High-Pressure Geoscience: New Tools and Expanding Outreach

Russell J. Hemley
Geophysical Laboratory/CDAC* Carnegie Institution of Washington Washington, DC
*Carnegie/DOE Alliance Center

3.63

3.35

1.35

0.24

P (Mb

ar)

Earths Interior: 1920

Jupiter

THE EARTH AND BEYOND

Materials-based understanding of planetary and astrophysical bodies Planets and bodies outside our solar system New observations and space missions Implications for life elsewhere in the universe

Materials Science Impacts and Opportunities:

FUNDAMENTAL LIMIT

Pressures and temperatures Energetic photon/particle flux Chemical extremes Electromagnetic extremes Multiple extremes

performance

TODAY

lifetime Improved peformance in materials Realize the potential of unexplored extremes

tr an sf or m at io na e at m a ri

l ls

Challenge of Creating Earth Interior Conditions

Geophysical Laboratory Four Post Press 1910 The (Bridgman) unsupported area seal

The whole high-pressure field opened almost at once before me, like the vision of a promised land, with the discovery The Physics of High Pressure (1931).

High-Pressure Technology:
TOOLS FOR IN SITU MEASUREMENTS
Energy (keV)

Axial 2 x 2.5 mm diamonds

Radial 2 mm Be

Sup p o rting se a ts

Alumina layer

Sample

Platinum electrodes Metallic gasket

20 m 0m
I
Platinum electrodes

Evolution of Light Sources

X-ray to infrared (diffraction limited)

History of X-ray Sources

A new generation of large facilities is coming on line

X-ray Sources
NSLS II

Neutron Sources

D
SNS

D
Dedicated beamline (SNAP) >100 GPa neutron scattering

Higher brightness synch. Dynamic compression Energy Recovery Linacs Fourth Generation Sync.

Pulsed Power
ZR

Laser Sources
NIF

Magnetic compression Ultrahigh P-T conditions Static/dynamic

Ultrahigh P-T conditions Static/dynamic Stellar interiors

Only a small fraction of synchrotron advantages has been tapped for high-pressure geoscience

Brilliance High energy Energy resolution Spatial resolution Temporal resolution Polarization Coherence

Rapid advances and impacts in high pressure

Enormous potential to be harnessed As yet unexplored

Selected Technical Grand Challenge Questions

Reaching higher P-T conditions (1 TPa and 1 eV)? How small can we probe under extreme conditions (<1 nm)? Can we develop techniques that probe multiple length scales? What is required to go from point measurements to imaging? How can we address the problem of time scales (Ga to fs)? What are the properties of heterogeneous phases/complex assemblages (e.g., interfaces/grain boundaries)? Can we achieve a precision, accuracy, and resolutions enjoyed under ambient conditions?

Sample volumes of ~1 mm3 to pressures of 1 Mbar or more at temperatures of 5000 K, PACEM Prewitt Report 1987

OVERVIEW
SELECTED TOOLS X-ray Neutron Lasers/optical Transport Ex situ Analytical High P-T Devices

Cosmic Abundances

ROCK

METAL

VOLATILES

Post-Modern Mineral Physics post-perovskite

ppv(Mg,Fe)SiO3

2% higher density than pv Post-perovskite phase soaks up iron Core-mantle reactions Double transitions in D

Higher P-T behavior of post-perovskite phases and modeling super Earths

pt_all copy

[Valencia et al., Icarus (2006)]

[Umemoto et al., Science (2006)]

Predicted breakdown of post-perovskite at higher pressures (TPa range) New phases and structures?

New high P-T structures continue to be documented: (Mg,Fe)SiO3 >120 GPa

D But what is the postperovskite structure?

Cmcm

Pmcm (Fe-rich)
[Yamanaka et al., submitted]

Structure depends on Fe content Fe spin/magnetic/electronic state Other components Core-mantle reactions

Complex minerals at the nanoscale: beyond powder diffraction, nanomineralogy, texture

New minerals, high-pressure forms of chromite, discovered in shocked meteorite & synthesized in DAC
[Chen et al., PNAS (2003)]

Infrared spectroscopy of microdiamonds in zircon

[Dobrzhinetskaya et al., EPSL (2007)]

CCD

CCD

Measurements with sub-10 nm beams Diffraction/spectral imaging

Current state of the art: 200 nm focused x-ray beams

[Wang et al., in preparation]

Separate submicron Pt, Re, Fe samples

A

Single-crystal XRD on submicron powders

Observe 20 GPa/m P gradiant & peak-pressure in 1-m area

190 nm beam

5 m beam

Novel pressure-induced magnetic transition in magnetite

[Ding et al., Phys. Rev. Lett. (2008)]

Magnetic transition

Magnetite: Fe3+A (Fe2+,Fe3+) BO4

XMCD

XES

15GPa

4-ID-D beamline for XMCD

Energy calculation of HS-IS of Fe2+ in octahedral site

E. R. Morris and Q. Williams, J. of Geophy. Res. 102, 18139 (1997)

Electric resistivity anomaly

16-ID-D for XES

16-ID-B for Diffraction

Structural anomaly

Importance of multiple complementary techniques

The Earths Core: Observations and Questions

Nature of the dense fluid? Origin of the dynamo? Anisotropy and super-rotation? Substructure (innermost inner core)?
Carnegie Institution

