Grantee Research Project Results

Final Report: Field Testing of Palladium-Catalyzed Hydrodehalogenation for Chlorinated Hydrocarbon Removal from Groundwater

EPA Grant Number: R825689C078
Subproject: this is subproject number 078 , established and managed by the Center Director under grant R825689
(EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
Center: Solutions for Energy, AiR, Climate and Health Center (SEARCH)
Center Director: Bell, Michelle L.
Title: Field Testing of Palladium-Catalyzed Hydrodehalogenation for Chlorinated Hydrocarbon Removal from Groundwater
Investigators: Reinhard, Martin , Roberts, Paul V.
Institution: Stanford University
EPA Project Officer: Hahn, Intaek
Project Period: January 1, 1995 through January 1, 2000
Project Amount: Refer to main center abstract for funding details.
RFA: Hazardous Substance Research Centers - HSRC (1989) RFA Text |  Recipients Lists
Research Category: Hazardous Substance Research Centers , Land and Waste Management

Objective:

This project aims to (1) establish the viability of hydrogen/palladium treatment for halogenated hydrocarbon removal by determining the catalyst lifetime and reaction kinetics in a continuous-flow packed bed reactor; (2) identify competitors/inhibitors in the process and minimize their effects; (3) quantify hydrogen consumption and determine effective supply methods; (4) scale up, optimize and implement the process at the field-scale.

Summary/Accomplishments (Outputs/Outcomes):

Palladium has been demonstrated to catalyze the reduction of halogenated hydrocarbons to alkanes by hydrogen. Batch studies with palladium indicate a rate of reaction several orders of magnitude higher than in the zero-valent iron system (another method currently under study). Chlorinated ethenes, including PCE and vinyl chloride, were completely removed from tap water within ten minutes at room temperature by 0.5% palladium on alumina at 0.1 atm of hydrogen pressure. (Schreier and Reinhard, Chemosphere, 31(6) pp 3475-3487, 1995.) This quick reaction time demonstrates palladium's great potential for application in pump-and-treat groundwater remediation. Although palladium has been used as a reduction catalyst for years in organic chemistry applications, the system has not yet been well characterized for groundwater treatment.

This project entails construction and testing of bench-scale continuous-flow reactors. For testing, we have been using artificially contaminated deionized (DI) water, groundwater from Livermore, California, and groundwater from the California Central Valley. Two bench-scale systems have been constructed, one which is operated in the flow-through mode and one which is operated in a rotating basket-mode. Base-line tests with deionized (DI) water have indicated 99% TCE removal at inlet concentrations ranging from 1.5 to 25 mg/L with no noticeable decrease in catalyst activity over 5 months. When actual ground waters is used, the catalyst is deactivated at rates that depend on water quality. The approach to identify deactivating water quality parameters has been to correlate the water quality with catalyst deactivation time and then to study the effect of the hypothesized parameters in separate experiments.

Efforts are directed towards establishing the reactivities of different VOCs and getting a better understanding of the catalyst performance under groundwater treatment conditions, specifically (1) quantifying the competing effects of oxygen and TCE reduction, (2) improving the methodology to characterize catalyst deactivation using spectroscopic methods, and (3) characterizing the effects of the water matrix on the process. We developed the methodology to evaluate samples of catalyst in column and rotating basket reactors and different water matrices. A model was evaluated for examining the column performance in the presence of different catalyst poisoning substances and competing electron accepting substances. The rates of reductive dehalogenation of the most prevalent VOCs were measured in pure (Milli-Q) water. Tetrachloroethylene, trichloroethylene, the DCE isomers, carbon tetrachloride and 1,2-dibromo-3-chloropropane appear to react at diffusion limited rates with no evidence for catalyst deactivation. Freon 113 and chloroform react markedly slower, by approximately 80 and 90%, respectively, and the rates of 1,1- and 1,2-dichloroethane were too small to measure. In groundwater, rates were generally slower. Possible deactivating agents are carbonic acid, bicarbonate and carbonate ions. The field-scale test conducted by the Lawrence Livermore National Laboratory to treat TCE and tritium contaminated groundwater in a treatment well using a submersed Pd reactor is ongoing.

