Geothermal Technologies Office 2017 Peer Review

Impact of mineral reactions on shear zone permeability is uncertain at EGS conditions because key rate reactions are unknown

Increased fracture permeability

after reaction with CO2-brine at 200Public° ServiceC (Smith of Colorado Ponnequin et al, Wind 2013 Farm ) The Viability of Sustainable, Self-Propping Shear Zones Susan Carroll, Megan Smith, in Enhanced Geothermal Systems: Measurement of Kristin Lammers Reaction Rates at Elevated Temperatures Lawrence Livermore National Laboratory Project Officer: Elisabet Metcalf; Total Project Funding: $900,000 Track 3 - EGS Geoscience November 13-15, 2017 This presentation does not contain any proprietary confidential, or otherwise restricted information. LLNL-PRES- 739695 1 | US DOE Geothermal Office eere.energy.gov Relevance/Impact of Research

• GTO Need: Kinetic data are critical to designing and optimizing shear zone permeability for EGS systems. Increased fracture permeability aperture heights after reaction Increasedwith CO2-brine fracture at permeability 200°C (Smith et al, 2013) after reaction with CO2-brine at 200°C (Smith et al, 2013)

flow velocities

2 | US DOE Geothermal Office eere.energy.gov Relevance/Impact of Research

• Kinetic Knowledge Gap Shear Zone Minerals at Desert Peak Objective – Expand geochemical kinetic Plagioclase database for fracture Quartz minerals identified in EGS shear stimulation zones to K-spar 300°C.

• Current Technology Illite Mica Baseline Specifications

– Current kinetic data and rate depth, ft equations are lacking for many shear zone minerals Illite at EGS temperatures and Smectite ° are rare even to 100 C. Chlorite

Lutz et al, 2010

relative weight % 3 | US DOE Geothermal Office eere.energy.gov GTO Goal: Secure the Future with Enhanced Geothermal Systems

• Results will allow chemical affects to be included in modeling, allow realistic estimates of risk from chemical reactions, and assist in designing economically viable EGS systems.

• Rate equation – Temperature –pH – Solution chemistry – Surface area

– New rate laws for 4 minerals (25 to 300C) – 111 new experiments + literature values

4 | US DOE Geothermal Office eere.energy.gov Scientific/Technical Tasks

• Detailed characterization of solids before and after reaction – TEM/SEM/XRD/BET • Measure dissolution rates for shear zone minerals in mixed flow reactors – chlorite, illite, and biotite – pH 3 – 10 – 100 - 300°C – • Desert Peak, Raft River, Bradys Hot Spring (~200°C) • Newberry (200-300°C) • Derive dissolution rate equations to be used in reactive-transport simulations

5 | US DOE Geothermal Office eere.energy.gov Scientific/Technical Approach

• Rate ~ ∆ [solution composition] x flow rate / surface area

0.02 0.05 100°C 250°C 0.04 0.015 0.03 silica 0.01 0.02 magnesium 0.005 0.01 concentration, mM concentration, 0 0 0 255075100 0 255075100 time, h time, h

6 | US DOE Geothermal Office eere.energy.gov Theoretical f(∆Gr) terms slows rates only when the solution is very close to equilibrium

7 | US DOE Geothermal Office eere.energy.gov Summary: Rock-water interactions have the potential to alter shear zone permeability

• Chlorite, biotite, illite, muscovite, and K feldspar are key fracture filling minerals in EGS shear zones • Measured rates and derived equations so that they can be used to assess the role of geochemistry for EGS permeability using reactive transport codes. • Illite, muscovite, feldspar are significantly more reactive than chlorite and biotite. – 100 to 1000 times faster • The high reactivity of illite, muscovite, feldspar is likely to drive chemical alteration in shear zones. Rapid dissolution and secondary precipitation will likely impact flow and permeability in geothermal reservoirs. • Peer-reviewed publication of new rate laws and with the Geothermal Data Repository 8 | US DOE Geothermal Office eere.energy.gov Chlorite (Mg4.29Al1.48Fe0.10)(Al1.22Si2.78)O10(OH)8 Single rate equation from 25 to 275ºC

9 | US DOE Geothermal Office eere.energy.gov Biotite K2(Mg,Fe,Al)6(Si,Al)8O20(OH)4 Single rate equation from 25 to 280ºC

10 | US DOE Geothermal Office eere.energy.gov Illite K1.55(Na0.04,Ca0.02)Al2.90(Fe0.70,Mg0.54,Ti0.05)Si6.75Al1.25O20(OH)4 Single rate equation from 5 to 280ºC

11 | US DOE Geothermal Office eere.energy.gov Muscovite K2(Al,Mg,Fe)4(Si,Al)6O20(OH)4 Single rate equation from 5 to 280ºC

12 | US DOE Geothermal Office eere.energy.gov K-Feldspar: Working on a rate equation that accounts for reaction affinity

-6.00 200 C, Berger et al., 2002 200 C, current study -6.50 250 C, current study )

-1 280 C, current study s

-2 -7.00

-7.50

-8.00 log rate (mol m -8.50

-9.00 246810 pH

13 | US DOE Geothermal Office eere.energy.gov K-Feldspar: Working on a rate equation that accounts for reaction affinity

14 | US DOE Geothermal Office eere.energy.gov Summary: Rock-water interactions have the potential to alter shear zone permeability

• Chlorite, biotite, illite, muscovite, and K feldspar are key fracture filling minerals in EGS shear zones • Measured rates and derived equations so that they can be used to assess the role of geochemistry for EGS permeability using reactive transport codes. • Illite, muscovite, feldspar are significantly more reactive than chlorite and biotite. – 100 to 1000 times faster • The high reactivity of illite, muscovite, feldspar is likely to drive chemical alteration in shear zones. Rapid dissolution and secondary precipitation will likely impact flow and permeability in geothermal reservoirs. • Peer-reviewed publication of new rate laws and with the Geothermal Data Repository 15 | US DOE Geothermal Office eere.energy.gov Accomplishments, Results and Progress

Status • Complete Deliverable • Final report documenting updated EGS mineral kinetic database (2/15/2017) Publications • Smith, M. M., Carroll, S. A. (2017) Biotite dissolution kinetics at temperatures above 100 °C, Chemical Geology (in revision) • Lammers, K. Smith, M. M., Carroll, S. A. (2017) Muscovite dissolution kinetics as a function of pH at elevated temperature. Chemical Geology, https://doi.org/10.1016/j.chemgeo.2017.06.003 • Smith M., Dai, Z., Carroll, S. (2017) Illite dissolution kinetics from 100 to 280 °C and pH 3 to 9. Geochimica et Cosmochimica Acta, 209, 9-23, http://dx.doi.org/10.1016/j.gca.2017.04.005 • Smith, M. M., Carroll, S. A. (2016) Chlorite dissolution kinetics at pH 3 – 10 and temperatures to 275°C, Chemical Geology, 421, 55-64, http://dx.doi.org/10.1016/j.chemgeo.2015.11.022

16 | US DOE Geothermal Office eere.energy.gov This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under contract DE‐AC52‐07NA27344.

17 | US DOE Geothermal Office eere.energy.gov