Grantee Research Project Results

1999 Progress Report: Degradative Solidification/Stabilization Technology for Chlorinated Hydrocarbons

EPA Grant Number: R822721C552
Subproject: this is subproject number 552 , established and managed by the Center Director under grant R828598
(EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
Center: Organotypic Culture Models For Predictive Toxicology Center
Center Director: Rusyn, Ivan
Title: Degradative Solidification/Stabilization Technology for Chlorinated Hydrocarbons
Investigators: Batchelor, Bill , Carraway, Elizabeth
Institution: Texas A & M University
EPA Project Officer: Aja, Hayley
Project Period: September 1, 1996 through March 31, 2000
Project Period Covered by this Report: September 1, 1998 through March 31, 1999
RFA: Gulf Coast Hazardous Substance Research Center (Lamar University) (1996) RFA Text |  Recipients Lists
Research Category: Hazardous Waste/Remediation , Targeted Research

Objective:

The objective of the proposed research is to identify combinations of reagents (surfaces, electron carriers, and electron donors), reaction conditions that are appropriate for use in degradative solidification/stabilization systems and to demonstrate the feasibility of using one combination in a commercial degradative solidification / stabilization (ds/s) treatment systems.

Progress Summary:

The high pH screening experiments showed that Fe(II) could degrade Tetrachloroethene (PCE) in the in the presence of Portland cement at 40°C. When 100 times the stoichiometric amount of Fe(II) was used, removal of PCE occurred with a half-life of 5.6 days.. Experiments were carried out to further characterize Fe(II) systems using batch slurry reactors at room temperature. Cement was found to catalyze or participate in the PCE degradation reaction, because PCE removal was minimal in the absence of cement or in the presence of solid phases such as tricalcium silicate and hydrated lime. In Fe(II)/cement systems, PCE degradation occurred over the investigated pH range (10.6-13.8), but was optimal at pH ~12.1 with the half-life of 4.8 days when [Fe(II)] = 39.2 mM. Under this condition, 94.4% of PCE was transformed into non-chlorinated carbons, which consist of acetylene (82.1%), ethylene (17.6%), and ethane (0.33%). Product analyses showed that chloride was released from PCE almost stoichiometrically and that production of chlorinated intermediate compounds was minimal. The PCE degradation rate increased as [Fe(II)] increased from 9.8 mM to 98 mM, but it did not change substantially when [Fe(II)] increased from 98 mM to 196 mM. The presence of humic substances (500 mg TOC/L) in the Fe(II)/cement system did not significantly change the rate of PCE degradation. The effectiveness of Fe(II) with a contaminated soil that was solidified with cement was tested. PCE was spiked into soil/cement mixtures containing various amount of Fe(II) (5,388 mg - 53,880 mg/kg soil) to yield a concentration of 100 mg/kg soil. Half-lives of PCE ranged from 14 to 124 days, which are well suited to the time spans allowable for remediation of contaminated soils in situ. TCE was the only chlorinated product observed in the solid phase experiments and its presence was transitory with the amount being less than 7% of the initial amount of PCE on a molar basis. The component-based leach models were developed to describe one-dimensional diffusive transport of the contaminant under the assumption of linear sorption and first-order degradation. The single-component model can be solved analytically and its simulation shows that the contaminant leaching can be determined by first and second Damköler numbers and dimensionless time. The numerical simulation of three-component (contaminant, H+, calcium) model can describe the effect of pH on degradation. For moderate pH systems, the dechlorination of PCE by zero-valent zinc in the presence of hydroxyapatite (Ca5(PO4)3OH) was characterized with respect to the optimal pH, the identity and distribution of reaction products, and the effects of the hydoxyapatite. In the pH experiment, the rates of PCE dechlorination at four moderate range pH (6, 7, 8, 9) were compared. The estimated half-lives of PCE calculated by using a first-order decay model were 21, 1.3, 0.65, and 0.73 hours at initial pH of 6, 7, 8, and 9, respectively. It was also observed that distribution and persistence of the reaction products were affected by pH. In the absence of hydroxyapatite, TCE was produced from the reduction of PCE and was very resistant to subsequent degradation over the duration of the experiment (720 hours). However, in the presence of hydroxyapatite, an enhancement of TCE reduction was observed, though the rate was very low compared to that of PCE. In particular, Zn²⁺ released by oxidative dissolution of the metallic zinc was effectively removed in the solution by the hydroxyapatite. The system optimized during the characterization phase was further investigated to its heavy metal (Cd²⁺) stabilization capacity. The results indicate that the system composed of zero-valent zinc and hydroxyapatite can simultaneously achieve the dechlorination of PCE and the stabilization of Cd²⁺ as well as Zn²⁺. However, some indication of redox reaction between zinc and Cd²⁺ was observed and such peripheral reaction resulted in decreased rate of TCE reduction. To minimize the production of undesirable PCE reduction products (TCE, trans-DCE), zinc coated with palladium was incorporated into the system as an alternative to the plain zinc. The results indicate that Pd/Zn (0.06 % Pd by mass) achieved complete removal of PCE reduction products in a short period of time (48 hours by 1 g of Pd/Zn reacted to 0.2 mM of PCE), while giving comparable PCE reduction rate to the plain zinc. In the soil medium, however, the system was shown to be not as effective as in the aqueous medium, probably because of PCE/TCE partitioning into soil organic matter and hindrance in PCE/TCE mass transport by the soil.

