cider 12 deep time - university of california, …...cider 12 deep time earth materials i...
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CIDER 12 Deep Time
Earth Materials I Introduction to Earth Materials (Hirschmann) Earth Materials II Exp. Studies Related to Early Earth Proc (Rubie) Earth Materials III The Mantle (Li) Tutorial IV: Equations of State (Li) Earth Materials IV Accretion, Magma Oceans, Core Formation (Rubie) Tutorial V: Molecular Dynamics (Caracas) Earth Materials V Transport Properties (Williams) Earth Materials VI The Core (Li)
July 16-28, 2012 KITP, Santa Barbara CA
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Earth’s Mantle
P: 136 GPa T: 3000 K x: ? t: ?
How are Earth processes controlled by material properties?
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Interpret 1D Seismic Profile + Rock Records: X-T-t
Dziewonski and Anderson 81 PEPI
LAB Melt, water TZ Discontinuities Depth: Phase transitions Width: Fe partition, phase equilibria Magnitude: Density, velocity Topography: Clapeyron slope, kinetics D” Phase transitions Deep time MO overturn: Density
Frost 08 Element
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Explain Seismic Tomography + Geochemical Domains: X-T-t
Garnero/McNamara 08 Science
Kellogg et al. 99
Stracke 05 G3
Plate Tectonics Slab, Plume: Density, viscosity, conductivity Mantle Convection Rayleigh #: Density, viscosity, conductivity, heat capacity CMB Interaction Partition, transport
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Iron Plays a Critical Role in Mantle Evolution
Jie (Jackie) Li, University of Michigan
Phase transition Partitioning Oxidation state Spin crossover Density, velocity, elasticity Transport properties
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Phase Transition: Coordination Number
Fei 98 UHPM
Pauling’s Rules
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Phase Transition Affects Density and Velocities
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Phase Transition in Mg2SiO4 Produces Density/Velocity Jumps
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Clausius-Clapeyron Slope G = U + PV -TS GA = UA + PVA -TSA GB = UB + PVB –TSB
For an infinitesimal change in P and T dGA = VAdP - SAdT dGB = VBdP - SBdT
Along the boundary GA = GB dGA = dGB i.e. VAdP - SAdT = VBdP – SBdT ΔVB-AdP = ΔSB-AdT dP/dT = ΔSB-A/ΔVB-A
Phase boundary (curve) dP/dT = Slope of tangent to curve Sign and value of slope
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Sign of Clapeyron Slope Indicates Thermal Effect
dT/dP = ΔV/ΔS
α to β transition (410 km) Positive Clapeyron slope (common) β smaller molar volume, smaller molar entropy Exothermic
γ to PV+FP transition (660 km) Negative Clapeyron slope (uncommon) PV+FP smaller molar volume larger molar entropy Endothermic
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TZ Topography / Barriers to Convection
gamma
Pv+Fp 660 km
resistance to plume rising
resistance to slab sinking
gamma
Pv+Fp gamma
Pv+Fp
boundary pushed downwards
boundary pushed upwards
dT/dP = ΔV/ΔS = 769 K/GPa�Assuming linear slope�
For slab dT ~ -500 K, dP ~ 0.6 GPa (15 km)�For plume dT ~ +200 K, dP ~ -0.3 GPa (7.5 km)
Fei et al. 2004
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D” Topography and Structure
Shim 08 AREPS Lay et al. 08 Nature Geo.
Double Crossing PPv lens
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Iron Lowers and Broadens Phase Boundaries Mw or Fp Phase Rule f = c + 2 – p
Fei 1998 UHPM
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Iron Shifts and Broadens Pv-PPv Transition
Mao 07 AGU mono Mao et al. 06 Science Mao et al. 06 PNAS
Pv contains more iron than PPv Hirose 08 AM
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Iron Increases Density and Lowers Sound Velocities
Stixrude 07 ToG
ρ = m/V ρVp2 = K + 4G/3 ρVS
2 = G
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Iron’s Valence State / Oxidation State
Fe [Ar]3d64s2
metallic
Fe2+ [Ar]3d6
ferrous Fe3+ [Ar]3d5
ferric
3Fe2+ = 2Fe3+ + Fe0
Wood et al. 06 Nature
Fe3+ + Al3+ = Mg2+ + Si4+
Fe3+ + Fe3+ = Mg2+ + Si4+
McCammon 97 Nature
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Crystal Field Splitting in Iron
Cubic, octahedral site
Spherical, degeneracy
Orthorhombic 8-12 C.N. site
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Pressure-Induced Spin Crossover in Fe2+
Δ Π
High Spin
Low Spin
Δ
Π
HS IS LS
Intermediate Spin
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Probe Electronic Structure Mössbauer spectroscopy • Conventional • Synchrotron - Energy domain - Time domain Nuclear Forward Scattering
X-ray emission spectroscopy • Local moment • Kβ’/Kβ
Isomer shift
Quadrupole splitting
Struzhkin 04, JPCM
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Pressure-Induced Spin Crossover in Fp and Pv
HS LS
Badro et al. 03 Science
1.5
1.0
0.5
0.0
Nor
mali
zed
inten
sity,
a.u.
70707060705070407030
Energy, eV
Al free, low spin Al free, 2 GPa Al free, 100 GPa Al bearing, 100 GPa
Lin et al. 07 Science Badro et al. 04 Science
Li et al. 04 PNAS
Lin et al. 08 Nature Geo
McCammon et al. 08 Nature Geo
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Spin Crossover Influences Physical Properties
Density & elasticity Lin et al. 05, 07 - Fp Fei et al. 05 – Pv
Radiative conductivity - Fp Badro et al 04 - blue shift Tsuchiya et al. 06 - red shift Goncharov et al 06 - red shift
Electric conductivity - Fp Ohta et al. 07
Vs
Pressure
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Limited Effects of Spin Crossover on Partitioning
Badro et al 03, 05 - Pv/Fp Li et al. 04; Li 07 - Pv/Fp Irifune et al. 10 - Pyrolite
Spin crossover gradual Fe3+ strongly prefers pV
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Birch-Murnaghan EoS
Finite strain theory: Eulerian strain Thermodynamics Macroscopic view
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“Hot” BM EoS T
P
T0
Isobaric heating
Isothermal compression
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Elasticity: Atomic Potential and Lattice Dynamics
Lattice dynamics: The Core
Microscopic view Bulk modulus Thermal expansion
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Mie-Grüneisen-Debye EoS - γ
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Mie-Grüneisen-Debye EoS – γ, q
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Modified Mie-Grüneisen-Debye EoS – γ, q0, q1
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Post-Spinel Transition and 660-km Discontinuity
Fei et al. 04 JGR Fei et al. 04 PEPI
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Perovskitic Lower Mantle
Murakami et al. 12 Science
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Conclusions and Outlook
Material properties under deep mantle P-T-x-t conditions key to understanding the state and history of the mantle but poorly constrained
State of the art Experimental: ~ 4 Mbar (400 GPa), ~ 6000 K Analytical: time second spatial 10 nm
Planetary perspectives
CIDER
Brooks Bays Weber et al. 11 Science