Effect of Pitting Corrosion Promoters on the Treatment of Waters Contaminated with a Nitroaromatic Compounds Using Integrated Reductive/Oxidative Processes

EPA Grant Number: R831276C008
Subproject: 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: Lasat, Mitch
Project Period: 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) RFA Text |  Recipients Lists
Research Category: Hazardous Waste/Remediation , Targeted Research

Objective:

Contamination with nitroaromatic compounds (NACs) such as 2.4,6-trinitrotoluene (TNT), 2,4 dinitrotoluene, 2,6-dinitrotoluene, and nitrobenzene is prevalent around United States Department of Defense (DoD) ammunition production facilities employed to support military activities. Past improper wastewater disposal techniques, such as direct discharges into drainage ditches, local streams, and settling lagoons have created soil, sediment, surface water, and groundwater contamination around these manufacturing facilities. Gulf Coast States such as Alabama, Louisiana, and Texas have ammunition production facilities listed on the Superfund National Priority List (NPL). Surface and groundwater contaminants of concern at these sites include TNT, 2,4 dinitrotoluene, 2,6-dinitrotoluene, nitrobenzene, and other nitroaromatic explosives. Treatment techniques, such as advanced oxidation processes (AOPs), which rely on the strong oxidation capability of the hydroxyl radical ( OH· ), as well as anaerobic and aerobic biodegradation, have been investigated for the treatment of NACs contaminated waters. However, these techniques are not cost effective as stand-alone treatment processes due to the generation of recalcitrant and/or regulated reaction by-products.

It is proposed that the integration of zero-valent metallic (ZVM) species followed by AOPs can mineralize and/or transformed NACs into low molecular weight non-toxic compounds. The aromatic amines formed during the reduction reaction with zero-valent iron are more oxidizable than the parent compound. In order to minimize the deactivation of the metal caused by the adsorbed amine by-products, it is proposed to add pitting corrosion promoters (for example, NaCl) to the contaminated water prior to the ZVM step. Pitting is a localized formed of corrosion Which causes continuous metal oxidation via the creation of acidic micro-environments within the metallic species. Steady metal oxidation in this case, translates into the continuous generation of electrons that react with the adsorbed species on the metal surface. It is also proposed that bi-metallic species of iron/manganese could be synthesized with the capability to reduce and oxidize nitro and amino aromatic compounds. This type of metallic species could transformed NACs into non-toxic low molecular weight organic and inorganic compounds in one single treatment step, reducing significantly capital and operating treatment costs.

Approach:

The main purpose of the proposed research is to generate data that can be used for the development of a reductive/oxidative integrated technology for the treatment of waters contaminated with NACs. The idea is to develop a cost effective technology that can mineralize and/or transform the NACs into low-molecular weight non-toxic compounds, which cannot be done using today's technologies as stand-alone treatment processes. Other secondary objectives include: 1. Validate/discover NACs reduction and nitroamines oxidation mechanisms by ZVMs and advanced oxidation, respectively, using computational chemistry. 2. Evaluate the effect of different pitting corrosion promoters on NACs reduction and nitroamine oxidation kinetics using iron or manganese and AOPs, respectively, and determine the optimum operating conditions for both processes. 3. Synthesize bi-metallic iron/manganese species and analyze the reaction by-products obtained during the application of these bi-metallic species for the treatment of water contaminated with selected NACs, 4. Develop a kinetic rate expression that couples metal corrosion with NACs degradation and a kinetic expression for nitroamines (NACs reduction by-products) mineralization using AOPs, and 5. Validate the kinetic mechanism using NACs contaminated groundwater from a former army ammunition production facility.

Expected Results:

All the reaction mechanisms developed during the proposed research activities will provide essential information during risk assessment and evaluation of remediation strategies of NACs contamination. The concept of integrated reductive/oxidative technologies. experimental procedures, rate expressions, and design calculations that will be evaluated and developed during the proposed research could be applied for the treatment of waters containing organic pollutants with structural, chemical, and physical properties similar to NACs. Such as azo dyes and some pesticides. Additionally, the novel concept of hyphenated technologies and bimetallic reduction agents could potentially be applied for the treatment of other recalcitrant organic contaminants such as polycyclic aromatic hydrocarbons and polychlorinated biphenyls. These contaminants are included in the Environmental Protection Agency list of priority pollutants.

Publications and Presentations:

Publications have been submitted on this subproject: View all 2 publications for this subprojectView all 64 publications for this center

Journal Articles:

Journal Articles have been submitted on this subproject: View all 1 journal articles for this subprojectView all 18 journal articles for this center

Supplemental Keywords:

RFA, Scientific Discipline, Waste, Water, Contaminated Sediments, Environmental Chemistry, Remediation, Hazardous Waste, Hazardous, Environmental Engineering, corrosion promoters, hazardous waste treatment, advanced treatment technologies, contaminated sediment, hazardous waste storage, contaminated soil, reductive oxidative processes, groundwater remediation, ethanol, contaminated groundwater, hazardous wate, nitroaromatic compounds, oxidizing agents

Progress and Final Reports:

  • Final

  • 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).
    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