Theses and Dissertations

Issuing Body

Mississippi State University


Zappi, Mark E.

Committee Member

Schulz, Kirk H.

Committee Member

Kuo, Chiang H.

Committee Member

Bricka, R. Mark

Committee Member

Toghiani, Hossein

Date of Degree


Document Type

Dissertation - Open Access


Chemical Engineering

Degree Name

Doctor of Philosophy


College of Engineering


Dave C. Swalm School of Chemical Engineering


The Department of Defense (DoD) has numerous sites that contain groundwater contaminated with 2,4,6-trinitrotoluene (TNT). The currently applied technologies for treating TNT contaminated waters are carbon adsorption and chemical oxidation. Carbon adsorption is a non-destructive technology, which could create future liability issues and is inefficient at relatively low TNT concentrations. On the other hand, application of chemical oxidation for the treatment of TNT contaminated water generates trinitrobenzene (TNB), a by-product of the incomplete oxidation of TNT. TNB is regulated as strictly as TNT. Additionally, over 70% of the reactor required treatment time for meeting target levels is due solely for TNB removal. This study evaluated the potential integration of zero-valent metallic species and advanced oxidation for the treatment of waters contaminated with TNT. The idea was to reduce treatment time, and thus, operational costs, when advanced oxidation is used as a stand-alone treatment technology by reducing TNT prior to oxidation. The use of zero-valent metals as the first treatment step transformed TNT into reduced organic compounds which were easily oxidized. The effectiveness of zinc, iron, nickel, copper, and tin as TNT reducing agents was evaluated. Zinc and iron were selected for further study based on their performance degrading TNT. Then, the reduction mechanism (pathway) and associated by-products of TNT reduction using zinc were examined using a zinc specimen manufactured by Sigma Corporation. Three amines were identified during reduction : 2-amino-4,6-dinitrotoluene, 4-amino-2,6-dinitrotoluene, and 2,4-diamino-toluene. Other intermediates were observed but not identified. Many of these reduction by-products adsorbed strongly onto the metal surface, significantly reducing the rate of TNT degradation during aging experiments. The aging of the metallic species was modeled using a power decay law parameter with the rate expression for TNT degradation. Corrosion promoters such as KCl addition, ozonation, and peroxone were evaluated as alternatives to reactivate zinc and iron to achieve steady TNT degradation. The addition of KCl performed significantly better than ozonation and peroxone. Furthermore, addition of KCl during the reduction step using iron or zinc generated organics that were successfully mineralized by ozonation or peroxone.



Zero-Valent Metals||TNT Contaminated Waters||Advanced Oxidation Processes||Integrated Remediation Processes