Journal Articles on this Report : 3 Displayed | Download in RIS Format

Publications Views

Other subproject views:	All 6 publications	3 publications in selected types	All 3 journal articles
Other center views:	All 385 publications	251 publications in selected types	All 194 journal articles

Publications

Type	Citation	Sub Project	Document Sources
Journal Article	McNab WW, Ruiz R, Reinhard M. In-situ destruction of chlorinated hydrocarbons in groundwater using catalytic reductive dehalogenation in a reactive well: Testing and operational experiences. Environmental Science & Technology 2000;34(1):149-153.	R825689C078 (Final) R825689C093 (Final)	Abstract: ACS Exit
Journal Article	Schuth C, Disser S, Schuth F, Reinhard M. Tailoring catalysts for hydrodechlorinating chlorinated hydrocarbon contaminants in groundwater. Applied Catalysis B:Environmental 2000;28(3-4):147-152.	R825689C078 (Final) R825689C093 (Final) R825421 (2000)	Abstract: Science Direct Exit
Journal Article	Siantar DP, Schreier CG, Chou CS, Reinhard M. Treatment of 1,2-dibromo-3-chloropropane and nitrate-contaminated water with zero-valent iron or hydrogen/palladium catalysts. Water Research 1996;30(10):2315-2322.	R825689C054 (Final) R825689C078 (Final)	not available

Supplemental Keywords:

Groundwater, treatment, chlorinated solvents, palladium catalyst, reaction kinetics, PCE, vinyl chloride, groundwater remediation, California., RFA, Scientific Discipline, Toxics, Geographic Area, Waste, Sustainable Industry/Business, National Recommended Water Quality, cleaner production/pollution prevention, Sustainable Environment, Physics, Environmental Chemistry, Remediation, Chemistry, State, Technology for Sustainable Environment, Microbiology, Environmental Microbiology, Hazardous Waste, New/Innovative technologies, Environmental Engineering, Groundwater remediation, Hazardous, reductive dehalogenation, groundwater solutes, chlorinated solvent, catalysts, chlorinated hydrocarbons, Trichloroethylene, treatment, groundwater contamination, halogenated hydrocarbons, California (CA), Vinyl chloride, hydrodehalogenation, palladium catalyst, TCE, chlorinated solvents, groundwater

Progress and Final Reports:

Original Abstract

1995

1996

1997

1998

Main Center Abstract and Reports:

R825689    Solutions for Energy, AiR, Climate and Health Center (SEARCH)

