Progress Update Carbon Sequestration Initiative

1. Progress UpdateCarbon Sequestration Initiative John LaFemina and Pam Hughes February 2, 2010 Ellyn Murphy

2. CSI Objective Understand supercritical geochemistry impact on the caprock and other points of potential failure Develop tools to improve rigor in reservoir modeling Support PNNL’s China effort through tools that enhance collaboration & allow management of emissions chemistry underground Accelerate the safe deployment of geologic sequestration with underpinning basic science in geochemistry and subsurface flow and transport. 5 year, $15M investment by the Laboratory

3. Approach A computational platform and a suite of experimental capabilities that facilitates collaboration to rapidly advance scientific understanding. • A computational platform - Geologic Sequestration Software Suite (GS3): • Model development and execution • Simulator development and validation • Reference data catalog and data mining • An experimental suite – In Situ Supercritical Suite (IS3): • Probe reactions under supercritical conditions • Processes that impact the integrity of the caprock • Geochemistry of co-sequestration • User communities that identify and address science needs and translate the science to technology • Applications user community • Research user community 3

4. Initiative Structure Ellyn Murphy, Initiative Lead Alain Bonneville, Chief Scientist Geologic Sequestration Software Suite (GS3) Focus Area - TBD In Situ Supercritical Suite (IS3) Focus Area - Kevin Rosso GS3 Core Architecture & Simulation Interface – Gorton In situ NMR of CO2 Trapping Mechanisms – Hoyt & Hu In situ Imaging of Mineral- scCO2 Reactions with AFM – Lea Data Assimilation Tools for CO2 Reservoir Modeling – Rockhold Multiscale Investigations of CO2 Behavior – Tartakovsky Real-time Optical Spectroscopy Platform– Wang In Situ High Pressure XRD Schaef Advanced Scalability for STOMP – Yabusaki, Scheibe, & Lin Ultrascalable Solvers for Subsurface Science – Hammond Micromodel Pore-Scale Studies Oostrom GS3 Numerical Model Development - Williams GS3 – Benchmarking & Validation Platform - White 4

5. IS3 – Instrumentation to Probe Reactions in the Caprock Under Supercritical Conditions “Virtually no thermodynamic or kinetics data for wet CO2-mineral reactions” • Role of water activity in mineral transformations – water activity thresholds? • Mechanistic characterization of reactions under high pressure and temperature • Relevant time-scales for mineral transformations with respect to fluid flow through fractures. • Predict the conditions for fluid transmission through fractures; fracture opening/self-sealing • Representation of water-wet CO2 reactions in simulators Caprock Dry CO2 Wet CO2 Water Saturated CO2 CO2 pore-space fraction Injection Well Caprock Confined Saline Aquifer 5

6. IS3 – In Situ Supercritical Suite Hyperbaric Hydrothermal AFM High-Pressure/ Temperature MAS NMR Micromodel System Real-Time Optical Spectroscopy Cell In Situ High Pressure XRD 6

7. IS3 – In Situ Supercritical Suite 7

8. In situ Molecular Probes: NMR David W. Hoyt and Jian Zhi Hu (PI’s) Ja Hun Kwak and Jesse A. Sears (Collaborators) No direct molecular probes exist for mineral carbonation in situ Objective: • Develop and apply first high-pressure MAS NMR capability for in situ characterization of mineral carbonation mechanisms and kinetics. • Lay groundwork for in situ high-pressure NMR probe by studying early stages of mineral carbonation reactions at pressure up to 80 atm using ex situ MAS NMR. Progress: • In situ probe development task • The sample rotors and sample preparation chamber have been successfully designed, built and gas pressurized to 2000 psi, meaning a significant breakthrough in NMR in situ high pressure detection has almost been achieved.   • Ex situ NMR task: • Kwak J.; Hu J.; Hoyt D. W.; Sears J.; Wang C.; Rosso K.; Felmy A. Metal Carbonation of Forsterite in Supercritical CO2 and H2O Using Solid State 29Si, 13C NMR Spectroscop. J. Phys. Chem. In Press, 2010. • Hu; Kwak; Hoyt; Sears; Rosso; Felmy. Studies of metal carbonation of forsterite in supercritical CO2 and H2O using solid state NMR spectroscopy. ACS 239th National Meeting, San Francisco, Speaking Presentation. March 21-26, 2010. • Hu; Kwak; Hoyt; Sears; Rosso; Felmy. Probing Metal Carbonation Reactions of CO2 in a Model System Containing Forsterite and H2O Using Si-29, C-13 Magic Angle Sample Spinning • NMR Spectroscopy. AGU, San Francisco. Post Presentation. Dec. 17, 2009.

