1. Biological Treatment of Groundwater Containing Perchlorate Using Fluidized Bed Reactors August 23-24, 2000 Bill Guarini

2. ACKNOWLEDGMENTS AEROJET CORPORATION:Craig Fegan Gerry Swanick Mike Girard US FILTER:Casey Whittier Gene Mazewski Bob Hines ENVIROGEN:Paul Hatzinger Sam Frisch Scott Drew Dave Enegess

3. Presentation Outline 1.Envirogen/USFilter Partnership 2.Perchlorate Biological Degradation 3.Selection of Reactor Type 4.Fluidized Bed Reactor 5.Case Histories -Pilot -Full-Scale 6.Summary

4. Envirogen-USFilter Relationship Joint Marketing for Perchlorate and MTBE applications Envirogen focus - microbiology and biocatalysts USFilter focus - systems and hardware Strong synergy between the two organizations

5. Bacterial Metabolism Requirements: Energy Source (organic or inorganic) Electron Acceptor (O 2, NO 3, SO 4, CO 2 ) Carbon Source (organic or CO 2 ) Macronutrients (N,P,S) Mineral Ions (Ca, K, Mg, Fe, Cu, Zn, Co, et al.) Vitamins and/or Amino Acids

6. Terminal Electron Acceptor: ClO 4 - ClO 3 - ClO 2 - O 2 + Cl - (perchlorate) (chlorate) (chlorite) H 2 O Biological Perchlorate Reduction

7. Organic Pollutants e-e- H2OH2OO2O2 Biomass + CO 2 Benzene (substrate) Nutrients (N,P)

8. Perchlorate e-e- Cl - + H 2 O Biomass + CO 2 Substrate ClO 4 - Nutrients (N,P)

9. O2O2 H2OH2O Groundwater + Substrate NO 3 - N2N2 Denitrification ClO 4 - Cl - SO 4 - S-S- CO 2 CH 4 Methanogenesis + 800 Redox (mV) - 250 Utilization of Electron Acceptors

10. Bioreactor System Options for Treatment of Organic Chemicals FLUIDIZED BED REACTOR SYSTEM CONTAMINATED WATER OR WASTEWATER FEED pH CONTROL NUTRIENTS OXYGEN OXYGENATOR TREATED EFFLUENT MEMBRANE BIOLOGICAL REACTOR SYSTEM 50,00010,000 2,0001,000200 100 10 CONTAMINATED WATER OR WASTEWATER FEED FLOWRATE, GPM OXYGEN TREATED EFFLUENT pH CONTROL NUTRIENT(S) STATIC BED REACTOR SYSTEM CONCENTRATION, mg/l 100,000

11. FLUIDIZED BED REACTOR EFFLUENT FEED (i.e., CONTAMINATED GROUNDWATER) NUTRIENT(S) ELECTRON DONOR INFLUENT RECYCLE BED HEIGHT CONTROL SYSTEM FBR Flow Schematic

12. FBR Advantages High biomass concentration means long SRT and short HRT High volumetric efficiency translates to compact system Simplicity of operation minimizes need for operator attention Small impact from changing feed conditions, as feed is combined with recycle before entering the reactor

13. Key Mechanical Components Device and method used to distribute influent flow to the reactor Device and method used to control the expansion of the fluidized bed due to biofilm growth Method to control electron donor dosage rate

14. Pilot-Scale Laboratory Testing for Perchlorate

16. Laboratory-Pilot FBR Treatability -Application: Groundwater treatment -Feed:6-10 ppm C1O 4, 1-2 ppm NO 3 -N -Effluent:< 4 ppb C1O 4 (NO 3 -N not measured) Treatability -Application: Groundwater / Process water -Feed:400 ppm C1O 4, 480 ppm C1O 3, 20 ppm NO 3 -N -Effluent:< 0.02 ppm C1O 4, < 1 ppm C1O 3 < 1 ppm NO 3 -N

17. Laboratory-Pilot FBR Study –Application:Media Comparison, sand vs. GAC –Feed: 20-25 ppm ClO 4 –Effluent: < 4 ppb ClO 4 Study –Application:Electron Donor Comparison (Ethanol, Methanol, Acetate) –Feed: 20-25 ppm ClO 4 –Effluent: < 4 ppb ClO 4 (EtOH), < 20 ppb (HAc), ~1 ppm (MeOH), < 4 ppb (EtOH/MeOH)

18. FBR Media Performance Comparison with ethanol

19. Electron Donor Performance Comparison with silica sand FBR media

20. Treatment of High Concentration Perchlorate Waters using Pilot FBRs

21. Treatment of Chlorate and Nitrate in Pilot FBRs

22. Full-Scale FBR Treatment of Perchlorate

23. Full-Scale FBR Installation (Perchlorate Reduction) Design Basis –4,000 gpm –Four reactors –Ethanol as electron donor –GAC media –Volumetric ClO 4 loading = 44 lb/day/kcf

26. Full-Scale FBR Performance

27. Summary GAC media yielded quicker startup and showed more resiliency than sand. Ethanol is a more effective electron donor than methanol. Biological treatment to below quantitation limits has been demonstrated for high and low concentration waters. Consistent treatment of perchlorate to below quantitation limits has been demonstrated in a full-scale FBR system for more than 1 year.