Phase diagram and Polymorphism of Fe

9000

7000

Fe

Shock Wave

Theory

Temperature (K)

5000

3000

Inner Core

0 100 200 300 400
Static

1000

Pressure (GPa)

[Hemley & Mao , Internat. Geol. Rev. (2001)]

Wide P-T stability of hcp T of Earths center ~ 5800 K Observations of a high P-T bcc phase
[Dubrovinsky et al., Science (2007])
Carnegie Institution

Example of sodium at megabar pressures

Structural complexity Unusual melting relations

[Gregoryanz et al. Phys. Rev. Lett.. (2005)]

[Gregoryanz et al., Science (2008)]

X-ray diffraction of iron at 50 GPa: liquid structure 2420 40K crystalline

Gasket

laser

NaCl

Iron
X-ray

2540 55K diffuse scattering appearing

6

Liquid Iron
5

Percus-Yevick

=0.206 nm,

58 GPa - 2975 K

=0.21 nm,

Extend to higher P-T Complex alloys

[Shen et al. (2006)]

2650 35K molten

S(Q)

50 GPa - 2650 K

=0.215 nm,

42 GPa - 2680 K 1 27 GPa - 2585 K 0 1 bar, 1823 K, Waseda -1 0 20 40 Q, 1/nm 60 80 100 =0.218 nm,

Microtomographic imaging of amorphous materials

Accurate EOS of melts to megabar pressures

0.05
0.04

0.00
0.03

P=10.7GPa
V / VP

-0.05 -0.10 -0.15

0.02

0.01

V / V0

-0.20 -0.25 -0.30

0.00 0 20 40

(b)
Time (Minutes)
60

Trigonal Se -0.35

(a)
-0.40 0 2 4 6 8 10

Monoclinic Se

12

14

Pressure (GPa)

Accurate P-V EOS of a-Se Pressure-induced expansion of Se [Liu et al., PNAS (2008)] on crystallization

Hydrogen:
The most abundant element in the cosmos

Hydrogen in massive planets Jovian Planet Interiors Extrasolar Planets

[Guillot et al. (2002)]

Outer planet interior structures? Presence of a Jovian cores? Hydrogen mixtures and reactivity?

Phase diagram and continuing puzzles of dense hydrogen

10000

Critical point

Hydrogen
MOLECULAR FLUID

Magro et al., theory NONMOLECULAR METALLIC FLUID Shock wave, Weir et al.

Temperature (K)

Scandolo, theory

Bonev et al., theory

1000

Gregoryanz et al., DAC

Critical Point? Triple point

Ross et al., theory Datchi et al., DAC I MOLECULAR SOLID

Loubeyre et al., DAC Quantum fluid III II Orientationally ordered

100

Orientationally disordered

10

100

Pressure (GPa)
[after Goncharov & Crowhurst, Phase Transtions (2007)]

Predicted metallic superfluid in ultradense hydrogen

Combined P-T-H? Can we create and image these structures?

Pressure dependence of bonding and electronic structure probed by inelastic x-ray scattering
5-50 eV
Axial 2 x 2.5 mm diamonds

0-100 meV
Radial

0.05-100 keV

X-RAY
Su p p o rtin g se a ts

2 mm Be

ELECTRONIC STATE (K-edge, Band Gap)

OPTICAL

Diamond window opaque above 5 eV Q dependence Scatter into excited states

Origin of unusual bonding in dense oxygen
[Meng et al., PNAS (2008)]

VIBRATIONAL STATE GROUND STATE

Excitons and band gap of He by x-ray spectroscopy

He at 11.9 GPa, E0=9.693 keV

hcp 4He at threefold compression shows excitons at ~25 and 28 eV. 25-eV exciton -- strong q dependent of intensity and position 28-eV exciton -- no dispersion. band structure calculation reproduced the electronic excitations. He 1s2 1s2p (1P) transition has an upward energy shift due to overlap of the excited 2p orbital with electron wave functions of the surrounding He.

8
130 deg

7 6 5 4 3 2 1 0 15 25 35

110 deg 90 deg 85 deg 80 deg 75 deg 70 deg 65 deg 60 deg 55 deg 50 deg 45 deg 40 deg 35 deg 30 deg 25 deg

Extend to higher pressures and other systems

IXS experiment
[Mao et al, to be published]

Theory (E Shirley)

Novel behavior of high-density H2O ice

Pressure-induced
freezing: solid ice layers? Mobile protons contribute the magnetic field?
~ 70 K ~0.1 MPa

~ 2000 K
~10 GPa

[Lin et al. GRL (2005); Goncharov et al., Phys. Rev. Lett., (2005); Goldman et al. Phys. Rev. Lett. (2005]]

~ 5000 K ~300 GPa

Direct measurements of conductivity X-ray spectroscopy Megabar neutron scattering