9. In situ Molecular-Scale Probes: AFM AS Lea, SR Higgins (Wright State), KG Knauss (LBNL), JE Amonette Fine-scale imaging capability for mineral carbonation in situ is absent • Build the world’s first hyperbaric hydrothermal atomic force microscope (H2AFM) capable of imaging mineral carbonation reactions at the mineral-fluid interface in scCO2 to study reaction mechanisms and kinetics. Objective: Progress: • Designed and built a prototype test cell that demonstrated the equivalent noise for a cantilever in a scCO2 environment less than an AFM in its standard configuration indicating imaging of atomic steps is possible. • Designed and built a fully functional AFM head capable of imaging mineral surfaces at pressures up to 100 atm and temperatures up to about 80 C. • Demonstrated that the fully functional AFM head is capable of imaging atomic steps on calcite under ambient conditions using sub-optimal vibration isolation conditions. • Submitted proposal to DOE-EGS for chemical reaction model development in Enhanced Geothermal Systems. • Oral presentation accepted for ACS geochemical division.

10. In situ Molecular-Scale Probes: Optical Zheming Wang, Chris J. Thompson, Alan G. Joly, and John Loring • Develop a modularized optical spectroscopic platform that integrates a supercritical CO2 generation and manipulation system with a wide range of optical and laser spectroscopies to study the structure of water in scCO2, adsorbed water at mineral interface, and rates of mineral transformations. No sufficiently versatile probes exist for mineral carbonation in situ Objective: Progress: • An in situ scCO2 – transmission mode IR spectrometer system has been developed and tested, and a reflective mode system is near completion • Experimental results indicated feasibility of the system for investigation of water dissolution and forsterite carbonation reaction in scCO2; Measured water solubility data match well with literature values • Real-time simultaneous observation of the formation of carbonate-bicarbonate species and water in scCO2 and on mineral surface can be accomplished; Results was presented at the ‘09 AGU meeting

11. In situ High Pressure XRD (HXRD) HT Schaef and KM Krupka Caprock mineral transformation kinetics in the presences of H2O rich scCO2 are required for modeling long term CO2 storage • Develop HXRD capability to probe scCO2 reaction processes at fluid-solid interfaces in model cap rock mineral systems • Mineral dissolution kinetics • Secondary mineral precipitation • Quantification of mineral phases • Impacts of mixed gas systems Objective: Challenges: • Designing a high pressure x-ray transparent reactor to function at pressure and temperature conditions relevant to carbon sequestration. • Quantifying dissolution and precipitation kinetics of important caprock minerals. Progress: • Procurement and characterization of minerals (brucite, portlandite, antigorite, and larnite) for initial use in pressure cell testing. • Pressure reactor design completed and released to vendor for procurement (01/20/10).

12. Micromodel Pore-Scale Studies Mart Oostrom (PI), JW Grate, C Zhang Capillarity, mass transfer, interfacial tension,and wettability impact caprock sealing efficiency and storage capacity • Increase understanding of pore-scale mechanisms influencing (hydrodynamic and capillary) trapping and caprock integrity through high-pressure pore-scale experiments in micromodels. Objective: Challenge: • Development of visualization techniques at supercritical conditions during fluid displacment at the micrometer scale. Progress: • Developed solvatochromic dye imaging method for wetting and nonwetting fluid pairs (to be submitted to J. of Colloid and Interface Science). • Designed high-pressure flow cell for displacement studies. • Identified method for micromodel wettability alterations.