Future Activities:

Experiments on applying the cement/Fe(II) technology to contaminated soils using solid-phase systems will continue. Partitioning experiments will be completed to aid applying slurry phase kinetics to solid phase systems. Attempts will be made to use x-ray diffraction spectroscopic analysis to identify the key reductant species in systems with cement and Fe(II).

Journal Articles:

No journal articles submitted with this report: View all 2 publications for this subproject

Supplemental Keywords:

solidification/stabilization, reductive dechlorination, ferrous iron, zero-valent metal, chlorinated ethenes., RFA, Scientific Discipline, TREATMENT/CONTROL, INTERNATIONAL COOPERATION, Waste, Water, ENVIRONMENTAL MANAGEMENT, Hazardous, Remediation, Chemical Engineering, Environmental Chemistry, Analytical Chemistry, Contaminated Sediments, Hazardous Waste, Treatment Technologies, Bioremediation, Ecology and Ecosystems, Environmental Engineering, Risk Assessment, risk based modeling, bioremediation of soils, biotransformation, contaminated sediment, sediment treatment, hazardous waste management, hazardous waste treatment, chlorinated hydrocarbons, chemical contaminants, transport models, contaminated soil, risk characterization, electron donor, remediation technologies, stabilization remediation , biodegradation, environmentally acceptable endpoints, degradative solidification, PCE, environmental technology, soil and groundwater remediation, hazardous waste site, toxics, contaminated waste sites, heavy metal contamination, contaminants in soil, contaminated soils, decontamination of soil

Progress and Final Reports:

Original Abstract

1997

1998

Final

Main Center Abstract and Reports:

