Uranium Fate and Mineral Transformations upon Remediation with Ammonia (NH3) Gas

Authors

Silvina A. Di PietroFollow

Document Type

Dissertation

Degree

Doctor of Philosophy (PhD)

Major/Program

Chemistry

First Advisor's Name

Yong Cai

First Advisor's Committee Title

Committee chair

Second Advisor's Name

Hilary P. Emerson

Second Advisor's Committee Title

Committee member

Third Advisor's Name

Yelena Katsenovich

Third Advisor's Committee Title

Committee member

Fourth Advisor's Name

Jim E. Szecsody

Fourth Advisor's Committee Title

Committee member

Fifth Advisor's Name

Christopher J. Dares

Fifth Advisor's Committee Title

Committee member

Sixth Advisor's Name

David Chatfield

Sixth Advisor's Committee Title

Committee member

Keywords

uranium; remediation; ammonia; Hanford Site; phyllosilicate minerals; DOE

Date of Defense

3-24-2021

Abstract

The fission of uranium (U) for plutonium production was a major activity at the U.S. Department of Energy’s (DOE) Hanford Site in Washington State during World War II and Cold War. This endeavor resulted in the generation of over two million liters of high-level radioactive waste, most of which still remains in 177 underground storage tanks. Due to the improper storage and aging of these tanks in addition to other waste releases across the Site, approximately 200,000 kg of U have been released into the vadose zone. The objective of this study was to determine whether the application of the reactive gas, ammonia (NH₃), could be effective for sequestration of U in vadose zone conditions such as those at the Hanford Site.

The goal of this novel technique is to elevate the pH and induce mineral dissolution. As the NH₃ dissipates and the pH returns to neutral conditions, adsorption and co-precipitation processes are expected to immobilize U. The targeted mineral dissolution and secondary precipitate formation processes are not well understood at these conditions including their impact on U behavior.

The experimental results suggest that, as a result of pH manipulation with NH₃, investigated minerals (illite, muscovite, and montmorillonite) undergo incongruent dissolution. In addition, several analytical techniques were applied to compare ammonia-treated and circumneutral pH-treated minerals. Characterization studies showed that physicochemical transformations occurred, such as recrystallization of mineral edges and particle size and surface area increase. These behaviors are indicative of secondary precipitate formation, which was confirmed by comparisons of Al:Si ratios in solution and the solid phase, suggesting U sequestration. Furthermore, U distribution calculations between the solid and liquid phases indicate a significant increase in solid phase U with treatment, while geochemical software modeling provided a way to predict U species and secondary mineral phases upon alkaline treatment.

These findings show the scientific community that NH₃ gas injection is an effective technology to decrease the mobility of the uranyl ion. This technology may be particularly valuable to unsaturated areas where contamination remedies are needed in situ without the addition of liquid amendments.

Identifier

FIDC009686

ORCID

ORCID ID: 0000-0002-7633-9284

Previously Published In

Di Pietro, S. A., Emerson, H. P., Katsenovich, Y., Qafoku, N. P., & Szecsody, J. E. (2020). Phyllosilicate mineral dissolution upon alkaline treatment under aerobic and anaerobic conditions. Applied Clay Science, 189, 105520.

Recommended Citation

Di Pietro, Silvina A., "Uranium Fate and Mineral Transformations upon Remediation with Ammonia (NH3) Gas" (2021). FIU Electronic Theses and Dissertations. 4645.
https://digitalcommons.fiu.edu/etd/4645