Date of Award


Degree Name

Doctor of Philosophy



First Advisor

Dr. Daniel P. Cassidy

Second Advisor

Dr. Duane R. Hampton

Third Advisor

Dr. David A. Barnes

Fourth Advisor

Dr. Anna M. Jelaso-Langerveld


The efficacy of CaO2 for use in modified Fenton's (MF) reactions was investigated in this study, with the goal of developing a CaO2-based MF oxidation technology for use in in situ chemical oxidation. Traditionally, liquid H2O2 (HP) is used, and is injected into the subsurface in excess to ensure a sufficient radius of influence. CaO2 was investigated as an alternative source of H2O2 for MF reactions.

First, the rate of dissolution of powdered CaO2 and the yield of HP was investigated. Our results showed that the rate of dissolution of CaO2 and the corresponding yield of HP increases with decreasing pH. At a pH of 6 CaO2 is dissolved within 4 hours and the yield of HP is 82% of theoretical. The use of CaO2 as a source of H2O2 for the MF oxidation of tetrachloroethene (PCE), and 2-propanol, a hydroxyl radical scavenger, was used to demonstrate that the removal of PCE was due to oxidation by hydroxyl radicals. A comparison was made between HP and CaO2 based MF reactions with respect to PCE oxidation. The data indicate that CaO2 is able to sustain MF reactions longer and more efficiently than HP (i.e., less moles HP per mol PCE consumed).

A comparison was made between biological and modified Fenton (MF) chemistry with respect to the effectiveness of treating hydrocarbon-contaminated soil. The MF treatment was performed using both HP with Fe3+ and a CaO2-based oxidant to allow for comparisons between different MF oxidants. The MF treated systems had temporarily elevated surfactant concentrations with respect to both the control and biologically treated soils, indicating surfactant production during chemical hydrocarbon oxidation. Enhanced total petroleum hydrocarbon (TPH) removal was observed as a result of MF treatment with hydrocarbon removal being greater with the CaO2 treatment relative to HP treatment. At the end of the treatment period there was no significant decrease in viable bacterial numbers between MF and biological treatments.

Access Setting

Dissertation-Open Access

Included in

Geology Commons