R828598    Organotypic Culture Models For Predictive Toxicology Center

Subprojects under this Center: (EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
R822721C529 Environmentally Acceptable Endpoints: Risk Based Remediation Using Bioremediation
R822721C552 Degradative Solidification/Stabilization Technology for Chlorinated Hydrocarbons
R822721C569 Treatment and Product Recovery: Supercritical Water Oxidation of Nylon Monomer Manufacturing Waste
R822721C620 Colloidal Fouling of Membranes: Implications in the Treatment of Textile Dye Wastes and Water Reuse
R822721C626 Catalytic Hydroprocessing of Chlorinated Organics
R822721C627 The Interaction of Microbial Activity and Zero Valent Iron Permeable Barrier Technology
R822721C630 Microbial Cometabolism of Recalcitrant Chemicals in Contaminated Air Streams
R822721C633 Catalyst Lifetime Studies for Chlorocarbon Steam Reforming
R822721C635 Electrokinetic/Surfactant-Enhanced Remediation of Hydrophobic Pollutants in Low Permeability Subsurface Environments
R822721C636 Transformation Reactions of Nitroaromatic and Nitrogen Heterocyclic Compounds on Granular Activated Carbon (GAC) Surfaces: Enhancement of GAC Adsorption in Natural and Engineered Environmental Systems
R822721C640 Environmentally Friendly Organic Synthesis in Supercritical Fluids
R822721C645 Development and Evaluation of an Integrated Model to Facilitate Risk-Based Corrective Action at Superfund Sites
R822721C651 Adjustable Biopolymer Chelators for Cadmium, Lead and Mercury
R822721C653 New Electrochemically Smart Catalysts for Hazardous Waste Management and Development of Capillary Electrophoresis for Analysis of their Products
R822721C655 Soil Sampling in South Alabama Oil Fields
R822721C659 Subsurface Contamination Site Characterization via a Computer-Aided Visual Tool
R822721C661 New Insoluble supports for Protein Immobilization for Use in Metalloprotein Affinity Metal Chromatography
R822721C663 Soil Remediation with Ultra-High-Efficiency Hydrocyclones
R822721C669 Solid Acid Catalyzed Alkylation in Supercritical Fluids
R822721C679 Regeneration/Reactivation of Carbon Adsorbents by Radio Frequency (RF) Induction Heating
R822721C687 Improved Halogen Resistance of Catalytic Oxidation
R822721C696 Phytoremediation and Bioremediation of Land Contaminated By PAHs, PCBs, and TNT
R822721C697 Fundamental and Kinetic Investigation of Sorbent Technology for Optimum Mercury Emission Control
R822721C700 Effects of Natural and Cyclic Variations on Contaminant Fate and Transport
R822721C703 Enhancement of DNAPL Dissolution Rates by Dechlorinating Anaerobes
R826694C620 Colloidal Fouling of Membranes: Implications in the Treatment of Textile Dye Wastes and Water Reuse
R826694C625 Enhanced Treatment of DNAPLs Contaminated Soils and Groundwater Using Biosurfactants: In-Situ Bioremediation
R826694C626 Catalytic Hydroprocessing of Chlorinated Wastes
R826694C627 The Interaction of Microbial Activity and Zero Valent Iron Permeable Barrier Technology
R826694C629 Biofiltration of BTEX in Petroleum-Contaminated Soil Remediation Off-Gas
R826694C630 Microbial Cometabolism of Recalcitrant Chemicals in Contaminated Air Streams
R826694C633 Catalyst Lifetime Studies for Chlorocarbon Steam Reforming
R826694C635 Electrokinetic/Surfactant-Enhanced Remediation of Hydrophobic Pollutants in Low Permeability Subsurface Environments
R826694C636 Transformation Reactions of Nitroaromatic and Nitrogen Heterocyclic Compounds on Granular Activated Carbon (GAC) Surfaces: Enhancement of GAC Adsorption in Natural and Engineered Environmental Systems
R826694C640 Environmentally Friendly Organic Synthesis in Supercritical Fluids
R826694C645 Development and Evaluation of an Integrated Model to Facilitate Risk-Based Corrective Action at Superfund Sites
R826694C651 Adjustable Biopolymer Chelators for Cadmium, Lead, and Mercury Remeidation
R826694C659 Subsurface Contamination Site characterization Via a Computer-Aided Visual Tool
R826694C661 New Insoluble supports for Protein Immobilization for Use in Metalloprotein Affinity Metal Chromatography
R826694C669 Solid Acid Catalyzed Alkylation in Supercritical Reaction Media