13. Initiative Structure Ellyn Murphy, Initiative Lead Alain Bonneville, Chief Scientist Geologic Sequestration Software Suite (GS3) Focus Area - TBD In Situ Supercritical Suite (IS3) Focus Area - Kevin Rosso GS3 Core Architecture & Simulation Interface – Gorton In situ NMR of CO2 Trapping Mechanisms – Hoyt & Hu In situ Imaging of Mineral- scCO2 Reactions with AFM – Lea Data Assimilation Tools for CO2 Reservoir Modeling – Rockhold Multiscale Investigations of CO2 Behavior – Tartakovsky Real-time Optical Spectroscopy Platform– Wang In Situ High Pressure XRD Schaef Advanced Scalability for STOMP – Yabusaki, Scheibe, & Lin Ultrascalable Solvers for Subsurface Science – Hammond Micromodel Pore-Scale Studies Oostrom GS3 Numerical Model Development - Williams GS3 – Benchmarking & Validation Platform - White 13

14. Current Landscape for geologic sequestration modeling • Lifecycle Workflows • conceptual model evolution • data storage and quality assurance • generations of modeling teams • simulation complexity & execution • Advancing Scientific Simulators • national laboratory, academic, commerical • verification, diagnostics, validation • availability, licensing, training, qualification • Diverse Support Tools • commercial packages • spreadsheets and text editors • scripts • Projects • commercial-scale • pilot-scale • proposals 14

15. high low

16. Futurefor geologic sequestration modeling • Interdisciplinary Teams • protocols for modeling best practices • Knowledge Management • data provenance • data transparency & protection • historical archive • Flexibility • commercial tools • integrated tools • tool registry • innovative data assimilation • Scientific Simulators • infusing new science • accelerating scientific advances • code diagnositics and validation • scalable computing • Analytics and Visualization • Optimization& Stochastic Realizations 16

17. Flexible Structure for modeling process and data management Site & Project Data Reference Data Catalog Model Development Data Management System Scientific Simulator Advancement Simulation Execution Validation, Diagnostics, & Monitoring Visualization & Analytics 17

18. Platform Architecture from a component perspective External Tools User Environment Integrated Tools Provenance & Metadata Stores and Archives

19. GS3 Core Architecture and Framework I. Gorton, G.D. Black, K.L. Schuchardt, and S.K. Wurstner Integrated tool set for simulation development, execution, and analytics Objective: Transform the application, verification, and advancement of computational tools for geologic sequestration through a system that accommodate collaborative teams, integrates seamlessly with data management and existing subsurface modeling capabilities, and provides a macro perspective for scientific discovery. Progress: Flexible and scalable collaborative system architecture created and demonstrated Tools for ingesting geo-sciences data into GS3 so it can be easily exploited by modelers Prototype collaborative system for end-users to manage and share model versions and associated simulation results as they evolve 1 refereed conference paper published and nominated for best paper; EM ASCEM project based on GS3

20. GS3 Data Assimilation Tools M.L. Rockhold, E.C. Sullivan, G.V. Last, C.J. Murray, and G.D. Black Streamline data assimilation process for reservoir model development • Advance and accelerate process of CO2 reservoir model development through design and implementation of procedures and software tools for processing and analyzing geologic and geophysical data while leveraging commercial and open-source reservoir characterization and visualization software Objective: Progress: • Performed review of key data types, analyses, and selected software applicable to reservoir model development (Rockhold et al. 2009) • Developed prototype rock properties catalog (Devoto et al. 2009) • Implemented geophysical well log viewer for GS3 wiki (in collaboration with GS3 architecture and framework group) • Designed conceptual-mathematical model pages for GS3 wiki to facilitate comparisons between different models (implementation in progress for Sim-SEQ) • Linkages from GS3 wiki to open-source software (in progress)

21. GS3 Numerical Model Development M.D. Williams, S.K. Wurstner, PD Thorne, AP Kuprat, DH Bacon • Provide for comprehensive and efficient development of simulations for geologic sequestration at specific sites, providing PNNL with a transformational tool that advances the state-of-the-art of geologic sequestration modeling. Current numerical model development tools are inadequate for collaborative and efficient generation of simulator input files Objective: Challenge: • Selection of web-based codes/platform with required functionality and ability to integrate with GS3 Progress: • Developing simple GUI test problems in Java for forms and 3D viewing. Initial scoping tests showed that more functionality was needed than provided within MediaWiki and its available extensions.

