Geochemistry of CO2 Storage

Alexandra Hakala
Geosciences Division, Office of Research and Development National Energy Technology Laboratory Pittsburgh, PA

Geochemistry plays an important role in all aspects of a geological CO2 sequestration system
Monitoring techniques Groundwater aquifers Liability issues EPA Class VI rules (also includes injection well integrity) Other subsurface resources Seals: Wells and Natural Rocks Storage formation CO2 plume behavior Long-term permeability and porosity
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Primary focus is on carbonate geochemistry

Primary considerations for CO2 geochemical effects include: Mineral dissolution Metal and other trace element mobility
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http://acmg.seas.harvard.edu/people/faculty/djj/book/bookchap6-18.gif

CO2 solubility in water changes with salinity, pressure, temperature

Dealing with supercritical CO2 at depth Behavior of CO2 and geologic fluids within the reservoir will differ from shallow systems due to P, T effects on CO2 solubility Need to account for CO2 thermophysical behavior both under storage formation conditions for predicting reservoir behavior, and in all aspects of the system when performing site and risk assessments
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Duan, Z. and Sun, R. An improved model calculating CO2 solubility in pure water and aqueous NaCl solutions from 273 to 533 K and from 0 to 2000 bar. Chemical Geology 193 (2003) 257-271.

A variety of reactive materials are present in all areas of a sequestration system

Solids Sandstones Carbonates Shale Basalts Cement Steel Fluids Brine and Saline fluids Oil Low-TDS waters
Mt. Simon Sandstone Cores (MRCSP / Indiana Geologic Survey) Lower Tuscaloosa Sandstone (in reactors) (SECARB/TX-BEG)

Class H Well Cement Reacted with H2S and CO2

Basalt Cores (Big Sky)

A variety of pressure, temperature and baseline geochemical conditions exist in geologic CO2 sequestration systems
Carbonate chemistry, pH effects primary focus; also solvent effects (e.g., organics) Potential co-constituents of a CO2 stream Can the system handle trace amounts of H2S, SO2, O2, byproducts of CO2 capture systems? P,T conditions will affect thermodynamics and kinetics of different reaction processes Ion exchange, sorption, dissolution, precipitation Also need to consider possible secondary geochemical effects and geochemical monitoring tools Redox, microbiology, organics, isotope geochemistry

Geochemistry plays an important role in all aspects of a geological CO2 sequestration system
Monitoring techniques Groundwater aquifers Liability issues EPA Class VI rules (also includes injection well integrity) Other subsurface resources Seals: Wells and Natural Rocks Storage formation CO2 plume behavior Long-term permeability and porosity
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Lower Tuscaloosa Sandstone (SECARB Cranfield Injection Site)

Minimal short-term geochemical reactivity Clay protection of carbonates Longer term reactions may occur

Field Experiment Data

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Lab Experiment Data

Lu, J.; Kharaka, Y.; Thorsden, J. J.; Horita, J.; Karamalidis, A.; Griffith, C.; Hakala, J. A.; Ambats, G.; Cole, D. R.; Phelps, T. J.; Manning, M. A.; Cook, P. J.; Hovorka, S. Geochemical interactions in the Lower Tuscaloosa reservoir at the Cranfield CO2 sequestration site, Mississippi, USA Under Review.

Geochemical Reactions Microbiological Studies

Which microbial communities affect geochemical processes in CO2 storage formations and in shallow groundwaters? What geomicrobiological processes need to be included as part of predictive modeling efforts?
Characterize the influence of microbes on supercritical CO2 storage in candidate storage formations (basalt, sandstone, depleted oil reservoirs) Determine how native microbes respond to supercritical CO2

Lower Tuscaloosa Sandstone (MS) (SECARB / TX Bureau of Economic Geology) Wallula Pilot Well Basalt (WA) (BSCSP) Wellington Oil Field (KS) (SWP / Kansas Geological Survey)
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Science base enables a more reliable assessment of the impact of critical processes at the system level.
wellbore permeability will increase

wellbore permeability will not increase

Based on conservative assumptions Avoid areas with wellbores

avoid depleted oil and gas reservoirs

Require use of CO2-resistant cement

higher costs & limited field-use experience

Based on limited experience base Potentially underestimate long-term costs

liability; wellbore maintenance; etc.

