1. Development / Optimization of the new High-Efficiency Nano-Catalyst Immobilization Technology for ex-situ treatment of contaminated waters K. Cross, Cross Consulting Engineers, Cardiff, CA and Charles Schaefer, Ph. D., Shaw Environmental, Inc., Lawrenceville, NJ

2. Overall Introduction and Outline Section 1: Overview of treatment w micro/nano-particles Section 2: HENCI Technology Overview HENCI TOP Phase 1 tests of late ’04 Section 3: Phase 2 Testing Objectives and key issues Scope of Experiments HENCI Reactor sub-optimization and sizing Section 4: Phase 3 Pilot Test Objectives Approach Potential Sites HENCI System Process PID’s Cost Evaluations

3. Section 1 Micro / Nano-Catalyzed Remediation Overview

4. Micro/Nano-Catalysis Highlights NanoTech now has ~2000 Application Categories - all sectors http://azonano.com/Applications.asp CNST / CBEN at Rice University: “We developed high-performance nano-scale catalysts for treating particularly challenging contaminants in water that must be removed to a very low level.” In-Situ Success with Pd/Fe on TCE by Zhang, Schrick, et. al. Rapid, Complete, Inexpensive Breakdown of ~50 (so far) ubiquitous recalcitrant carcinogenics at sub-ppb levels Cl’d Olefinics, Cl’d Aromatics, THMs, Pesticides, PCHs, PCBs, Dyes, NDMA, TNT, Cr2O2,AsO3, NO, Hg, Ni, City Redlands, CA Env. Council: “TCE and PCPs contamin- ating about half the wells in Midwest and Western U.S. Many in Redlands have been closed due to the high levels of TCE”

5. Ex Situ Treatment of Waters Containing Organic Contaminants Groundwater Drinking water Leachate Wash Down Bio-reactors Activated Carbon UV-oxidation Thermal CATOX

6. Zero Valent Metal Particles for Treatment of Organic Contaminants MetalDiameter (µm) Surface Area (m 2 /g) Composition ZVI filings1,0001.0Fe 0 MZVI802.0Fe 0 NZVI0.0125Fe 0 Metal Catalysts1.0190  60% Pd or Ni on alumina support Bimetallic MZVI/NZVI 0.0125Fe 0 doped with 0.1% Pd or Ni

7. Zero Valent Metal Particles Zero Valent metals have been show to treat a wide range of compounds: Chlorinated solvents Explosives (e.g., TNT, RDX) NDMA Nitrate Perchlorate (?) Limited use in ex situ treatment systems due to: Longevity Matrix Effects Particle Retention

8. Conceptual Model RX RH + X - + Fe 2+ Fe H+H+ Un-catalyzed ZVI Catalyzed ZVI RX Fe 2+ + H 2 Fe H+H+ Catalyst RH + X - H2OH2O H+H+ e-e-

9. Reactor Data  3 hour residence time 10g Ni catalyst TCE converted to ethane No sulfate reduction No nickel in effluent Influent DO = 8 mg/L Influent = artificial groundwater containing TCE, sulfate, nitrate, carbonate, and manganese

10. Reactor Data  3 hour residence time 10g Ni catalyst No sulfate reduction Influent DO = 8 mg/L Nitrate reduction Influent = artificial groundwater containing sulfate, nitrate, carbonate, and manganese

11. Catalyst regeneration using dilute acid Reactor Data Influent = artificial groundwater containing sulfate, nitrate, carbonate, and manganese Influent TCE  1 ppm

12. Geochemical Effects on observed PCE Degradation Rate Constants Ni NZVI pH  7.2

13. Batch Data - Mixtures Timescale of weeks NDMA inhibits PCE decay 1 st -order decay Negligible sorption NZVI Treatment

14. Section 2 HENCI Overview

15. As Previously noted, due to their size (and also structure / morphology), micro/nano-particles rapidly degrade many dissolved contaminants However, due to their small size, there has been no way to cost-effectively immobilize large quantities of MNPs in a flow-through reactor HENCI cost-effectively immobilizes most nano- & micro-catalysts in a new and novel way, free of the main technical and financial drawbacks inherent to today’s less viable technologies: Homogeneous, Dense Dispersion – no channeling Insignificant Del-P even at high flows = Low Cost Often NO NEW CONTACT MATERIALS exposed to stream HENCI High-Efficiency Nano-Catalyst Immobilization

