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2004 Progress Report: Effect of Pitting Corrosion Promoters on the Treatment of Waters Contaminated with a Nitroaromatic Compounds Using Integrated Reductive/Oxidative Processes
EPA Grant Number: R831276C008Subproject: this is subproject number 008 , established and managed by the Center Director under grant CR831276
(EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
Center: Gulf Coast HSRC (Lamar)
Center Director: Ho, Tho C.
Title: Effect of Pitting Corrosion Promoters on the Treatment of Waters Contaminated with a Nitroaromatic Compounds Using Integrated Reductive/Oxidative Processes
Investigators: Hernandez, Rafael , Kuo, Chiang Hai
Institution: Mississippi State University
EPA Project Officer: Krishnan, Bala S.
Project Period: December 1, 2003 through November 30, 2004
Project Period Covered by this Report: December 1, 2003 through November 30, 2004
Project Amount: Refer to main center abstract for funding details.
RFA: Gulf Coast Hazardous Substance Research Center (Lamar University) (1996)
Research Category: Hazardous Waste/Remediation , Targeted Research
Description:
Objective:The main goal of this research project is the development of a reductive/oxidative integrated technology for the treatment of waters contaminated with nitroaromatic compounds (NACs). The idea is to develop a cost-effective technology that can mineralize and/or transform NACs into low-molecular weight nontoxic compounds, which cannot be done using today’s technologies as stand-alone treatment processes. The specific objectives of the research project are to: (1) evaluate the effect of different pitting corrosion promoters on 2,4-dinitrotoluene (DNT) reduction and byproducts oxidation kinetics using iron or manganese and advanced oxidation processes (AOPs), respectively, and determine the optimum operating conditions for both processes and the toxicity of the effluents from the oxidation step operating at optimum conditions using Microtox; (2) synthesize bimetallic iron/manganese species and analyze the reaction byproducts obtained during the application of these bimetallic species for the treatment of water contaminated with DNT (this will be the first time that iron/manganese bi-metallic species are synthesized and evaluated for the treatment of DNT contaminated water); and (3) develop a kinetic rate expression that couples metal corrosion with NACs degradation and a kinetic expression for nitroamines (DNT reduction byproducts) mineralization using AOPs.
Progress Summary:The effect of corrosion promoters on DNT degradation by iron or manganese was evaluated using the recirculated batch reactor described elsewhere. The experiments were conducted under anaerobic conditions (< 0.5 mg/L O2 dissolved in water) and 4 g/L iron or manganese. The initial DNT concentration in all the experiments was 20 mg/L. Figure 1 shows the effect of adding ferric chloride (FeCl3) or sodium chloride (NaCl) to DNT contaminated water (synthetic) on the DNT reaction with zero valent iron (ZVI). In the absence of corrosion promoters, 30 percent of the initial DNT was removed in 3 hours. A noticeable increase in DNT degradation can be observed at a concentration as low as 5 μM FeCl3. Higher FeCl3 concentrations accelerated further the rate of reaction of DNT with ZVI. The highest FeCl3 concentration examined was 3 mM, which yielded 100 percent DNT disappearance in 3 hours. A comparison of DNT degradation using 3 mM FeCl3 or NaCl indicates faster DNT degradation kinetics are obtained in the presence of FeCl3. This result could be attributed to the fact that FeCl3 is a better corrosion promoter compared to NaCl and thus causes a larger rate of electron generation. It is these electrons that react with DNT adsorbed onto the metal surface forming reduction byproducts.
Results for the DNT degradation using zero-valent manganese in the presence of FeCl3 or NaCl are presented in Figure 2. In this case, only the highest concentrations of FeCl3 or NaCl (3 mM) evaluated had a significant effect on DNT degradation. In this case, addition of FeCl3 also resulted in faster DNT degradation. It appears the manganese oxide layer is more resistant to oxidation than ZVI. A relatively high concentration of a corrosion promoter is necessary to break it, obtain access to the metallic surface, and accelerate the corrosion process and DNT degradation.
Figure 1. Effect of FeCl3 or NaCl on DNT Degradation by ZVI
Figure 2. Effect of FeCl3 or NaCl on DNT Degradation by Zero-Valent Manganese
The calculated surface area normalized first order rate constants for the reaction of DNT with ZVI or manganese in the presence of 3 mM FeCl3 were 0.245 and 0.176 L/m2minute, respectively. These rate constants are orders of magnitude higher than several values reported for reactions of ZVI with NACs. The reaction acceleration obtained by adding corrosion promoters could reduce significantly capital and operating costs of treating NACs-contaminated waters using zero-valent metals.
The initial surface areas of the metals were 0.0537 m2/g iron and 0.0405 m2/g manganese. The surface areas at the end of the reaction period (in the presence of 3 mM FeCl3) were 2.8053 m2/g and 0.3922 m2/g for ZVI and manganese, respectively. The large increase in the surface area of ZVI suggested formation of dislocations, cracks, and pits on its surface. Figure 3 shows scanning electron micrographs of the ZVI surface before and after reaction with DNT. Prior to reaction, the ZVI surface was smooth and nonporous, which explains the relatively small surface area. Figure 3 (right micrograph) indicates that numerous pits were formed during reaction, causing the surface area increase. The appearance of pits on the ZVI surface also indicates the main corrosion mechanism was pitting, a form of localized corrosion that occurs in the presence of aggressive anionic species such as chloride. The salt that forms inside the pits hydrolyzes and generates hydrochloric acid (HCl). The induced pits act as continuous sources of electrons and the microacidic (HCl) environment generated inside the pits minimizes passivation, autocatalyzes metal pitting, and accelerates DNT degradation.