R826694C679 Regeneration and Reactivation of Carbon Adsorbents by Radio Frequency Induction Heating
R826694C696 Phytoremediation and Bioremediation of Land Contaminated By PAHs, PCBs, and TNT
R826694C697 Fundamental and Kinetic Investigation of Sorbent Technology for Optimum Mercury Emission Control
R826694C700 Effects of Natural Cyclic Variations on Contaminated Fate and Transport
R826694C703 Enhancement of DNAPL Dissolution Rates by Dechlorinating Anaerobes
R826694C705 A Pilot Plant for Producing Mixed Ketones from Waste Biomass
R826694C722 The Effects of an Oily-Phase on VOC Emissions from Industrial Wastewater
R826694C724 Mercury Removal from Stack Gas by Aqueous Scrubbing
R826694C725 Transport, Fate and Risk Implications of Environmentally Acceptable Endpoint Decisions
R826694C731 Development and Application of a Real-Time Optical Sensor for Atmospheric Formaldehyde
R826694C734 An Advanced System for Pollution Prevention in Chemical Complexes
R828598C001 Field Study Abstract: A Model of Ambient Air Pollution in Southeast Texas Using Artificial Neural Network Technology
R828598C002 Hollow Fiber Membrane Bioreactors for Treating Water and Air Streams Contaminated with Chlorinated Solvents
R828598C003 Fugitive Emissions of Hazardous Air Pollutants from On-Site Industrial Sewers
R828598C004 Biofiltration Technology Development
R828598C005 A Risk-Based Decision Analysis Approach for Aquifers Contaminated with DNAPLs
R828598C006 In-Situ Remediation for Contaminated Soils Using Prefabricated Vertical Drains
R828598C007 Membrane Technology Selection System for the Metal Finishing Industry
R828598C008 Sequential Environments for Enhanced Bioremediation of Chlorinated Aliphatic Hydrocarbons
R828598C009 Waste Minimization in the Magnetic Tape Industry: Waterborne Coating Formulations for Magnetic Tape Manufacture
R828598C010 Soil Remediation by Agglomeration with Petroleum Coke
R828598C011 Recovery of Dilute Phosphoric Acid in Waste Streams Using Waste Gas Ammonia: The Regenerative MAP/DAP Process
R828598C012 Stochastic Risk Assessment for Bioremediation
R828598C013 Selective Removal of Heavy Metals from Wastewater by Chelation in Supercritical Fluids
R828598C014 Optimization of Treatment Technologies for Detoxification of PCB Contaminated Soils
R828598C015 Wastewater Remediation by Catalytic Wet Oxidation
R828598C016 Permanence of Metals Containment in Solidified and Stabilized Wastes
R828598C017 Combustion Enhancement by Radial Jet Reattachment - Low Generation of Hazardous Gases and High Thermal Efficiency
R828598C018 A Process To Convert Industrial Biosludge and Paper Fines to Mixed Alcohol Fuels
R828598C019 Homogeneous Catalysis in Supercritical Carbon Dioxide
R828598C020 Ultrasonic Enhancement of the Removal of Heavy Metals
R828598C021 The Binding Chemistry and Leaching Mechanisms of Advanced Solidification/Stabilization Systems for Hazardous Waste Management
R828598C022 Development of an Air-Stripping and UV/H2O2 Oxidation Integrated Process To Treat a Chloro-Hydrocarbon-Contaminated Ground Water
R828598C023 A Comparative Study of Siting Opposition in Two Counties
R828598C024 Sonochemical Treatment of Hazardous Organic Compounds II: Process Optimization and Pathway Studies
R828598C025 Laser Diagnostics of the Combustion Process within a Rotary Kiln Incinerator
R828598C026 Use of Inorganic Ion Exchangers for Hazardous Waste Remediation
R828598C027 Kaolinite Sorbent for the Removal of Heavy Metals from Incinerated Lubricating Oils
R828598C028 Destruction of Chlorinated Hydrocarbons in Process Streams Using Catalytic Steam Reforming
R828598C029 Integrated Process Treatment Train (Bioremediation {Aerobic/Anaerobic} and Immobilization) for Texas Soils Contaminated with Combined Hazardous Wastes
R828598C030 Photo-Oxidation by H2O2/VisUV of Off-Gas Atmospheric Emissions from Industrial and Environmental Remediation Sources
R828598C031 Concentrated Halide Extraction and Recovery of Lead from Soil
R828598C032 Biodegradable Surfactant for Underground Chlorinated Solvent Remediation
R828598C033 A Software Guidance System for Choosing Analytical Subsurface Fate and Transport Models Including a Library of Computer Solutions for the Analytical Models
