What monitoring techniques are appropriate and effective for detecting CO2 migration in groundwater: isotope-based monitoring Philippe Négrel Acting in complicity with Pauline Humez. Results from Pauline s PhD Thesis mardi 2 septembre 2014
The foundations: CO 2 geological storage option > 2
The foundations: Potential CO 2 leakage scenarios Tools development towards monitoring program > 3
Key questions for monitoring > A site specific plan Constraints Objectives, depending on the stage of the project > Spatial dimension Resolution of the system Footprint of monitored area > Temporal dimension Frequency Duration > Baseline acquisition Initial state > Integrate various methods Need for combining adequate methods Key questions for isotope monitoring > Capacity of the isotope tools to detect and track CO 2 leakage, > Experimental approach to better constrain and understand water-rock-co 2 interaction, > Find geochemical indicators, > Testing phase on site, > Specifications and procedure on the applicability and the choice of isotopic tools, > Addition of modeling phase, > And the future > 4
BASIC KNOWLEDGE OF ISOTOPES 1 2 H He 1.008 4.00 3 4 5 6 7 8 9 10 Li Be B C N O F Ne 6.94 9.01 10.81 12.01 14.01 16.00 19.00 20.18 11 12 13 14 15 16 17 18 Na Mg Al Si P S Cl Ar 23.00 24.31 26.98 28.09 30.97 32.06 35.45 39.95 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 39.10 40.08 44.96 47.90 50.94 52.00 54.94 55.85 58.93 58.71 63.55 65.38 69.72 72.59 74.92 78.96 79.90 83.80 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe 85.47 87.62 88.91 91.22 92.91 95.94 98.91 101.07 102.90 106.40 107.90 112.40 114.80 118.70 121.80 127.60 126.90 131.30 55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn 132.90 137.30 138.90 178.50 181.00 183.90 186.20 190.20 192.20 195.10 197.00 200.60 204.40 207.20 209.00 (210) (210) (222) 87 88 89 104 105 Fr Ra Ac** Ku Ha (223) (226) (227) (258) (260) Dimitri I. Mendeleïev 58 59 60 61 62 63 64 65 66 67 68 69 70 71 *Lanthanides Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu 140.10 140.90 144.20 (145) 150.40 152.00 157.30 158.90 162.50 164.90 167.30 168.90 173.00 175.00 90 91 92 93 94 95 96 97 98 99 100 101 102 103 **Actinides Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr 232.00 231.00 238.00 237.00 239.10 (243) (247) (247) (251) (254) (257) (256) (254) (258) So friendly > 5
Isotopes definition Isotope : Chemical elements with the same atomic number (same name and same position in the Mendeleiev table) but which differ by their atomic mass. Atomic mass p n p X Atomic number 16 8 O neutron proton electron 18 8 O > 6
> 7
> 8
The radiogenic isotopes Rb/ Sr Decay constant time daughter initial parent > 9
The stable isotopes > 10
THE ISOTOPE FRAME OF CO 2 LEAKAGE MONITORING > 11
Watch out for possible leaks > water quality in the aquifers interbedded between the storage zone and the surface, and the quality of the overlying cap rock. > sensitive points must be controlled and monitored by reliable permanent measurement systems (geophysical and/or geochemical). > CO 2 in geochemical reactions : disappearance of the sign in water. > 12
Link between CO 2 and the isotope «answer» Monitoring > Define an Objective CO 2 leakage detection > Decide Where to Monitor Storage site(s) > Decide What to Monitor Isotope tools but see below > Prioritize > Comparison isotope capabilities and site characteristics > Develop a Plan > Select Tools that Match your Strategy Isotope tools but see above Isotope toolbox > The following geochemical tracers are potentially capable of recording the changes in water quality as a result of CO2 intrusion: migration and reactions of CO 2 using the d 13 C, d 18 O and dd of the water molecule as oxygen being impacted by the CO 2, water rock interactions using strontium, neodymium, boron, lithium and lead isotopes, formation of secondary phases using the calcium, lithium, boron isotopes (carbonate precipitation, formation of clay) with specific isotope fractionations, evolution of redox fronts using chromium, zinc, selenium, uranium, iron, sulphur, antimony, copper isotopes whose fractionation is linked to the redox state of the water. > 13
Stable isotopes and CO 2 > 14
Stable isotopes and CO 2 > 15
«innovative» isotopes Toolbox for tracing hydrosystems, mixture of waters, water-rock interactions etc. 1 2 H He 1.008 4.00 3 4 5 6 7 8 9 10 Li Be B C N O F Ne 6.94 9.01 10.81 12.01 14.01 16.00 19.00 20.18 11 12 13 14 15 16 17 18 Na Mg Al Si P S Cl Ar 23.00 24.31 26.98 28.09 30.97 32.06 35.45 39.95 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 39.10 40.08 44.96 47.90 50.94 52.00 54.94 55.85 58.93 58.71 63.55 65.38 69.72 72.59 74.92 78.96 79.90 83.80 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe 85.47 87.62 88.91 91.22 92.91 95.94 98.91 101.07 102.90 106.40 107.90 112.40 114.80 118.70 121.80 127.60 126.90 131.30 55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn 132.90 137.30 138.90 178.50 181.00 183.90 186.20 190.20 192.20 195.10 197.00 200.60 204.40 207.20 209.00 (210) (210) (222) 87 88 89 104 105 Fr Ra Ac** Ku Ha (223) (226) (227) (258) (260) 58 59 60 61 62 63 64 65 66 67 68 69 70 71 *Lanthanides Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu 140.10 140.90 144.20 (145) 150.40 152.00 157.30 158.90 162.50 164.90 167.30 168.90 173.00 175.00 90 91 92 93 94 95 96 97 98 99 100 101 102 103 **Actinides Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr 232.00 231.00 238.00 237.00 239.10 (243) (247) (247) (251) (254) (257) (256) (254) (258) C "Classical" U Research Ti "Future" As one stable isotope > 16