Subprojects under this Center: (EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
R825689C001 Interactions between Electron Acceptors in the Treatment of Wastewaters Containing Sulfate, Chlorophenols and Acetate
R825689C002 Enhancing Biodegradation with Sorption and Alternating Aerobic/Anaerobic Environments
R825689C003 Development and Verification of a Numerical Model to Predict the Fate and Transport of Chlorinated Phenols in Groundwater
R825689C004 Redox Transformations of Inorganic Pollutants: Coupling to the Biogeochemical Matrix
R825689C005 Hexavalent Chromium Sorption and Desorption in Natural Soils and Subsoils
R825689C006 Biotransformation of Ordnance Wastes Using Unique Consortia of Anaerobic Bacteria
R825689C007 The Effect of Environmental Conditions on Reductive Dechlorination Rates
R825689C008 Lead Sorption, Transport, and Remediation in Natural Soils and Subsoils
R825689C009 Degradation of Chlorinated Aliphatic Compounds by Nitrifying Bacteria
R825689C010 Remediation of Contaminated Soil from the Baldock Station Maintenance Facility
R825689C011 The Effect of Apparent EH, Compound Structure, and Electron Donor on Anaerobic Biotransformation of Trinitrotoluene and its Metabolites
R825689C012 The "Bubble Wall": A Passive In Situ System for Treatment and/or Containment of Contaminated Groundwater
R825689C013 Inhibition, Inactivation and Recovery: A Universal Model for Aerobic Cometabolic Degradation of Aliphatic Compounds
R825689C014 Development, Characterization, and Performance Evaluation of Ferrous-Ferric Oxide Adsorbents for Metal Removal from Contaminated Groundwater
R825689C015 Redox Transformations of Organic and Inorganic Contaminants in the Subsurface Environment
R825689C016 Demonstration of a Permeable Barrier Technology for the Bioremediation of Ground Water Contaminated with Waste Mixtures
R825689C017 Development of a Vitamin B12-Amended Bioremediation Process for the Reductive Dechlorination of Chlorobiphenyls at all Chlorine Positions
R825689C018 An Investigation of the Chlorinated Hydrocarbon Substrate Range of the Filamentous Fungus, Graphium sp.
R825689C019 Aerobic Cometabolism of Chloroform, 1,1,1-trichloroethane, 1,1-dichloroethylene, and Other Chlorinated Aliphatic Hydrocarbons by Microbes Grown on Butane and Propane
R825689C020 Cytochrome P-450: An Emerging Catalyst for the Cometabolism of Chlorinated Aliphatic Hydrocarbons and Methyl tert-butyl Ether?
R825689C021 In-Situ Measurement of TCE Degradation Using a Single-Well "Push-Pull" Test
R825689C022 Development and Characterization of Redox Sensors for Environmental Monitoring
R825689C023 Assessing Metal Speciation in the Subsurface Environment
R825689C024 Simultaneous Removal of the Adsorbable and Electroactive Metals from Contaminated Soils and Groundwater
R825689C025 Multisolute Sorption and Transport Model for Copper, Chromium, and Arsenic Sorption on an Iron-Coated Sand, Synthetic Groundwater System
R825689C026 Development of Alkoxysilanes as Slow Release Substrates for the Anaerobic/Aerobic Transformation of Chlorinated Solvents
R825689C027 Aerobic Cometabolism of Chlorinated Aliphatic Hydrocarbons by Toluene-Oxidizing Bacteria
R825689C028 Development and Characterization of Sensors and Field Instrumentation for Monitoring of Environmental Redox Conditions
R825689C029 Aerobic Cometabolism of Methyl tert-butyl Ether by Microorganisms Grown on Aliphatic Hydrocarbons
R825689C030 Biotransformation of Lead and Chromate by Bacteria
R825689C031 Magnetic Resonance Studies of Heavy Metals in Clays, Zeolites and Ceramics
R825689C032 Probing the Redox Properties of Environmental Systems: Natural Phenolic Materials
R825689C033 Reductive Dehalogenation at Carbon and Derivatized Carbon Electrodes
R825689C034 Detection of Microorganisms Capable of Anaerobic Degradation of Hazardous Substances in Natural Environments
R825689C035 Treatment of Complex Mixtures
R825689C036 Oxidation of Chlorinated Solvents by Methanotrophs
R825689C037 Detection and Assessment of Subsurface Contamination
R825689C038 Design of Reliable and Cost-Effective Mitigation Schemes
R825689C039 Gaseous Stripping of Nonaqueous Phase Liquids from the Vadose Zone
R825689C040 Anaerobic Microbial Transformation of Homocyclic and Heterocyclic Polynuclear Aromatic Hydrocarbons
R825689C041 Effects of Sorption on Biodegradation of Halogenated Organics
R825689C042 Trace Metal Removal Processes
R825689C043 FASTCHEM Applications and Sensitivity Analysis
R825689C044 Long-term Chemical Transformation of 1,1,1-Trichloroethane (TCA) and Freon 113 under Aquifer Conditions
R825689C045 In-Situ Anaerobic Biological Treatment of Aromatics in Groundwater
R825689C046 Use of Starvation and Stress Promoters for Biodegradation of Hazardous Wastes
R825689C047 Determining and Modeling Diffusion-Limited Sorption and Desorption Rates of Organic Contaminants in Heterogeneous Soils
