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Spent Fuel and Waste Science and Technology
Surface Complexation and Ion Exchange Database Development Phase 1: Clay Minerals
M. ZavarinLawrence Livermore National Laboratory
SFWST Annual Working Group MeetingLas Vegas, Nevada
May 22-24, 2018
LLNL-PRES-751626This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. Lawrence Livermore National Security, LLC
Spent Fuel and Waste Science and Technology
TitleMay 23, 2018
Overview of Activity
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We need to develop self-consistent surface complexation/ion exchange models, in concert with thermodynamic models, for nuclear waste repository performance assessment
This issue was expressly identified in the recent NEA Sorption project reports
Some progress on this issue has been made only recently in various international nuclear waste repository programs
The best path forward for developing such databases remains an open question, particularly in cases where generic repositories are being investigated resulting in a need to predict radionuclide sorption behavior over a very broad range of solution and mineralogic conditions.
Spent Fuel and Waste Science and Technology
TitleMay 23, 2018
Effect on Repository Performance or Safety Case Confidence
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A simple Kd approach is likely to be insufficient from the standpoint of Performance Assessment– Relies on conservative
assumptions A surface complexation/ion
exchange modeling approach is more defensible (state of the art) and allows for evaluation of alternative scenarios and hydrobiogeochemicaluncertainties. – However, an SC/IE approach is
likely too cumbersome for PA modeling
– The “smart-Kd” approach has been suggested (pursued in Germany)
From Stockman et al. http://dx.doi.org/10.1016/j.chemosphere.2017.08.115
Spent Fuel and Waste Science and Technology
TitleMay 23, 2018
Integration with GDSA/PA and/or the Safety Case
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Identify range of parameter space in GDSA/PA and/or Safety Case
Use combined TDB and SC/IE database to extract partitioning info across range of parameter space
Produce Smart Kd tables
Apply to GDSA/PA and/or Safety Case to account for parameter and condition uncertainty
Spent Fuel and Waste Science and Technology
TitleMay 23, 2018
Example: U(VI) on QuartzSCM
Mineral Area
Site
pK 1 pK 2 logK Chemical Equation Literature DDL Quartz 0.2 4.81 5.62 -5.72 »Si-(OH)2 + UO2<2+> = »Si-O2-UO2 + 2 H<1+> AZBN00a
DDL Quartz 0.2 4.81 5.62 -5.51 »Si-(OH)2 + UO2<2+> = »Si-O2-UO2 + 2 H<1+> AZZBN01 DDL Quartz 10 10 -1.6 7.6 -7.259 »X-OH + UO2<2+> + H2O = »X-O-UO2(OH) + 2 H<1+> JHLCH99 DDL Quartz 10 10 -1.6 7.6 9.529 »X-OH + UO2<2+> + CO3<2-> = »X-O-UO2CO3<1-> + H<1+> JHLCH99 DDL Quartz 10 10 -1.6 7.6 -1.978 »X-OH + UO2<2+> = »X-O-UO2<1+> + H<1+> JHLCH99 DDL Quartz 0.05 -7.2 -16.75 »SiOH + 3 UO2<2+> + 5 H2O = »SiO-(UO2)3(OH)5 + 6 H<1+> NB10 DDL Quartz 0.05 -7.2 0.3 »SiOH + UO2<2+> = »SiO-UO2<1+> + H<1+> NB10 DDL Quartz 0.05 -7.2 -5.65 »SiOH + UO2<2+> + H2O = »SiO-UO2(OH) + 2 H<1+> NB10 DDL Quartz 0.31 2.3 -1.24 7.06 -0.3 »Si-OH + UO2<2+> = »Si-O-UO2<1+> + H<1+> PJTP01 DDL Quartz 0.31 2.3 -1.24 7.06 -18.7 »Si-OH + UO2<2+> + 3 H2O = »Si-O-UO2(OH)3<2->+ 4 H<1+> PJTP01 DDL Quartz 0.03 2.3 7.2 0.3 »Si-OH + UO2<2+> = »Si-O-UO2<1+> + H<1+> PTBP98 DDL Quartz 0.03 2.3 7.2 -16.75 »Si-OH + 3 UO2<2+> + 5 H2O = »Si-O-(UO2)3(OH)5 + 6 H<1+> PTBP98 DDL Quartz 0.03 2.3 7.2 -5.65 »Si-OH + UO2<2+> + H2O = »Si-O-UO2(OH) + 2 H<1+> PTBP98 DDL Quartz 0.1 2.31 7.2 -8.45 »Si-OH + UO2<2+> + 2 H2O = »Si-O-UO2(OH)2<1-> + 3 H<1+> VT98 NE Quartz 0.33 0 -4.95 »Si(w)-OH + UO2<2+> + H2O = »Si(w)-O-UO2(OH) + 2 H<1+> DK01 NE Quartz 0.33 0 1.06 »Si(s)-OH + UO2<2+> = »Si(s)-O-UO2<1+> + H<1+> DK01 NE Quartz 0.33 0 -3.19 »Si(s)-OH + UO2<2+> + H2O = »Si(s)-O-UO2(OH) + 2 H<1+> DK01 NE Quartz 0.33 0 -2.56 »Si(s)-OH + UO2<2+> + H2O = »Si(s)-O-UO2(OH) + 2 H<1+> DK01 NE Quartz 0.33 0 -4.98 »Si(w)-OH + UO2<2+> + H2O = »Si(w)-O-UO2(OH) + 2 H<1+> DK01 NE Quartz 0.33 0 1.2 »Si(s)-OH + UO2<2+> = »Si(s)-O-UO2<1+> + H<1+> DK01 NE Quartz 0.33 0 -4.64 »Si(w)-OH + UO2<2+> + H2O = »Si(w)-O-UO2(OH) + 2 H<1+> DK01 NE Quartz 0.33 0 -0.03 »Si(w)-OH + UO2<2+> = »Si(w)-O-UO2<1+> + H<1+> DK01 NE Quartz 0.33 0 -5.28 »Si(w)-OH + UO2<2+> + H2O = »Si(w)-O-UO2(OH) + 2 H<1+> DK01 NE Quartz 0.33 0 10.183 »Si(w)-OH + UO2<2+> + CO3<2-> = »Si(w)-O-UO2CO3<1-> + H<1+> DK01 NE Quartz 0.33 0 -3.28 »Si(s)-OH + UO2<2+> + H2O = »Si(s)-O-UO2(OH) + 2 H<1+> DK01 NE Quartz 0.33 0 -4.73 »Si-OH + UO2<2+> = »Si-O-UO2(OH) + 2 H<1+> KCKD96 NE Quartz 0.33 0 -5.32 »Si(w)-OH + UO2<2+> + H2O = »Si(w)-O-UO2(OH) + 2 H<1+> KCKD96 NE Quartz 0.33 0 -2.65 »Si(s)-OH + UO2<2+> + H2O = »Si(s)-O-UO2(OH) + 2 H<1+> KCKD96 NE Quartz 0.33 0 -2.56 »Si(s)-O(0.5)H + UO2<2+> + H2O = »Si(s)-O(0.5)-UO2(OH) + 2 H<1+> K02b NE Quartz 0.33 0 -7.78 »Si(w)-O(0.5)H + UO2<2+> + CO2 + H2O = »Si(w)-O(0.5)-UO2CO3(OH)<2-> + 3 H<1+> K02b NE Quartz 0.33 0 -6.56 »Si(w)-O(0.5)H + UO2<2+> + H2O = »Si(w)-O(0.5)-UO2(OH) + 2 H<1+> K02b NE Quartz 0.33 0 -5.57 »Si(s)-O(0.5)H + UO2<2+> + H2O = »Si(s)-O(0.5)-UO2(OH) + 2 H<1+> K02b NE Quartz 0.33 0 -6.5 »Si(w)-O(0.5)H + UO2<2+> + CO2 + H2O = »Si(w)-O(0.5)-UO2CO3(OH)<2-> + 3 H<1+> K02b NE Quartz 0.33 0 -5.28 »Si(w)-O(0.5)H + UO2<2+> + H2O = »Si(w)-O(0.5)-UO2(OH) + 2 H<1+> K02b TL Quartz 0.32 0.00184 8.4 1.98 »Si(s)-OH + UO2<2+> = »Si(s)-O-UO2<1+> + H<1+> FDZ06 TL Quartz 0.32 0.00184 8.4 -1.88 »Si(s)-OH + UO2<2+> + H2O = »Si(s)-O-UO2(OH) + H<1+> FDZ06
RES3t output of SC data for one metal-mineral pair
Spent Fuel and Waste Science and Technology
TitleMay 23, 2018
Example: U(VI) on quartz
6
AZBN00a
AZBN01
DK01DK01
DK01
DK01
DK01
FDZ06
JHLCH99
JHLCH99
KCKD96
PJTP01
PTBP98
PTBP98
PJTP01DK01
DK01
RES3t referenced data for one metal-mineral pair
Spent Fuel and Waste Science and Technology
TitleMay 23, 2018
Example: U(VI) on quartz
Comparison of data and simultaneous model fits to ALL U(VI)-quartz data
Significant scatter at low sorbed/aqueous ratios is a result of inherent uncertainties associated with samples with little to no U(VI) sorption
>SiO- logK = -3.85 ± 0.04>SiOUO2OH logK = -4.56 ± 0.04
(-2.56 to -5.32 in RES3t database)>SiOUO2(OH)2
- logK = -10.71 ± 0.04>SiOUO2CO3
- logK = 2.02 ± 0.04
Non-electrostatic model, 2.3 sites/nm2, one site type
Spent Fuel and Waste Science and Technology
TitleMay 23, 2018
Relationship to R&D Priority Ratings
8
Task #
Task Name/
(and Work Package
number -- if needed or helpful for
more specificity)
Brief Task Description
includingRelevance (and/or input) to PA/GDSA
(nPA = not direct input to PA)
Personnel/Lab
Code(if
applicable)
Importance to Safety Case
