Mark Fuhrmann U.S. NRC Office of Nuclear Regulatory Research

1. The NEA Sorption Projecta multinational cooperative program to advance the use of Thermodynamic Sorption Models Mark Fuhrmann U.S. NRC Office of Nuclear Regulatory Research

2. Background • Adsorption is a primary process that controls concentrations of trace elements in groundwater. • Adsorption is accumulation of ions from solution onto surfaces of minerals or onto/into organic matter. • It is due to the electric charge on solid surfaces attracting oppositely charged ions in solution. • Minerals have different abilities to adsorb elements. • Ions from solution attach to surfaces by forming several types of bonds with atoms on the solid.

3. Contaminants in/on Solids (Charlet and Manceau, 1993)

4. Definition of Kd • Adsorption is quantified as the Partition Coefficient (Kd). For contaminant transport: • Kd = [x] on solid phase / [x] in liquid phase • Units of mL/g or L/kg • This relationship defines how much a contaminant moves relative to the flow of water.Rf = 1 +(rb / Φ) Kd Where: rb = bulk density of soil (g/cc) (e.g. 1.2 – 2.0) Φ = bulk porosity (e.g. 0.30) Rf = retardation coefficient

5. Kd = 0 Kd = 1 Kd = 10 Effect of Adsorption on Contaminant Transport From: Freeze and Cherry

6. Kd can be determined experimentally • ASTM C-1733-10 Distribution Coefficients of Inorganic Species by the Batch Method • HOWEVER! Kd can change with many factors: • Water chemistry, especially pH • Mineral surfaces • Subtle changes in • chemistry may result • in big changes in • sorption. Uranium on ferrihydrite, Payne 1999

7. Thermodynamic Sorption Models (TSMs) • TSMs are a developing technique that is an alternative to experimentally defined Kd • Treat adsorption like aqueous speciation and can describe adsorption under variable chemical conditions >SOH0 + M2+ ↔ SOM+ + H+ • A TSM coupled within a reactive transport model can be used to simulate the spatial and temporal character of the Kd distribution that is due to evolving chemical conditions.

8. Thermodynamic Sorption Models require • Assumption of chemical equilibrium • Definition of the chemical components • Identification of all species that can be formed • Mass balance • Mass Action Law for each species • Thermodynamic Data Base • Activity Coefficient calculations • Requires thermodynamic data specific to the system. Parameter acquisition is needed.

9. Objective of the NEA Sorption Project To clarify and demonstrate how TSMs can serve to improve confidence in Kd values used to represent radionuclide sorption in Performance Assessment models. Project had three phases 1. 1997-1999 illustrated advances and diversity of TSMs 2. International comparative modeling exercise of 7 well characterized Test Cases. 20 teams participated. Result was a critical evaluation of modeling approaches. 3. “ A Guideline Document”

10. NEA Sorption Project phase II • Teams chose many combinations of modeling • approaches: • Model designs (1 or 2 site surfaces, surface • site densities, radionuclide surface species) • Key model components • Choice of fitting procedures • Modeling results sometimes clustered around • the data and sometimes it did not. • Main finding was that variability was due to • choices (sometimes poor ones) made by teams.

11. Comparison of model results to data for 8 teams Ni sorption on Na-montmorillonite

12. NEA Sorption Project phase III • TSM Guideline Document • M. Ochs, T.E. Payne and V. Brendler Objective: to provide recommendations and guidelines for TSM development and application to PAs and to educate modelers and the ‘safety case’ community about appropriate and useful TSM applications. Guideline document does not give instructions but provides discussions of effects that modeling choices have on the results. Contains practical guidance and observations.

13. NEA Sorption Project phase III • THEORETICAL BASIS OF TSMs AND OPTIONS IN MODEL development • Determination of Parameters for Thermodynamic Sorption Models • Approaches for applying TSMs to Intact and Complex Materials • GENERAL Guidelines and recommendations

14. Applying TSMs to Intact and Complex Materials • Two approaches: • Component Additivity: TSMs are determined on single minerals and then results are added together in proportion to minerals in a natural material. • Generalized Composite: adsorption on the whole substrate is described by mass laws written with generic surface functional groups. The stoichiometries and formation constants for each mass law are determined by fitting experimental sorption data (macroscopic dependence of adsorption as a function of pH and other relevant conditions) for the mineral assemblage as a whole.

15. Guideline DocumentTopics addressing TSMs of natural materials • Approaches for applying TSMs to intact and Complex Materials • Real substrates (What makes them complex?) • Complex mineralogy • Complex solution chemistry • Intact/compacted state • Determination and estimation of TSM parameters in real systems • Modeling adsorption on mineral assemblages: CA vs GC • Sensitivity analysis for complex systems: CA vs GC • Sample characterization • Surface site density and surface area • Surface protolysis • Radionuclide surface equilibria • Surface charge behavior and EDL correction terms

16. Normalized sensitivity of adsorption to different model parameters Generalized Composite Model Component Additivity Model Co adsorption on a South Carolina soil containing kaolinite, gibbsite, goethite and hematite, and 2:1 layer silicates Test case 7 from Phase II. Complex system, only a few teams tried this. The generalized Composite models clustered a bit better around the data.

17. Summary • Phase II of the NEA Sorption Project identified many approaches to Thermodynamic Sorption Modeling but many practical problems exist in implementing these complex models. • Phase III has tried to address these problems by providing practical, direct guidance to modelers. • Report is in the camera ready form and should be out very soon.