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Title: Chemical Environment at Waste Package Surfaces in a High-Level Radioactive Waste Repository

We have conducted a series of deliquescence, boiling point, chemical transformation, and evaporation experiments to determine the composition of waters likely to contact waste package surfaces over the thermal history of the repository as it heats up and cools back down to ambient conditions. In the above-boiling period, brines will be characterized by high nitrate to chloride ratios that are stable to higher temperatures than previously predicted. This is clearly shown for the NaCl-KNO{sub 3} salt system in the deliquescence and boiling point experiments in this report. Our results show that additional thermodynamic data are needed in nitrate systems to accurately predict brine stability and composition due to salt deliquescence in dust deposited on waste package surfaces. Current YMP models capture dry-out conditions but not composition for NaCl-KNO{sub 3} brines, and they fail to predict dry-out conditions for NaCl-KNO{sub 3}-NaNO{sub 3} brines. Boiling point and deliquescence experiments are needed in NaCl-KNO{sub 3}-NaNO{sub 3} and NaCl-KNO{sub 3}-NaNO{sub 3}-Ca(NO{sub 3}){sub 2} systems to directly determine dry-out conditions and composition, because these salt mixtures are also predicted to control brine composition in the above-boiling period. Corrosion experiments are needed in high temperature and high NO{sub 3}:Cl brines to determine if nitrate inhibits corrosionmore » in these concentrated brines at temperatures above 160 C. Chemical transformations appear to be important for pure calcium- and magnesium-chloride brines at temperatures greater than 120 C. This stems from a lack of acid gas volatility in NaCl/KNO{sub 3} based brines and by slow CO{sub 2}(g) diffusion in alkaline brines. This suggests that YMP corrosion models based on bulk solution experiments over the appropriate composition, temperature, and relative humidity range can be used to predict corrosion in thin brine films formed by salt deliquescence. In contrast to the above-boiling period, the below-boiling period is characterized predominately by NaCl based brines with minor amounts of K, NO{sub 3}, Ca, Mg, F, and Br at less than 70% relative humidity. These brines are identified as sulfate and bicarbonate brines by the chemical divide theory. Nitrate to chloride ratios are strongly tied to relative humidity and halite solubility. Once the relative humidity is low enough to produce brines saturated with respect to halite, then NO{sub 3}:Cl increases to levels and may inhibit corrosion. In addition to the more abundant NaCl-based brines some measured pore waters will evaporate towards acid NaCl-CaCl{sub 2} brines. Acid volatility also occurs with this brine type indicating that chemical transformations may be important in thin films. In contrast to the above-boiling period, comparison of our experimental data with calculated data suggest that current YMP geochemical models adequately predict in-drift chemistry in the below-boiling period.« less
Authors:
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Publication Date:
OSTI Identifier:
877844
Report Number(s):
UCRL-TR-212566
TRN: US0601713
DOE Contract Number:
W-7405-ENG-48
Resource Type:
Technical Report
Research Org:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
12 MANAGEMENT OF RADIOACTIVE WASTES, AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; 58 GEOSCIENCES; 54 ENVIRONMENTAL SCIENCES; ACID CARBONATES; BOILING POINTS; CALCIUM; CHLORIDES; CORROSION; HALITE; HIGH-LEVEL RADIOACTIVE WASTES; NITRATES; SULFATES; THERMODYNAMICS; THIN FILMS; WASTES