Multi isotopes characterization > 17
THE EXPERIMENTAL APPROACH > 18
Context and Objective > Impacts of CO 2 geological storage and CO 2 leakage into fresh groundwater > Case study: Albian aquifer, Paris Basin [Glauconite minerals] > Experimental approach to better constrain and understand water-rock-co 2 interaction find geochemical indicators of weathering > 19
Albian aquifer, Paris Basin W SW ( PA R IS ) E N E A N G E R S T O U R S O R L E A N S M E LU N M E AU X R E IM S V E R D U N M E T Z 0 0 1000 1000 2000 2000 A N T E T R I A S S I C Tertiary 3000 Low perm ability layers 3000 M A IN R E SE RVO IR S Albian sands Wealdian sands Lusitanian lim estones D ogger lim estones Rhetian sandstones Keuper sandstones Bundsandstein sandstones Targets for storing CO 2 : > 20
Experimental approach CO 2 (g) Liquid phase Solid phase BEFORE Composition Isotope signature Chemistry Isotope signature Mineralogy Isotope signature Chemistry CO 2 CO 2 +Water+rock Liquid phase Solid phase AFTER Chemistry Isotope signature Mineralogy Chemistry > Selection of Albian water and solid samples (Humez et al. 2012) > PTFE batch reactors with CO 2 & controlled batch reactor without CO 2 & ph equipped reactor > L/S=10, pco 2 = 2 bar > CO 2 -water-rock contact time: 1 day, 1 week, 2 weeks and 1 month A series of water for geochemistry and isotope investigations: focus on δ 13 C DIC (fate of CO 2 (g)) and δ 11 B (minerals contribution) and major and trace elements > 21
CO 2 -water-rock interaction > Evidence of CO 2 reactivity by Ca vs. δ 13 C DIC > Possible mechanisms involved: (δ 13 C of injected CO 2 (g) = -40 ) o Glauconite dissolution: - Slow kinetics - Increased Ca conc. Up to 1 day of CO 2 -water-glauconiteinteraction o Carbonate dissolution? No carbonate in the system o Glauconite surface reaction: - rapid kinetics - large reactive surface area - Increased proton due to CO 2 dissolution CO 2 (g) =CO 2 (aq) CO 2 (aq) +H 2 O = HCO 3- + H + - Increased Ca conc. > ((Glauco_OH)(Glauco_O)) 2 Ca + 2H + K1 > 4Glauco_OH + Ca 2+ > 22
CO 2 -water-glauconite interaction > Evidence of surface reactions and dissolution in the system glauconite-water-co 2 > Necessary to confirm these processes by additionnal tracing: δ 11 B as a tool to discriminate between surface reaction and dissolution mechanisms > 23
B isotope systematic in clays «Free B»in interlayer position B bound in tetrahedral site of silicate framework [Williams et al. 2006] Compartment 1 Compartment 2 Total boron of bulk clay = Structural boron + free boron The δ 11 B of the B substitued in the tetrahedral sheet is more negative than the bulk clay due to preference of 10 B for tetrahedral coordination (Palmer and Swihart, 1996) Evidence of «large» B isotope variation between: Surface processus Dissolution processus > 24
Tracing the weathering of glauconite by B isotope Glauconites are the main B-bearing phase control on the evolution of the aqueous B Without CO 2 Implication of glauconite mineral in CO 2 -water-rock interaction CO 2 -water-rock interaction Free boron of glauconite (surface reaction processus) B in the structure of glauconite (more negative value ~ -4 ) Information about boron compartments involved during experimentation > 25
And the rest > 26
TO CONCLUDE YES BUT > Are isotope tools efficient in a less constraint system? > Are isotope tools robust at larger scale? from lab to site > 27
CO 2 FIELDLAB project Oslo 8 m CO 2 18/8/11 31/8/11 7/9/11 12/9/11 19/9/11 Monitoring network baselin e Inj. CO 2 Relaxation Objectives: Starting sampling End sampling. δ 11 B, δ 7 Li, 87 Sr/ 86 Sr, δ 34 S SO4, δ 18 O SO4, Financement: > 28
Multi-components system > 29
Multi-components system 5 m 10 m 15 m δ 11 B, δ 7 Li, 87 Sr/ 86 Sr, δ 34 S SO4, δ 18 O SO4, δ 18 O H2O, δ 2 H H2O > 30
AND THE FUTURE > Identify CO 2 and water-rock-co 2 interactions new experimental approaches using various minerals to reconstruct the rock > Define the contribution of the different geochemical processes to the chemical and isotope variations Testing the rest of the isotope from the tool box > coupling geochemical tools, isotope tools and modelling for early detection of CO 2 leakage including complex cases Understanding of the system dynamic at the whole scale, > Adapt and test isotope tools according to site specificities > Capability of the isotope tools to track CO 2 leakage further and further away from the injection > 31
Additional reading > 32
Additional reading II > 33