R825689C048 Dispersion Modeling of Volatile Organic Emissions from Ground-Level Treatment Systems
R825689C049 Subsurface Mixing of Nutrients and Groundwater for in-Situ Bioremediation
R825689C050 Test-Bed Evaluation of In-Situ Bioremediation of Chlorinated Aliphatic Compounds by Toluene Oxygenase Microorganisms
R825689C051 Demonstration of in-Situ Bioremediation of Chlorinated Aliphatics by Methanotrophs at St. Joseph
R825689C052 Aquifer Remediation Design in the Presence of Kinetic Limitations
R825689C053 Determination of Macroscopic Transport Parameters for Biologically Reacting Solutes in Aquifers
R825689C054 Transformation of Chlorinated Hydrocarbons by Reduced Metallocoenzymes--Kinetic Model Development and Applications to Environmental Systems
R825689C055 Microbial Degradation of Toluene Under Sulfate-Reducing Conditions--The Role of Iron
R825689C056 Transformation of TCE by Methanotrophic Biofilms
R825689C057 Heavy Metals in Ceramic Matrix: Heavy Metals/Clay Interactions in Ceramic Processing
R825689C058 Radon-222 Method for Locating and Quantifying Contamination by Residual Non-Aqueous Phase Liquids in the Subsurface
R825689C059 Process Submodel Formulation and Parameter Estimation for Simulation of Bioremediation
R825689C060 Enhancement of Biodegradation through the Use of Substituted Porphyrins to Treat Groundwater Contaminated with Halogenated Aliphatics
R825689C061 Field Test of In-Situ Vapor Stripping for Removal of VOCS from Groundwater
R825689C062 System Design for Enhanced In-Situ Biotransformation of Carbon Tetrachloride: Application to DOE's Arid Site Integrated Demonstration
R825689C063 Modeling Strategies for Optimizing In-Situ Bioremediation
R825689C064 Anaerobic Treatment of Chlorinated Solvent Contaminated Groundwater
R825689C065 In Situ Treatment of Chlorinated Solvents
R825689C066 Moffett Field In-Situ Bioremediation Study in Support of Full Scale Application
R825689C067 Full-Scale Evaluation of In Situ Bioremediation of Chlorinated Solvent Groundwater Contamination
R825689C068 Upscaling Pore-Scale Hydrodynamics and the Transport of Reactive Solutes
R825689C069 Pathways of Anaerobic Toluene Metabolism by a Sulfate-Reducing Bacterium, Strain PRTOL1
R825689C070 Anaerobic Ethylbenzene Oxidation in Denitrifying Strain EB1
R825689C071 Molecular Approaches to Optimize Starvation Promoter Dricen TCE Bioremediation in Pseudomonas
R825689C072 Modeling VOC Emissions from Hazardous Waste Sites
R825689C073 Reductive Transformation of Chlorinated Hydrocarbons by Reduced Ethenes Catalyzed by Vitamin B12 - Mechanistic and Kinetic Studies
R825689C074 Evaluation of Strategies for Full Scale Bioremediation of the Seal Beach Site Using Anaerobic Microbial Processes
R825689C075 Trace Element Adsorption in Porous Particle Packed Beds
R825689C076 Hydrologic and Biological Factors Affecting Aquifer Clogging During In-Situ Bioremediation
R825689C077 Full-Scale Evaluation of an Apparatus for Down-well Oxygen Transfer to Implement In situ Bioremediation at Edwards AFB
R825689C078 Field Testing of Palladium-Catalyzed Hydrodehalogenation for Chlorinated Hydrocarbon Removal from Groundwater
R825689C079 Physics of Dissolution of Nonaqueous Phase Liquids: Pore Networks and Field Simulations
R825689C080 Three-Phase Flow in Fractured Media
R825689C081 Effects of Redox Zones on the Fate and Transport of Contaminants in the Saturated Subsurface; Characterization and Simulation
R825689C082 Biochemical Mechanisms of PCE Dehalogenation by Strain MS-1, and its Potential for In-situ Bioaugmentation
R825689C083 A Large Scale Model for Anaerobic Bioremediation at the Seal Beach Site
R825689C084 Mechanisms, Chemistry, and Kinetics of Anaerobic Degradation of cDCE and Vinyl Chloride
R825689C085 Bioenhanced In-Well Vapor Stripping to Treat Trichloroethylene (TCE)
R825689C086 Effect of Chemical Structure on the Biodegradability of Halogenated Hydro-carbons
R825689C087 Trace Element Adsorption in Porous Particle Packed Beds
R825689C088 Arsenic Removal in High Capacity Porous Alumina Packed-Bed Reactors
R825689C089 Measurement of Interfacial Areas and Mass Transfer Coefficients Between Residual PCE and Water During Surfactant Enhanced Aquifer Remediation
R825689C090 Proof of Gene Expression During Bioaugmentation
R825689C091 Experimental and Mathematical Study of Biomass Growth in Pore Networks and its Consequences in Bioremediation
R825689C092 Gene probes for detecting anaerobic alkylbenzene-degrading bacteria
R825689C093 Investigation of Palladium Catalyzed Hydrodehalogenation for the Removal of Chlorinated Groundwater Contaminants: Surface Chemistry of Catalyst Deactivation and Regeneration
R825689C094 Aerobic Methanotrophic Transformation of Biphenyl, Monochlorobiphenyls, and Dichlorobiphenyls