Diffusion in Earths Deep Interior Insights from HighPressure

Diffusion in Earth’s Deep Interior: Insights from High-Pressure Experiments Jim Van Orman Department of Geological Sciences Case Western Reserve University

COnsortium for Materials Properties Research in Earth Sciences COMPRES is an NSFsupported consortium that supports study of Earth material properties, particularly at high pressures and temperatures (Earth interior conditions).

Interior of the Earth The crust and upper mantle are composed of the familiar silicate minerals. In the deep mantle, these transform to denser highpressure forms.

Mantle Mineralogy

To study these and other materials, COMPRES supports user facilities, including several synchrotron X-ray facilities where high-pressure experiments are performed. Advanced Photon Source

Synchrotron facilities also house very large presses that allow study of somewhat larger samples. Mounted on a stage that can move the press with micron precision to put the sample at the focal point of the X-ray beam.

Mafic melt viscosity experiment by Lara Brown, Chip Lesher, et al. , UC-Davis

Diffusion in Earth’s Deep Interior: Insights from High-Pressure Experiments What is Diffusion? Diffusion is the transport of matter by random hopping of atoms. It is a fundamental step in many important chemical and physical processes. http: //www. johnkyrk. com/diffusion. html

Atoms initially confined to a plane spread out with time according to a simple mathematical law, based on theory of a random walk. How rapidly they spread depends on the diffusion coefficient. Diffusion is *much* more rapid in gases and liquids than in minerals.

How can diffusion happen in a crystal? Gas Crystal

In a perfect crystal, diffusion is extremely difficult But crystals are never perfect. . . dislocations grain boundaries

Diffusion by a vacancy mechanism More vacancies = faster diffusion Vacancies move much faster than the atoms themselves

Diffusion in the Deep Earth (1): Maintaining a Heterogeneous Mantle Subduction makes the mantle chemically heterogeneous Convective and diffusive mixing On what length scales can the heterogeneity be preserved?

Diffusion in the Deep Earth (2): Chemical Transfer at the Core-Mantle Boundary

Diffusion in the Deep Earth (3): Diffusion and Viscosity diffusion coefficient viscosity Stokes-Einstein Equation

Diffusion in Deep Earth Materials at High Pressure 1. Solid Iron-Nickel Alloys (Inner Core) 2. Mg. O (Lower Mantle) What are the fundamental controls on the diffusion rates?

High-Pressure Experiments Pressure = Force/Area

Multi-Anvil Press Sample size ~1 mm

1. Diffusion in Iron-Nickel Alloys at High Pressure Fe Ni

Homologous Temperature Scaling For Close-Packed Metals Inner Core Does it hold at high pressure?

Fe-Ni Diffusion Profiles 12 GPa, 1600 o. C Yunker and Van Orman, 2007 Boltzmann-Matano

DFe-Ni vs Composition Yunker and Van Orman, 2007 12 GPa 1600 o. C 2 hr Melting curve 1 atmosphere

DFe-Ni vs Pressure at Constant Homologous Temperature Yunker and Van Orman, 2007

log. DFe-Ni vs Pressure Yunker and Van Orman, 2007

log. DFe-Ni vs Pressure Yunker and Van Orman, 2007

log. DFe-Ni vs Pressure Yunker and Van Orman, 2007

Inner core viscosity (Harper-Dorn creep regime) ~1011 - 1012 Pa s Suggests that inner core behaves like a fluid on the timescale of Earth rotation, and is free to super-rotate instead of being gravitationally locked to the mantle. Inner core anisotropy an active deformation feature, rather than growth texture?

2. Diffusion in Mg. O (Mg, Fe)O is thought to represent ~15 -20% of the lower mantle.

Prior Studies of Self-Diffusion in Mg. O (Atmospheric Pressure) Mg O Van Orman and Crispin, in press, Reviews in Mineralogy & Geochemistry

Diffusion in Mg. O at High Pressure Sample retrieved from experiment at 2000 o. C and 25 GPa 25 Mg, 18 O Experiments were designed to measure lattice and grain boundary diffusion of both Mg and O enriched Van Orman et al. , 2003

Van Orman et al. , 2003

Ab Initio Calculation

Cation diffusion in Mg. O is predicted to become slower with increasing depth in the lower mantle (except just above the core-mantle boundary).

A surprise: Al 3+ diffuses rapidly in Mg. O Al 2 O 3 Mg. O polyxtl Van Orman et al. , 2003 Mg. O xtl

Al 3+ impurities in Mg. O: Cation vacancies are created to maintain electrical neutrality. These are attracted to Al 3+ and tend to form pairs (and higher order clusters at low temperature). These defect associates have been known about for decades, but their influence on diffusion has been largely neglected. Al-vacancy pairs enhance the mobility of Al, but diminish the mobility of the vacancy (and thus the mobility of other cations that diffuse using vacancies).

Spinel Mg. Al 2 O 4 Mg. O E-probe scan Diffusion experiments to determine Alvacancy binding energy and pair diffusivity 1 atm to 25 GPa 1577 to 2273 K Van Orman et al. , 2009

Van Orman et al. , 2009 Diffusion profiles were fit to a theoretical model to determine binding energy and diffusivity of the Al-vacancy pairs. Binding energies for all experiments at atmospheric pressure are -50 ± 10 k. J/mol (2 s), consistent with theoretical values of -48 to -53 k. J/mol (Carroll et al. , 1988) and have no clear pressure dependence.

However… The diffusion coefficient of the Al-vacancy pair does depend on pressure. V = 3. 22 cm 3/mol (+/- 0. 25) Similar to pressure dependence for Mg self-diffusion (3. 0 cm 3/mol) Van Orman et al. , 2009

What about other trivalent cations? Crispin and Van Orman, 2010 Al (0. 535 Å)

log. D (m 2/s) Diffusivity and Ionic Radius (Angstroms)

Why is chromium so slow? • Cr 3+ 1 s 2 2 p 6 3 s 2 3 p 6 3 d 3 Crystal field effect

The crystal field effect seems to explain differences in the diffusivity of other transition metals. • Fe 2+ 6 d electrons – 3 t 2 g, 2 eg, 1 t 2 g • Co 2+ 7 d electrons – 3 t 2 g, 2 eg, 2 t 2 g Wuensch and Vasilos, 1962 • Ni 2+ 8 d electrons – 3 t 2 g, 2 eg, 3 t 2 g (Similar to Cr 3+)

Crispin and Van Orman, 2010

A transition in the electronic structure of Fe 2+ in Mg. O is one of the exciting discoveries in mineral physics in the last decade (Badro et al. , 2003). Marquardt et al. (2009) Science • At high pressure, the two electrons in eg orbitals in Fe 2+ move to t 2 g orbitals. • This so-called “spin” transition affects a wide range of properties (density, seismic wave speeds). • It may also have a strong influence on diffusion.

Crispin and Van Orman, 2010

Conclusion: How might electronic spin transitions affect diffusion length scales in the mantle? High Spin Low Spin? Spin transitions may slow the diffusion of transition metals significantly. This would: 1) Make chemical exchange across the core-mantle boundary more difficult. 2) Make chemical heterogeneity in the deepest mantle more difficult to erase.