R828598C034 Hydrodynamic Modeling of Leachate Recirculating Landfill
R828598C035 Measurement of Oxygen Transfer Rate in Soil Matrices
R828598C036 Sorbent Technology for Multipollutant Control During Fluidized Bed Incineration
R828598C037 Pollution Prevention by Process Modification Using On-Line Optimization
R828598C038 Pollution Prevention by Process Modification
R828598C039 Water Solubility and Henry's Law Constant
R828598C040 Transferring Technical Information on Hazardous Substance Research by Publishing on the World Wide Web
R828598C041 Stress Protein Responses to Multiple Metal Exposure in Grass Shrimp
R828598C042 Life-Cycle Environmental Costing for Managing Pollution Prevention in the Chemical and Petroleum Refining Industries: A Cross-Border Approach
R828598C687 Improved Halogen Resistance of Catalytic Oxidation Through Efficient Catalyst Testing
R828598C696 Phytoremediation and Bioremediation of Land Contaminated By PAHs, PCBs, and TNT
R828598C697 Fundamental and Kinetic Investigation of Sorbent Technology for Optimum Mercury Emission Control
R828598C700 Effects of Natural Cyclic Variations on Contaminated Fate and Transport
R828598C703 Enhancement of DNAPL Dissolution Rates by Dechlorinating Anaerobes
R828598C705 A Pilot Plant for Producing Mixed Ketones from Waste Biomass
R828598C722 The Effects of an Oily-Phase on VOC Emissions from Industrial Wastewater
R828598C724 Mercury Removal from Stack Gas by Aqueous Scrubbing
R828598C725 Transport, Fate and Risk Implications of Environmentally Acceptable Endpoint Decisions
R828598C731 Development and Application of a Real Time Optical Sensor for Atmospheric Formaldehyde
R828598C734 An Advanced System for Pollution Prevention in Chemical Complexes
R828598C743 Field Demonstration of Ultrasound Enhancement of Permeable Treatment Walls
R828598C744 Optical Fibers Coated With Titania Membrane/UV-Generating Crystal in a Distributed-Light Photoreactor for VOC Oxidation
R828598C749 Characterization and Modeling of Indoor Particulate Contaminants In a Heavily Industrialized Community
R828598C753 Adsolubilization and Photocatalysis in a Semiconducting Monolithic Reactor for Wastewater Treatment
R828598C754 Remote Detection of Gas Emissions in Industrial Processes
R828598C759 Searching for Optimum Composition of Phosphogypsum: Fly ash: Cement Composites for Oyster Culch Materials
R828598C761 Development of a Phytologically-Based Biosorptive Water Treatment Process
R828598C766 Chlorinated Solvent Impact and Remediation Strategies for the Dry Cleaning Industry
R828598C769 Soil/Sediment Remediation by Hot Water Extraction Combined with In-Situ Wet Oxidation
R828598C771 Fluoracrylate Polymer Supported Ligands as Catalysts for Environmentally Benign Synthesis in Supercritical Fluids
R828598C774 The Feasibility of Electrophoretic Repair of Impoundment Leaks
R828598C777 Surfactant Enhanced Photo-oxidation of Wastewaters
R828598C778 Stationary Power Generation Via Solid Oxide Fuel Cells: A Response to Pollution and Global Warming
R828598C786 Photocatalytic Recovery of Sulfur and Hydrogen From Hydrogen Sulfide
R828598C787 Biosurfactant Produced from Used Vegetable Oil for removal of Metals From Wastewaters and Soils
R828598C789 Genetic Engineering of Enzymatic Cyanide Clearance
R828598C791 Characterizing the Intrinsic Remediation of MTBE at Field Sites
R828598C799 Simultaneous Water Conservation/Recycling/Reuse and Waste Reduction in Semiconductor Manufacturing
R828598C801 Building Defined Mixed Cultures To Biodegrade Diverse Mixtures Of Chlorinated Solvents
R828598C802 Engineering of Nanocrystal Based Catalytic Materials for Hydroprocessing of Halogenated Organics
R828598C807 Commercial Demonstration of Hydrogen Peroxide Injection to Control NOx Emissions from Combustion Sources
R828598C809 Evaluating Source Grouting and ORC for Remediating MTBE Sites
R828598C810 Application of Total Cost Assessment To Process Design In the Chemical Industry
R828598C846 Quantitative Demonstration of Source-Zone Bioremediation in A Field-Scale Experimental Controlled Release System