22. Multiscale Investigations A.M. Tartakovsky, A. Marquez, G. Lin, S. Kerisit, and A.L. Ward Little known about chemical-physical interactions of CO2, water and mineral phases Objective: Develop multi-scale multi-phase flow and transport models to simulate a CO2 behavior in the caprock at the pore and sub-pore scale through innovative approaches such as hybrid models, novel architectures, and experimental mineral systems Progress: • New hybrid Kinetic Monte Carlo – continuum model to study dissolution rates for different T, pH and pressure • New pore-scale model for CO2 injection, entrapment and dissolution • New Lagrangian Particle Darcy-scale model for unstable downward migration of dissolved CO2 • Modeling micro-fluidic experiments. • 1 publication, 1 in press, AGU abstract and poster

23. Diagnostics, Validation and Intercomparison of Simulators MD White, P Hui, VL Freedman, and DH Bacon Simulator verification workshops and code comparison publications are static snapshots of the state of numerical simulation science for greenhouse gas sequestration in deep saline geologic reservoirs. • Develop a computational framework that makes validation and benchmarking a dynamic process; where, numerical solutions evolve with modeling capability advances and benchmark problem complexity evolves with growth in available field and experimental data. Objective: Challenge: • Collaborate with the scientific community to define an appropriate initial suite of problems; develop solutions to the defined problems using an array of numerical simulators from across the scientific community; and build user framework that makes the process dynamic. Progress: • Previous participation in the Las Cruces Trench unsaturated transport, Yucca Mountain nuclear repository, Hanford Site deep vadose zone transport, GeoSeq code intercomparison, and international gas hydrate code comparison activities supports the launch of this project.

25. Instrument development in EMSL FY09 Accomplishment III • The New Cell • Will be designed and machined based on the experience from the other two projects. • Will allow optical measurements with a NA approaching 0.9 (half-cone angle of 65º) • The Current Cell • Temperature up to 200 ℃ • Pressure up to 5000 psi • Numerical aperture of 0.14 • enough for FT-IR, Raman, fluorescence • not enough for nonlinear optical measurement (SHG, SFG) and most microscopy measurements 25

26. Rock-Water-scCO2 Reactions Aqueous Dissolved scCO2 Water Solvated in scCo2 Basalt • Long term static basalt experiments • Carbonate formation • Chemical variability • Variable rates Aragonite Calcite nodules Basalt • Whole rock experiments • Relatively fast • Variable rates • Secondary mineralization • Carbonates

27. GS3 Requirements • Support collaboration and data sharing • in/across sequestration studies • Flexible control over data visibility/change • Allow user contribution of content • Project data • Ad hoc • Harvest/make accessible reference data • Automated extraction/markup from papers/text/databases • Sophisticated search/query • Capture provenance • Source of data, model versioning, inputs/outputs to simulations • Launch jobs to a range of simulators on HPC platforms • E.g. STOMP, PFLOTRAN, TOUGH2, FEHM • Integrate with widely used and custom-built modeling tools • E.g. Petrel, Earthvision • simple mechanism for user created script driven integration • Exploit off-the-shelf infrastructure • Build as little code as possible ourselves 27

28. Managing the Geologic Storage Lifecycle • Simulation will determine site selection, permitting, design, operation and closure – thousands of simulations over decades • Increasing complexity of science-based simulators: • Greater accuracy in predicting subsurface fate and transport • More difficult to use • Immense data quantity and diversity