Thermodynamic Reference Database Helge C. Moog Gesellschaft für Anlagen- und Reaktorsicherheit (GRS) Helmholtz-Zentrum Dresden-Rossendorf, Institut für Radiochemie (HZDR-IRC) AF Consult (Switzerland) Karlsruhe Institute of Technology, Institut für Nukleare Entsorgung (KIT-INE) TU Bergakademie Freiberg, Institut für Anorganische Chemie

Model calculation Result 1 logK GG Result 2 Result 3 Thermodynamic Equilibrium Modeling in Practice Parameterfile 1 Data.dat Parameterfile 2 Data.dat Parameterfile 3 Data.dat Parameterfile 5 Data.dat Result 4 Result 5 Result 6 Parameterfile 4 Data.dat Parameterfile 6 Data.dat

Model calculation Result 1 logK GG Result 2 Result 3 Thermodynamic Equilibrium Modeling in Practice Parameterfile 1 Data.dat Parameterfile 2 Data.dat Parameterfile 3 Data.dat Parameterfile 5 Data.dat Result 4 Result 5 Result 6 Parameterfile 4 Data.dat Parameterfile 6 Data.dat Are the results comparable ???!

What do we need to perform a thermodynamic equilibrium calculation? 4 Parameterfile Thermodynamic Database Needed: an easy way to translate database modifications into parameter files

Basic idea Thermodynamic calculations of various institutions become comparable, by creating parameter files from a common database. 5 Parameterfile 1 Daten.dat Reference database Parameterfile 3 Daten.dat Parameterfile 2 Daten.dat Parameterfile 4 Daten.dat

: Foundation of a national joint project THEREDA  Creation of a consistent, mutually agreed and quality-assured reference database  Joining competences for a common sake  Easy access via the world wide web  Making available ready-to-use parameter files  serve as national reference  further communication among institutions  facilitate the creation of parameter files and thereby the development of a thermodynamic database

Parameter File Thermodynamic Database Exp. Data : Foundation of a national joint project THEREDA Lit. Data

Responsibilities within THEREDA For the first two 3-years project phases, THEREDA members have voted for H. C. Moog (GRS) as project coordinator InstitutionResponsibility, field of competence AF ConsultCement system GRSProject coordination, Databank, Cs, Rb, Sr, heavy metals HZDRWeb interface, sorption, U, Ra KIT-INEActinides, Th, Pu, Np, Pa, Am, Cm, Sm, Nd TU BAFSystem of oceanic salts

Other related projects 9

„A technical framework which ensures that dependent and independent data are stored in a manner which ensures internal consistency when independent data are modified“ Database Parameterfile ?

Quality assurance and workflow in THEREDA 11 Guidelines Data Capture Databank Benchmark Calculations Parameter Files User QA Correctness Double Reading Check internal calculations Plausibility Documentation Data Assessment Class Category Quality Source Feedback Quality Objectives Transparency Consistency Comprehensiveness Uncertainties Data Assessment

Benchmark calculations 12  To be performed with parameter files created automatically from the databank  Demonstrate that calculational results match with lab data or expert judgment  Make sure that results are the same with several codes (or give reasons why they can not because of shortcomings of the code)  At any new release: repeat earlier benchmarks and make sure that the results still agree with earlier ones  Is a means of control for the user to check the accurateness of the downloaded parameter file

Interface Modules Content Management System DBMS Web Server Client Internet Technical Basics

How it is used Generic Datafile Specification by the user: Elements Interaction Model Code THEREDA-DB Parameter File - GWB - PHREEQC - CHEMAPP - EQ3/6 - …

Access via World Wide Web (interface for users)  Export of data as CSV or MS-Excel ©  Tool-Tips with additional information (formation reaction, classification of data, references)

Graphical user interface (for editors only)  Addition and modification of phases, phase constituents, data etc.  Operated with a normal web browser  Extensive control and edit functions  Allows de-centralized operation of a single database

Data structure: Phases and Phase constituents 17 aq UO2 2+ Phase Constituent Phase U 4+ UO 2 (OH) + Elements 1 U, 2O, -2 EA1 U, -4 EA1 U, 3 O, 1 H, -1 EA

Data structure: Phase constituent types and Reactions 18 UO 2 2+ Secondary Master Primary Master U 4+ Products UF 2 2+ ReactantCoefficient UF2 +1 U F -2

Principal structure of THEREDA 19 Phases (containing of Phase Constituents) Assignment of Sets, Validities, Interactions…

Principal structure of THEREDA Phases Assignment of Sets, Validities, Interactions… Data: PitzerData: SITData: EDH Interaction Coefficients

„Released Data“  „Non-released Data“ R1 ( ) System of oceanic salts Na +, K +, Mg 2+, Ca 2+, Cl -, SO 4 2-, H +, H 2 O(l) R2 ( ) System of oceanic salts + CO 2 (g), CO 3 2- Hydrated cement phases Without carbonate: Am(+III), Cm, Nd Not yet released Actinides, Fission- and activation products Pa, Th, U, Np, Pu, Am Rb, Sr, Tc, Cs, Sm, Ra

Criteria for releases 22  Completeness of data for the systems considered  Completeness of data assessment  Check of parameter files  Benchmark calculation: Equivalent results with all codes considered  Completed documentation of benchmark calculation

Current activities  Preparation of second release of data for  Carbonate / CO2  Hydrated cement phases  Am(III), Cm(III), Nd(III) (for carbonate-free systems only)  Completion (and test!) of export programs for  Geochemist‘s Workbench (GWB)  EQ3/6  Completion of graphical user interface (web-application, editors only)

Long-term usability  Usage of open-source programs  Low degree of abstraction of the data model  Documentation of databank structure  Flexible databank structure  Joint project of five research institutions

Conclusion  THEREDA offers a web-based, state-of-the-art thermodynamic reference database for aqueous systems in equilibrium with nuclear or non-nuclear waste forms in Germany  Joint-project of five research institutions  Comprehensive range of data  Access to code-specific parameter files  Means of directing future research and of quality assurance for government agencies, service provider, and research institutions  Future extensions of the thermodynamic database for nuclear and non- nuclear waste forms in Germany in conjunction with THEREDA

Possibilities of cooperation with THEREDA Common use of phases, phase constituents, classification schemes… Data: Pitzer - Thermodynamic data - Interaction coefficients - Speciation model Data: SIT - Thermodynamic data - Interaction coefficients - Speciation model Data: EDH - Thermodynamic data - Speciation model Common use of databank, internal calculations, web interface, export functions…

Cooperation  We are open for and very much interested in cooperation with other institutions related to  Database creation and management  Data selection and –evaluation  Comparison of models for specific systems  Implementation of more export formats for other codes  Bilateral cooperations with a member of THEREDA on specific issues  Usage of THEREDA as technical platform for the creation of other databases not consistent with the Pitzer model  Annual informal meetings to streamline common efforts on building a thermodynamic database

Thank you very much for your attention!