Microbial Activity and Carbonate Mineral Precipitation Control Mixing, Reaction and Transport in Porous Media

Transcription

1 Microbial Activity and Carbonate Mineral Precipitation Control Mixing, Reaction and Transport in Porous Media DOE Subsurface Biogeochemical Research (SBR) program, 7 th Annual Principal Investigator (PI) meeting April 30 May 2, 2012, Washington, DC. Robin Gerlach Associate Professor - Chemical and Biological Engineering Montana State University

2 Concept -

3 INL SFA program - Reactant mixing Initial deposition pattern precipitate Migrating mixing and precipitation zones pure A Supersaturated solution Subsequent focusing of precipitation and flow diversion Porous medium with homogeneous urease distribution urea CO 3 2- (Ca,Sr)CO 3 urea, Ca 2+ Pre-mix Urease enzyme or ureolytic microbe Example: in situ CO 3 2- production from ureolysis Reaction zone focusing Further focusing; isolated, residual precipitate in Situ Reactant Generation Solution A pure B Migrating mixing zone, stabilized precipitate Sequential Injection Solution B Precipitation zone focusing precipitate Parallel flow with mixing zone pure A pure B Parallel Injection INL SFA - Reactant mixing Redden et al.

4 Microbially Induced Calcium Carbonate Precipitation (MICP) Urea hydrolysis increases ph and alkalinity and thus the saturation state of calcium carbonate urease CO(NH 2 ) 2 + H 2 O NH 2 COOH + NH 3 NH 2 COOH + H 2 O NH 3 + H 2 CO 3 CO(NH 2 ) H 2 O 2 NH 3 + H 2 CO 3 2NH 3 + 2H 2 O 2NH OH - (Urea hydrolysis) (ph increase) rate limiting H 2 CO 3 + 2OH - HCO 3- + H 2 O+ OH - CO H 2 O CO Ca 2+ CaCO 3 (carbonate precipitation) Ureolysis is only one possible way to manipulate the saturation state of carbonates Mitchell, A.C.; Dideriksen, K.; Spangler, L.H.; Cunningham, A.B.; Gerlach, R. (2010). Environmental Science and Technology. 44(13): doi: /es903270w Mitchell, A.C. and Ferris, F.G. (2006). Geomicrobiology Journal, 23, Mitchell, A.C. and Ferris, F.G. (2006) Environmental Science and Technology, 40, Mitchell, A.C. and Ferris F.G. (2005) Geochimica et Cosmochimica Acta, 69, MSU Center for Biofilm Engineering

5 Risk of Cell/Urease Inactivation during Precipitation Process Pulsed flow static Pulsed flow Pulsed flow + Sr MSU Center for Biofilm Engineering

6 Risk of Cell/Urease Inactivation through Precipitation S. Parks MSU Center for Biofilm Engineering

7 Risk of Cell/Urease Inactivation through Precipitation Pulsed flow static Pulsed flow Pulsed flow + Sr E. Lauchnor MSU Center for Biofilm Engineering

8 Risk of Cell/Urease Inactivation during Precipitation Process Pulsed flow static Pulsed flow Pulsed flow + Sr Need to strike balance between growth and precipitation rate Might want to reduce permeability (or not) depending on desired outcome (application) MSU Center for Biofilm Engineering

9 Microscale (Phase Field) Modeling of Biofilm-Mediated Calcite Precipitation Constant Flow shear stress stretches biofilm, no gravity effect calcite accumulation mainly occurs at biofilm solvent interface potential for diffusion limitations due to calcite precipitation Zhang and Klapper (2010) Water Science and Technology. doi: /wst Zhang and Klapper (2011) International Journal of Non-Linear Mechanics. doi: /j.ijnonlinmec

10 SCHULTZ, L.; PITTS, B.; MITCHELL, A.C.; CUNNINGHAM, A.B.; GERLACH, R. (2011). Microscopy Today. September 2011: MSU Center for Biofilm Engineering

11 Ureolysis-driven CaCO 3 formation at tmospheric pressure under flow conditions 40 μm Grey: calcium carbonate (calcite?) auto-fluorescence Green: gfp Blue: sand grain Grey: calcium carbonate (calcite?) Red: Dead cells / extracellular DNA (Prop. Iodide) Green: Live cells (SYTO9) 150 μm 40µm SCHULTZ, L.; PITTS, B.; MITCHELL, A.C.; CUNNINGHAM, A.B.; GERLACH, R. (2011). Microscopy Today. September 2011: MSU Center for Biofilm Engineering gfp construct. M. Kaufman, images: J. Connolly

12 Continuous-Flow Ca-Sr-CO 3 Precipitation MSU Center for Biofilm Engineering L. Schultz

13 Visualizing the Effect of Biofilms on Fluid Dynamics Inoculated Reactor t = 2 min t = 4 min t = 10 min MSU Center for Biofilm Engineering t = 22 min S. Bugni

14 Ureolysis-driven precipitation of CaCO 3 40 minutes Total Ca injected: 84 mg plugging observed 80 minutes 200 minutes Total Ca injected: 6500 mg 340 minutes 620 minutes MSU Center for Biofilm Engineering L. Schultz, S. Bugni, E. Lauchnor, A. Phillips, J. Connolly

