Grantee Research Project Results

Adjustable Biopolymer Chelators for Cadmium, Lead and Mercury

EPA Grant Number: R822721C651
Subproject: this is subproject number 651 , 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: UT Center for Infrastructure Modeling and Management
Center Director: Hodges, Ben R.
Title: Adjustable Biopolymer Chelators for Cadmium, Lead and Mercury
Investigators: Holcombe, James , Iverson, Brent L.
Current Investigators: Holcombe, James , Iverson, Brent L. , Browning, Karen
Institution: The University of Texas at Austin
EPA Project Officer: Aja, Hayley
Project Period: September 1, 1998 through September 1, 1999
RFA: Gulf Coast Hazardous Substance Research Center (Lamar University) (1996) RFA Text |  Recipients Lists
Research Category: Hazardous Waste/Remediation , Targeted Research

Objective:

Environmental contamination by metals has increased, partly because metals represent a recirculating problem unlike many organic contaminants which are biodegradable or can be decomposed chemically or thermally. As a result, metal remediation should include not only extraction from the source but also reclamation. Ion exchangers present such an option if they can posses the apparently conflicting attributes: efficient binding or extraction and inefficient binding for metal release.

This project proposes to use the metal binding "philosophy" of nature through the novel used of polyamino acids immobilized on a stationary support to accomplish metal extraction. Initial studies will be directed at cadmium, lead and mercury remediation. These materials are relatively inexpensive plus have an extremely long lifetime and high capacity which make them a cost effective alternative to current technologies.

In general the goal was to obtain fundamental data and make preliminary evaluation on a totally novel metal chelation scheme in hopes of providing an alternative option for an ever growing problem of a recirculating problem (i.e., metal contamination) that has not had a satisfactory solution to date. Specifically, the goals for year two of this research proposal were to focus on the study of new materials for the development of ion-exchange systems for metal preconcentration and remediation. Specifically, several polyamino acid homopolymers and copolymers were to be characterized and evaluated for metal binding capability. Also, new methods of immobilization of the polymers as well as new substrates were to be investigated.
The specific tasks that were to be accomplished in year two were the following:

TASK 1: Evaluate and characterize various homopolymers with expectations of complete characterization of polycysteine, polyhistidine and polyaspartic acid.

TASK 2: Begin initial synthesis and characterization of copolymers for metal remediation.

TASK 3: Investigate the possibility of templating the homopolymer polycysteine and copolymers containing cysteine.

TASK 4: Initiate studies of more efficient methods of immobilization of the polymers as well as the evaluation of new substrates.

Approach:

We have shown a formation constant of 10¹³ for Cd on polycysteine (ca. 50 amino acid residues/chain) immobilized on a silica substrate with capacities of ca. 4 g Cd/kg support. This binding strength, for example, makes extraction of the metal from solutions containing such strong complexing agents as EDTA possible. This particular polyamino acid also shows a high propensity for soft acid metals (such as Cd, Pb and Hg) and thus optimizes the effective binding capacity even in the presence of other transition metal cations and common salts. Additionally, the bound metal is easily released by dilute acid stripping. These features are due, in part, to the tertiary structure associated the peptide which forms a sterically correct cage around the target metal that can be reversibly removed by acid denaturation.

Additionally, by forming disulfide linkages through on-line oxidation of the material, a templated chelator can be formed around the target which further increases the selectivity and effective capacity. The chemistry associated with polyamino acid formation is straight forward and has been known for 40 years so the diversity of materials that can be made available is extremely flexible and straight forward. This project has long reaching implications since the binding functionalities available on amino acids is extremely variable while the formation of the chelating chain always involves the same procedure, i.e., formation of peptide bonds.

Exchange rates for complexation are only limited by mass transport and not by binding kinetics. Thus, it functions as efficiently as any currently available exchanger. The material is also much more cost effective and selective than natural proteins, which are expensive to isolate or synthesize and appear to lose their selectivity when removed from the unique chemical environment within the cell. The robustness of the material can be attested to by the hundreds of cycles of harsh acid (e.g., 1M HNO3) and oxidation (e.g., H2O2) that we have subjected a column to over the past two and a half years. (This column still retains its initial binding characteristics and capacities!) In this study, evaluation and characterization will employ low pressure flow systems with micro-columns and either flame AA or ICP-MS detection. Evaluation of utility with "real world samples" will be conducted in cooperation with Dr. Ahmed (Radian, Corp.; Houston, TX).

Expected Results:

While a number of studies have used metal ions for chromatographic isolation of proteins, no one has yet attempted to immobilize a protein (yet alone the more rugged polyamino acid) in an effort to develop a useful metal chelator. Additionally, no one has yet devised an immobilized chelator whose selectivity can be "tuned" for a particular metal and whose selectivity can be altered on-line for another target metal.

The project combines the expertise of a bio-organic chemist and an analytical chemist with experience in trace metal analysis and metal extraction using biological-based systems. It further relies on the cooperation of an industrial partner involved in metal remediation and environmental research.

Publications and Presentations:

Publications have been submitted on this subproject: View all 16 publications for this subproject | View all 359 publications for this center

Journal Articles:

Journal Articles have been submitted on this subproject: View all 4 journal articles for this subproject | View all 90 journal articles for this center

Supplemental Keywords:

RFA, Scientific Discipline, INTERNATIONAL COOPERATION, Waste, POLLUTANTS/TOXICS, Environmental Chemistry, Remediation, Chemicals, Hazardous Waste, Chemistry and Materials Science, Hazardous, mercury, lead, metal ion removal, metal recovery, reclamation, metal extraction, biopolymer chelators, cadmium, extraction of metals, bioploymers, heavy metals, metal contamination, metal removal, ion exchange

Progress and Final Reports:

Final

Main Center Abstract and Reports:

R828598    UT Center for Infrastructure Modeling and Management

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