CO2+brine dissolves hydrated cement

CO2-Brine-Cement and CO2-Cement reactions behave differently

Unaltered cement

Altered cement

Supercritical CO2
Ca(OH)2 depleted zone (1) Degraded Zone (3) CaCO3(s) barrier (2)

CO2 saturated brine

Propagation of Fronts
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Kutchko, Strazisar, Dzomback, Lowry, & Thaulow, Environmental Science and Technology, (2007)

Different reaction effects are observed when H2S is present as a co-constituent in the laboratory

Kutchko, Strazisar, Hawthorne, Lopano, Miller, Hakala, Guthrie, Intl J. GHG Control (2011)

Prediction of groundwater aquifer response complicated due to system heterogeneities

Laboratory batch reaction experiments with Gulf Coast Aquifer samples

Observed change in pH values, mineral morphology after CO2 reaction with samples Elevation of Type I and II cations with initial CO2 flux Type I reached equilibrium, but Type II declined over time (sorption effect?) Rapid reactions of carbonate minerals contribute to observed changes in solution chemistry

Lu, Partin, Hovorka, Wong, Environ. Earth Sci. (2010)

Shallow aquifer samples from Illinois and Texas show CO2 reaction results similar to the Gulf Coast Aquifer
Laboratory experimental conditions using natural aquifer core samples pH decline after CO2 exposure Increase in Type I cations, some Type II cations (e.g., Fe) Increase in EPA-regulated elements, although concentrations remain below the MCLs for U and As

Little and Jackson, Environ. Sci. Technol. (2010)

Shallow CO2 injection groundwater monitoring at the ZERT site in Bozeman, MT

Rapid, systematic pH changes (7.0 5.6), alkalinity, and electrical conductance following CO2 injection Increase in Ca, Mg, Fe and Mn following injection Dissolution of carbonate minerals and desorption-ion exchange from lowered pH values

Kharaka, Thorsden, Kakouros, Ambats, Herkelrath, Beers, Birkholzer, Apps, Spycher, Zheng, Trautz, Rauch, Gullickson (2010) Environ. Earth Sci.

Modeling to predict aquifer-specific CO2-induced geochemical changes

Mineralogical properties of receiving aquifer dictate observed result of CO2 migration into shallow aquifers CO2 gas dissolution into groundwater and subsequent reactions will drive the evolution of carbonate chemistry and pH in the aquifer

Wilkin and DiGiulio, Environ. Sci. Technol. (2010)

Natural analog sites used to study geochemistry of aquifers with elevated CO2 and salinity
Natural analogs CO2 naturally upwelling through shallow aquifer in volcanic or geothermal settings
Rapid release pathways along faults Diffuse CO2 rising and flowing through aquifer

High alkalinity and carbonate dissolution buffers pH changes due to carbonate influx Keating et al. (2009)
Environ. Earth Sci.

Buffering capacity and unknown geochemical reactions complicate modeling efforts

Keating et al. (2009) Environ. Earth Sci.

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Ongoing collaboration between NETL-ORD, University of Pittsburgh, and LANL

Chimayo aquifer sample collection from surface outcrops (March 2009)

Roadcut Bedplane 2 Yellow (Lithosome A: silty-clayey fine sand) Roadcut Bedplane 1 Gray (Interbedded B & A, finegrained) Streamcut 2 Green (Lithosome B, sand and gravel channel Keating et al. (2009) Environ. Earth Sci. fills) Streamcut 1 Blue (Lower Lithosome B: silt, clay, fine sand floodplain sediment)

0.1 km

Google Earth

Keating et al. (2009) Environ. Earth Sci.

What is present in Chimayo sediments? If we determine what is present, can this information be used in reactive transport simulations? Tools for identifying trace element content Scanning Electron Microscopy Often, trace elements not concentrated enough to observe in elemental maps X-ray Absorption Spectroscopy Ideal for identifying speciation and distribution of elements in environmental samples, but limited access to facilities Sequential Extraction Techniques Relatively simple to perform and may yield useful information, but potential limitations with selectivity
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Ongoing collaboration between NETL-ORD, University of Pittsburgh, and LANL

Analysis of solids (Q-XRD and SEM) show quartz and clays with feldspars, kaolinite, calcite, hematite, other phases
Q-XRD, wt%

Quartz
Ba, Sr and Ca in randomly distributed phase (RCBP2-G)

4,000 S 3,000

Ba

Clay coating/ weathering

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Counts

2,000 O Sr Ca Ca

Ba

1,000

Ba Ba

Ongoing collaboration between NETL-ORD, University of Pittsburgh, and LANL

0 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

keV

Sequential extractions, CO2 batch reactions and synchrotron characterization provide information on trace elements
Ratio of [Extraction Step]/[Total]
0.04 Exchangeables/Carbonates MnOxides (Reducibles) FeOxides (Reducibles) Oxidizables

0.03

As K/Pb L1

350 m x 350 m

Fe K

0.02

0.01

0 As U

As(V) As(III)

Ongoing collaboration between NETL-ORD, University of Pittsburgh, and LANL

Future Geochemistry Research Needs

Organic geochemistry Secondary geochemical effects (e.g., redox, microbial reactions) Robust inputs for modeling efforts Needed for predictive tools, quantitative risk assessment Intermediate-term (between laboratory/short-term field and steady-state natural analog) conditions?