Figure 3. Scanning Electron Micrographs of the ZVI Surface Before and After Reaction With DNT in the Presence of 3 mM FeCl3
The small increase in manganese surface area during reaction with DNT in the presence of FeCl3 indicates manganese has more resistance to corrosion compared to ZVI. It seems manganese will maintain its metallic properties longer (slower rate of deactivation) than ZVI in the presence of corrosion promoters. Other experiments have shown that the yield and selectivity for some reduction byproducts depend on the metal identity. Presently, bimetallic manganese/iron species are being synthesized to optimize for corrosion resistance, yield, and selectivity of the reduction byproducts. These new metallic species will be integrated to advanced oxidation processes to mineralize the DNT reduction byproducts.
Future Activities:The bimetallic iron/manganese particles are being synthesized and will be evaluated for treating DNT-contaminated water. The bimetallic species will be integrated to an advanced oxidation process to mineralize the DNT byproducts generated during the reduction step. A paper will be submitted to Environmental Science & Technology or the Journal of Environmental Engineering. Additionally, papers will be presented at the 2005 Southern States Environmental Conference and the 2005 Annual Meeting of the American Institute of Chemical Engineers.
Journal Articles on this Report: 1 Displayed | Download in RIS Format
| Other subproject views: | All 2 publications | 1 publications in selected types | All 1 journal articles |
| Other center views: | All 472 publications | 140 publications in selected types | All 123 journal articles |
| Type | Citation | ||
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Hernandez R, Zappi M, Kuo C-H. Chloride effect on TNT degradation by zerovalent iron or zinc during water treatment. Environmental Science & Technology 2004;38(19):5157-5163. |
R831276C008 (2004) |
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peroxone, pitting corrosion, hybrid treatment processes, amines oxidation, waste, ecological risk assessment, environmental engineering, hazardous waste, advanced treatment technologies, bioremediation, contaminated waste sites, groundwater contamination, petroleum contaminants, hydrocarbon,
,
Water, Scientific Discipline, Waste, RFA, Remediation, Hazardous Waste, Environmental Engineering, Environmental Chemistry, Contaminated Sediments, Hazardous, oxidizing agents, nitroaromatic compounds, groundwater, hazardous waste storage, contaminated sediment, hazardous wate, reductive oxidative processes, contaminated soil, corrosion promoters, advanced treatment technologies, contaminated groundwater, groundwater remediation, hazardous waste treatment
Relevant Websites:
Progress and Final Reports:
Original Abstract
Main Center Abstract and Reports:
CR831276 Gulf Coast HSRC (Lamar)
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
R831276C001 DNAPL Source Control by Reductive Dechlorination with Fe(II)
R831276C002 Arsenic Removal and Stabilization with Synthesized Pyrite
R831276C003 A Large-Scale Experimental Investigation of the Impact of Ethanol on Groundwater Contamination
R831276C004 Visible-Light-Responsive Titania Modified with Aerogel/Ferroelectric Optical Materials for VOC Oxidation
R831276C005 Development of a Microwave-Induced On-Site Regeneration Technology for Advancing the Control of Mercury and VOC Emissions Employing Activated Carbon
R831276C006 Pollution Prevention through Functionality Tracking and Property Integration
R831276C007 Compact Nephelometer System for On-Line Monitoring of Particulate Matter Emissions
R831276C008 Effect of Pitting Corrosion Promoters on the Treatment of Waters Contaminated with a Nitroaromatic Compounds Using Integrated Reductive/Oxidative Processes
R831276C009 Linear Polymer Chain and Bioengineered Chelators for Metals Remediation
R831276C010 Treatment of Perchlorate Contaminated Water Using a Combined Biotic/Abiotic Process
R831276C011 Rapid Determination of Microbial Pathways for Pollutant Degradation
R831276C012 Simulations of the Emission, Transport, Chemistry and Deposition of Atmospheric Mercury in the Upper Gulf Coast Region
R831276C013 Reduction of Environmental Impact and Improvement of Intrinsic Security in Unsteady-state
R831276C014 Integrated Chemical Complex and Cogeneration Analysis System: Greenhouse Gas Management and Pollution Prevention Solutions
R831276C015 Improved Combustion Catalysts for NOx Emission Reduction
R831276C016 A Large-Scale Experimental Investigation of the Impact of Ethanol on Groundwater Contamination
R831276C017 Minimization of Hazardous Ion-Exchange Brine Waste by Biological Treatment of Perchlorate and Nitrate to Allow Brine Recycle
R831276C018 Integrated Chemical Complex and Cogeneration Analysis System: Greenhouse Gas Management and Pollution Prevention Solutions