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Analcime-wairakite formation during experimental cement-bentonite alteration at 200–300 °C

Journal Article · · American Mineralogist
DOI:https://doi.org/10.2138/am-2024-9490· OSTI ID:2571221
Engineered barrier system materials in nuclear waste repositories may undergo hydrothermal alteration in response to groundwater saturation and heating events over their long operational timescales. Hydrothermal interactions between engineered materials (e.g., bentonite buffers, cements, waste canister materials) and the host rock environment may drive alteration processes that affect the advantageous properties of some barrier materials. However, such alteration will also promote the formation of zeolites, hydrothermally formed minerals that may themselves act to isolate radionuclides. Understanding the environmental conditions that control radionuclide-sorbing properties of zeolites, such as Si/Al ratio or Na content, will be valuable for assessing the changing properties of engineered barrier materials in the case of an in situ heating event. Here, we present experimental work characterizing the formation of zeolites during hydrothermal interactions between generic clay and cement barrier materials, with a focus on the analcime-wairakite zeolite series, which has known radionuclide sorption and exchange properties. We present the results of hydrothermal experiments combining uncured ordinary Portland cement powder with steel and Wyoming bentonite in the presence of Opalinus clay and a synthesized Opalinus clay groundwater to simulate water-saturated conditions in an argillaceous rock repository. The experiments were conducted isothermally at 200 or 300 °C for 8 to 24 weeks. In contrast to analogous studies that did not include cement reactants, we observed the formation of analcime-group minerals in all experiments. The addition of cement resulted in lower Si/Al ratios in the zeolites compared to similar studies that did not include cement. The presence of cement as a reactant was interpreted to promote analcime formation at 200 °C. At 300 °C, we observed higher calcium and silica concentrations in the aqueous solutions as well as increased wairakite formation and decreased analcime formation compared to the experiments at 200 °C. These results show a fully realized analcime-wairakite solid solution that falls between Si/Al = 2 (ideal) and a trend of analcime minerals that have increasing Si/Al ratios with increasing Na/(Na+Ca). Our results show predictable relationships between the Si/Al ratio and the analcime-wairakite content under hydrothermal conditions and illustrate that repository material interactions may promote the formation of zeolites in the analcime-wairakite solid-solution series during heating events in the subsurface.
Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Nuclear Energy (NE), Office of Spent Fuel and Waste Disposition
Grant/Contract Number:
89233218CNA000001; NA0003525
OSTI ID:
2571221
Alternate ID(s):
OSTI ID: 2999171
Report Number(s):
LA-UR--23-34101; SAND--2024-06886O; SAND--2025-12802J; 10.2138/am-2024-9490; 1780162
Journal Information:
American Mineralogist, Journal Name: American Mineralogist Journal Issue: 7 Vol. 110; ISSN 1945-3027; ISSN 0003-004X
Publisher:
Mineralogical Society of AmericaCopyright Statement
Country of Publication:
United States
Language:
English

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