2 is Equivalent to 5-Log Reduction of Poliovirus Log Reduction y = x R 2 = y = x R 2 = Ozone Dose, mg/l Log Reduction MS2 Linear (Log Reduction MS2) Log Reduction Poliovirus Linear (Log Reduction Poliovirus) 83 CT-Values > 1 mg-min/l Yielded Non-Detect Total Coliform Total Coliform (cfu/100ml) 1,000, ,000 10,000 1, CT (mg-min/l) 0 sec 10 sec 18 sec 50 sec 93 sec 157 sec 2.2 cfu/100ml 84 42

43 Ozone Demonstrated 6.5 LR of Seeded MS2 for Contact Times as Low as 10 seconds in Media Filtered Water Log reduction of MS Peroxide addition did not impact disinfection of MS Transferred ozone dose (ppm) 10 sec 18 sec 50 sec 93 sec Peroxide 6.5 MS2 LR 85 Bromate Formation Only Occurs at High Ozone Doses, Peroxide Addition Mitigates Bromate Bromate, ppb Bromate Concentration in Media and Microfilter Effluent Applied Ozone Dose, mg/l >170 ppb of bromide present for all tests Ozone Only, MF 0.6 Molar Ratio, MF 2.6 Molar Ratio, MF Ozone Only, Sand 0.6 Molar Ratio, Sand 2.6 Molar Ratio, Sand 86 43

44 Ozone Provides Substantial Destruction of Select Microconstituents Anlayte Concentration, ng/l EPOC Microconstituent Reduction Using Reduction Sand Filter NP, 0.6 Molar Ratio TCS, Ozone Only TCS, 0.6 Molar Ratio BPA, Ozone Only BPA, 0.6 Molar Ratio Applied Ozone Dose, mg/l 87 Ozone Provides Substantial Destruction of Select Microconstituents EEQ - MF Eff. No Peroxide EEQ - Sand Eff. No Peroxide EEQ - Sand Eff. ~0.50 to 0.65 H2O2/O3 MR EEQ - Sand Eff. 2.2 H2O2/O3 MR Microconstituent Concentration, ng/l Applied Ozone Dose 88 44

45 UV/Peroxide Pilot at Pinellas County 89 EEQ Destruction at High Dose Values 25 UV Dose ~500 mj/cm 2 Microconstituent Concentration, ng/ EEQ, 45 66% UVT EEQ, % UVT Hydrogen Peroxide Dose, mg/l 90 45

46 Measureable Destruction at Recycled Water UV Dose Values log EEQ (C/C0) LP UV fluence (mj/cm 2 ) MP 5 mg/l of H 2 O 2 has been added prior to UV disinfection 91 UV/Peroxide & UV/PAA Pilot in Bradenton FL 92 46

47 High Peroxide Doses Result in Measurable Destruction Peroxide/UV, % UV Peroxide/UV, % UVT % DEET Removal 100% 90% 80% 70% 60% 50% 40% RED MS2 ~ 89 mj/cm 2 for 30% 56% UVT 20% RED MS2 >200 mj/cm 2 for 10% 63% UVT 0% Hydrogen Peroxide Dose, mg/l 93 Limited UV/PAA Synergy Seen for Compound Destruction % Bisphenol-A Removal PAA only, % UVT PAA/UV, % UVT PAA only, % UVT 100% 90% 80% 70% 60% 50% 40% 30% 20% 10% RED MS2 ~ 26 mj/cm 2 0% PAA Dose, mg/l 94 47

48 UV/TiO 2 Pilot Testing at the Mecklenburg Utilities Sugar Creek WWTP-Charlotte NC PhotoCat UV/TiO 2 Pilot Purifics, Inc 95 UV/TiO 2 Photocatalysis The positively charged holes create hydroxyl radicals and oxidize surface-absorbed contaminants The conduction band electrons reduce oxygen to form super oxide radicals and reduce surface- absorbed contaminants 96 48

49 PhotoCat UV/ TiO 2 Process Q Influent 10 m cartridge filter 1.7Q UV Tubes 0.7Q Aeration TiO 2 Return Slurry Stainless steel tube 3 mm Quartz sleeve UV lamp 97 Purifics PhotoCat UV/TiO 2 Process Q Influent 10 m cartridge filter 0.7Q 1.7Q TiO 2 Return Slurry UV Tubes Accumulator Ceramic MF membrane Effluent Q Aeration 98 49

50 UV/TiO 2 Pilot Study Pilot feed - Sugar Creek WWTP tertiary effluent 16 experiments conducted The UV/TiO 2 system was operated with different number of UV lamps in service 0, 4, 8, 12, 16, 20, and 32 lamps Power input of 0 to 0.6 kw/gal Seeded the pilot influent with MS2 Adenovirus NDMA 99 High Quality Effluent Produced 100 Number of particles per size channel, counts/ml 10 Purifics Effluent Test A- 20 lamps in operation (0.18 NTU, 75.9% UVT) Distilled Water Purifics effluent Test N-UV off, with TiO2 (0.21 NTU, 64% UVT) Particle diameter, m

51 Oxidation of Dissolved Organics by the PhotoCat Process UVT, % Energy per Gallon Treated (kw) 101 Removal of Dissolved Organics is primarily NOT from the Membrane UVT, % 65 Influent Effluent With TiO2 Without TiO

52 Robust Coliform Disinfection was Demonstrated Total Coliform, MPN/100mL Energy per gpm Treated (kw) 103 Robust Virus Disinfection Proven MS2, pfu/100ml Energy per gpm Treated (kw)

53 Triclosan Dose/Response Triclosan, ng/l 30 Run 1, 10/22/07 PM 25 Run 2, 10/23/07 20 Secondary Effluent, 10/22/07 AM Energy per gpm Treated (kw) 105 Carbamazapine Dose/Response Carbamazapine, ng/l 160 Run 1, 10/22/07 PM Run 2, 10/23/ Secondary Effluent, 10/22/07 AM Energy per gpm Treated (kw)

54 Hormonal Equivalency Removal by the PhotoCat Process Filtration of Estradiol Equivalency by PhotoCat Ceramic Membrane (with UV Lamps Off) EEQ, ng/l 5 Influent Effluent Oxidation of Estradiol Equivalency by PhotoCat 0 With TiO2 Without TiO2 EEQ, ng/l Run 1 Run Energy per Gallon Treated (kw) 107 Need for Future Research Long term system performance must be confirmed. Cleaning requirements of the pre unit bag and cartridge filters must be quantified. Determine the cleaning requirements of the ceramic MF membrane. Determine the need for quartz sleeve cleaning

55 Pilot Summary (Filtration) 109 Ozone is the Lowest Cost Pathogen and EDC Treatment Treatment Technology Dose Net Present Value EEQ Destruction NaOCl (free residual) 450 mg-min/l $10,044,000 ~75% MPUV + H2O2 100 mj/cm 2, 15 ppm H2O2 $14,762,000 >90% MPUV + PAA 100 mj/cm 2, 8 ppm PAA $28,427,000 60% Ozone 9 mg/l $12,260,000 >90% Ozone 6.6 mg/l $11,317,000 >90% Ozone + UV 4 mg/l, 100 mj/cm 2 $12,806,000 >90% TiO2/UV kw/mgd $19,508,000 >90%

56 Questions?

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