(ISC)
(H, M, or L --see ISC table definitions)
(Identify applicable
Safety Case element from the provided
figure)
Current "State of the Art" Level
(SAL = 1, 2, 3, 4, or 5 --see SAL table definitions)
(Give brief update to applicable state-of-the-
art "discussion(s)" shown in UFD Roadmap
App. A, i.e., those discussion(s) for the
highest scoring related FEPs)
Short-term (1 yr) R&D Priority Scores
& Brief FY19 Work Scope Proposal
(Priority Score = H, M, or L, based on
combined ISC and SAL -- see PS table
definitions)
(Also give Roadmap Score for related FEP)
Related UFD Roadmap
Issue(s)/FEP(s), and associated UFD Roadmap priority scores*
(Find highest scoring related
FEP in App. B of UFD Roadmap)
Other Notes/Comments
(e.g., type of linkage to PA-GDSA; inputs
required and/or linkages to other
models and experiments)
17
Thermodynamic and sorption
database(s)
• Probably nPA•Thermodynamic, surface complexation/ion-exchange databases
M. Zavarin, C. Duffin,
T. WoleryLLNL
N/A
ISC = Medium SC
elements 3.3, 4.2 and 4.3
SAL=5 or 3 Data and methods are known. However, an adequate representation in database for is not yet available and needs to be developed. Implementation in GDSA not developed.
Database improvements (TDB) and database development begins. Priority score: M
• Thermodynamic, surface complexation/ion-exchange databases, used as input to process models• Surface complexation unlikely to be represented in PA
Spent Fuel and Waste Science and Technology
TitleMay 23, 2018
Current State of the Art and Past Accomplishments
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Current State of the Art:– Abundant (though incomplete) RN-mineral data available in the literature with associated
modeled reaction constants using a variety of SC and IE formulations (Vanselow, Gapon, Non-electrostatic, Diffuse Layer, MuSIC, etc.)
– Various mineral-specific compilations of SC and IE data exist in the literature (e.g. Dzombakand Morel, Karamalidis and Dzomback, etc.)
– Comprehensive SC databases are available in various levels of development (RES3t, PSI, etc.)
– Kd compilations have been developed (e.g. YMP, JAEA)
Past Accomplishments:– Approach has been demonstrated with
U(VI)-quartz using compiled primary data and
refit to non-electrostatic models.
– Codes and approach identified to test
various geochemical models
Spent Fuel and Waste Science and Technology
TitleMay 23, 2018
Integration with International
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Development efforts are aligned with RES3t approaches and database developments (HZDR, Germany)
Coordinated with NEA-TDB and SFWST thermodynamic database development efforts
Spent Fuel and Waste Science and Technology
TitleMay 23, 2018
Future R&D & Integration Timeframe
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FY18-19 effort will focus on demonstrating database development for clay minerals
Based on reference compilations contained in RES3t and focused on montmorillonite
Developed for key radionuclides (Cs, Sr, U, Np, Pu)
Demonstrate “smart Kd” approach and application in GDSA
From Stockman et al. http://dx.doi.org/10.1016/j.chemosphere.2017.08.115
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Questions?
12
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Back-Up Slides
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