15 NMR Imaging of MICP in Porous Media Columns 5cm cm FRIDJONSSON, E.O.; SEYMOUR, J.D.; SCHULTZ, L.N.; GERLACH, R; CUNNINGHAM, A.B.; CODD, S.L. (2011) Journal of Contaminant Hydrology : doi: /j.jconhyd

16 Flow Dynamics observed by PGSE-NMR FRIDJONSSON, E.O.; SEYMOUR, J.D.; SCHULTZ, L.N.; GERLACH, R; CUNNINGHAM, A.B.; CODD, S.L. (2011) Journal of Contaminant Hydrology : doi: /j.jconhyd Blue: clean bead pack Red: biomineralaffected beadpack 25 ms 100 ms 50 ms 200 ms 400 ms 600 ms

17 Concept -

18 Biofilms and Biominerals for Sealing Potential CO 2 Leakage Pathways MITCHELL, et al. (2008) The Journal of Supercritical Fluids. 47(2): doi: /j.supflu MITCHELL, et al.(2009) IJGGC. 3: doi: /j.ijggc CUNNINGHAM, et al. (2009) Energy Procedia. 1(1): doi: /j.egypro MITCHELL, et al. (2010) : ES&T. 44(13): doi: /es903270w EBIGBO et al. (2010) AWR. 33: doi: /j.advwatres CUNNINGHAM ET AL. (2011) Energy Procedia. 4: doi: /j.egypro MSU Center for Biofilm Engineering

19 Various groups have studied MICP with varying success Fujita et al. (2008) field test INL: Although collateral impacts such as reduced permeability were observed, overall results indicated the viability of manipulating biogeochemical processes to promote contaminant sequestration Martinez, DeJong, Ginn et al. (2011) 0.5 m column test (experiment and modeling): stopped-flow produces a more uniform calcite distribution recommend reverse inoculation Tobler et al. (2012) 10 cm columns: ureolysis limited eventually by the encapsulation of the biofilm by calcite suggest pulsed injection and re-inoculation MSU Center for Biofilm Engineering

20 2ft Sand Column Experiments Images 1 mm A. Phillips, J. Stringam, 100 μm

21 Biofilm-Induced Calcium Carbonate Precipitation (2 ft columns) BIGBO A.; PHILLIPS, A; GERLACH, R.; HELMIG, R.; CUNNINGHAM, A.B.; CLASS, H.; SPANGLER, L. Modeling microbially induced carbonate mineral recipitation in porous media. Water Resources Research. Submitted. December 03, WR In revision.

22 X-ray CT Imaging of MICP in Porous Media Columns Clean Sand After Treatment Clean Sand Inlet 0 8 cm Middle cm Outlet cm Porosity 47% 31 % 23 % 24 %

23 Reservoir Scale Modeling of Biofilm-Mediated Mineral Precipitation Details in: Ebigbo, Helmig, Cunningham, Class, Gerlach (2010) Advances in Water Resources, doi: /j.advwatres BIGBO A.; PHILLIPS, A; GERLACH, R.; HELMIG, R.; CUNNINGHAM, A.B.; CLASS, H.; SPANGLER, L. Modeling microbially induced carbonate mineral recipitation in porous media. Water Resources Research. Submitted. December 03, WR In revision.

24 30 in x 15 in Sandstone Core Phillips et al., ES&T submitted

25 30 in Diameter Core Fracture Plugging 100,000 10,000 radial flow rather than fracture-dominated flow was observed Permeability (md) 1, nd sealing event 1 st sealing event Experiment Duration (days) Phillips et al., ES&T submitted

26 30 in Diameter High Pressure Reactor J. Eldring

27 Radial Flow Reactor Model Results - University of Stuttgart and Montana State University - Pore Space Occupied by Calcite A. Phillips, A. Ebigbo

28 Summary and Conclusions Biofilm-mediated MICP has potential for controlled manipulation of porous media porosity, permeability, and stability via single well access applications beyond geologic carbon sequestration and Sr co-precipitation Combined experimental and modeling approach designed to reveal & quantify microscale processes and include them into large scale models & experiments to ultimately enable field scale applications

29 Summary and Conclusions Ureolytically active gfp construct will allow for spatio-temporal analysis of MICP Applicability to biofilm and mineral precipitation influenced transport phenomena well-beyond ureolysis-based MICP Limitations: CaCO 3 (calcite) only mineral phase, ureolysis only driver for precipitation, no inclusion of molecular mechanisms of nucleation (e.g. homogeneous vs. heterogeneous)

30 Acknowledgements DMS DE-FG-02-09ER64758 DE-FE DE-FC26 04NT42262

31 Co-Authors Montana State University: A. Phillips (Ph.D. student), J. Connolly (Ph.D. student), E. Lauchnor (postdoc), L. Schultz (M.S. student), S. Bugni (M.S. student), A. Cunningham, I. Klapper, A. Mitchell, T. Zhang Oregon State University: F. Colwell, G. Iltis (Ph.D. student), M. Kaufman (M.S. student), S. Ostvar (Ph.D. student), M. Schuster, D. Wildenschild, B. Wood Idaho National Laboratory: L. Guo, H. Huang, G. Redden University of Stuttgart: A. Ebigbo (Ph.D. student), R. Helmig

32