16. What HENCI Means to the Process Engineer All advantages of a Continuous Packed-Bed Reactor No moving parts Nanoparticle agglomeration can be tuned out HENCI can immobilize any new macro-structured nanocatalysts which have high-µ or paramagnetic components Multiple Standardized HENCI units can be Manifolded Valved in series, parallel or any combination ‘on-line’ Process any combination of Inlet stream flow rate and concentration

17. Phase 1 Results (late 2004) Prototype Rxrs Immobilized ¼ g of BNPC’s per cm 3 @ ~2gpm Video Clip shows release of particles upon unit power-down Greater loading capacities very likely achievable HENCI Immobilization force more than adequate for all app’s Negligible Pressure Drops: allows High Flows, Long Reactors HENCI Prototypes operated with TCE - polluted inlet stream Preliminary Trial Report Circulated to NWRI Early ’05 TCE Run data yield fast Pseudo First-Order Rate Constants No effect on efficacy of catalyst by HENCI observed Verification of results is one task of phase 2

19. Section 3: Phase II Development 1: NMCR Database Gather data from Treatability Studies and literature Compile into ever-growing NMCR Database 2: Treatability Studies / RXR Development Build several bench-scale rxrs, install in Shaw’s Lab verify degradation of target contaminants in site groundwater determine the most appropriate metallic particles determine degradation kinetics reactor residence time estimate extent of particle “ change-out ” or regeneration Use data and experience to incorporate improvements to reactors Locations: Shaw Environmental, Inc. Lawrenceville, NJ Cross Consulting Cardiff, CA Objectives

20. 1. Batch Screening Tests Phase II Testing site groundwater degradation end products kinetics 2. Bench scale Reactor Testing reactant loading in HENCI reactor degradation rates daughter product generation reaction longevity hydraulic properties 3. Data Evaluation & Conceptual Design calculate rate constants reactor sizing and optimization

21. Reactor Sizing and Optimization 1st-order degradation rate constant for ZVI/Pd,  area ≥ 7130 m 2 /L to Key parameter:  area = m 2 /L of catalyst in reactor Basic Design Equation k´= k  area For 99.9% conversion,  = 12 minutes For 1 gpm flow, Reactor volume = 12 Gal Process Optimization Parameters RXR Eff = (% Conversion/ (T res x Mass BNMC ) ) Fluid Dyn. Eff = SA BET / (PSID / GPM / Axs) = SA BET / (PSID / v)  dEff / dPD goes thru max for each material  Scale-Up Using Optimal RXR t res  Reactor / system configuration det’d from Tres min and Inlet stream flowrate  Total DelP then allows pump sizing, system design, add controls

22. Section 4: Phase III - Pilot Demonstration Objectives Demonstrate HENCI particle retention system at the field scale Remediate in-field: Verify treatment effectiveness of target contaminants Evaluate long-term operation Identify potential design improvements and modifications

23. Potential Sites Picatinny Arsenal, Dover, NJ Existing P&T system operated by Shaw TCE  1000 µg/L Low ppb levels CT, DCE, VC Former Naval Surface Warfare Ctr, White Oak, MD former waste water discharge area TCE, TNT, RDX 19 th St. GAC Plant City of San Bernardino ~7ppb TCE, ~ 5ppb NDMA

24. Approach Construct and install HENCI System with selected nano/micro particles, controls, redundancies Treat and monitor for 3 to 4 months (  1 gpm flow) Perform O&M activities as needed Evaluate results with respect to overall treatment effectiveness and costs

25. Typical HENCI Process PID

26. Summary Rapid and cost-effective ex-situ treatment of a variety of contaminants HENCI technology applicable to wide range of nano/micro particles Significant Potential to revolutinize CHC Site remediation – Point-of-Distribution Systems: Pump/Treat, and USE! Reactor-based nanocatalysis will merit applications in other Environmental sub-sectors as Rural P.O.D., portable/Field unit, and other non-Groundwater applications arise Potential to Usher in new era in water remediation globally