~ 7000 K 800 GPa

There are new opportunities for extending neutron studies at high pressures

Spallation Neutrons and Pressure (SNAP) beam line at the Spallation Neutron Source (SNS)

[Courtesy of Gene Ice]

(3,5 ,11)
(3,5, 7)

(0,4 (1,7 ,10) ,15) (0,2 ,12) (0,0 ,2) (1,1, 7)

(2,4 ,14) (1,1 ,3) (1,1 ,5)

(1, 1,1 )

100x gain with neutron K-Bs Combine with 10x flux SNS and >100x sample volume

(3,7 ,7) (0,8 ,12) (0,6 ,14)

LAUE DIFFRACTION

Mixing hydrogen and water produces still additional phases: clathrates and hydrogen-filled ices
[Vos et al. Phys. Rev. Lett. (1993)]

H2

H2O
DECOMPRESSION

Means for H2 incorporation in

growing planetary bodies? Hydrogen storage material?

[W. Mao et al. Science (2002); Lokshin et al. Phys. Rev. Lett. (2004)]

Methane Clathrate Hydrates

Transformations under Pressure (<1 GPa) Major energy resource Planetary evolution Climate change Implications for biology

sI

sII

sH

Can methane can form abiogenically in terrestrial mantles?

CaCO3, FeO, H2O

Carnegie Institution

Can methane can form abiogenically in terrestrial mantles?

CaCO3, FeO, H2O

Formation of Methane at 5 GPa

C-H Stretch

Post Laser Heating

Ice VII

(c) Laser Heating Methane H2 H2

C2H6 C2H6 C3H8 C4H10 C3H8

5 GPa 2.5 GPa 4 GPa 2 GPa

CH4 products W/Ir

CH4 products Au/B H2 2 GPa

CaCO3 + FeO + H2O

[Scott et al. PNAS (2004)]

CH4 + CaO + Fe3O4

[Kolesnikov et al., submitted]
400

C2H6 3.3 GPa CH4 1.9 GPa

800 1200 1600 -1 Raman Shift (cm ) Carnegie Institution

Exploring surface chemistry under pressure

SFG probe

Chemistry of interfaces under pressure Non-linear optics (sum frequency generation) Combined static/dynamic

all-trans

gauche -defects

vibrational response function

1.0 0.5 s as

1.0 0.5 larger tilt angle

0.0 (b) 50 J 0.0 (a) 25 J 0 20 40 60 80 100 0 20 40 60 80 100 1.0 1.0 gauche elastic 0.5 defects 0.5 recovery created 0.0 (d) 200 J 0.0 (c) 100 J 0 20 40 60 80 100 0 20 40 60 80 100 delay time (ps)

laser shock pulse

[Patterson et al., Phys. Rev. Lett., (2007); Dlott et al., to be published;

Opening up a new field of exploring interfaces, grain boundaries, and heterogeneous materials under pressure

Direct observations demonstrate that microbial life can persist at extreme pressures
VIABILITY UP TO 1.6 GPa (300 K): Coexistence with Ice VI

[Sharma, et al. Science (2002)]

Formate Raman Spectroscopy

Shewanella MR1 AMBIENT

Life in ice at 1400 MPa (14 kbar)

Viability depends on species and strains and unusual morphology changes are observed A
Not all microbes respond alike.

C
[Griffin et al., to be published]

Pressurized E.coli elongate (A), divide upon depressurization (B) and finally return to normal size (C).

X-ray imaging of subcellular structure

These findings require new probes of structure-property relations in biomolecules

Lysozyme Single Crystal Diffraction of Cow Pea Mosaic Virus

Ambient

7 kbar

[Fourme et al. (2002)]

[Lin et al., Acta Cryst. D (2005)]

High-pressure genomics/proteomics Directed evolution

[after Bartlett, Sloan Workshop (2008)]

We are exploring only a limited domain of P-T space

Higher pressures (1 TPa or 10 Mbar) and temperatures (>1 eV) Larger sample volumes needed (x-ray inelastic scattering, imaging THz spectra >100 GPa) Further improve accuracy/precision and applications of multiple simultaneous Combined static/dynamic compression (100 TPa; and >100 eV)

H2

[Ichimura, Phys. Reports (1995)]

Theoretical Predictions UNCHARTED TERRITORY

Using nanobeams to measure anvil nanostrains and optimize pressure

30 nm resolution
[W. Mao, et al. to be published]

[Hemley et al., Science (1997)

5 m resolution

4 m

Xradia nanoscope with 30 nm resolution

SSRL Beamline 6-2

Expanding the temperature range Very high-temperature laser heating

Molten Carbon at ~9000 K
Temperature from Spectral Radiometry (3 GPa)

Temperature calibration Role of first principles theory

DFT MD Simulations

[Correa, Bonev, & Galli, PNAS (2006)]

[Xu et al., to be published]

Dynamic compression: first synchrotron measurements

Sandia, WSU gas-gun

Time resolved IR reflectivity at U2A (NSLS) for temperature calibration (to 8 GPa)

[Dolan et al., to be published]

Dynamic compression: first synchrotron measurements

Sandia, WSU gas-gun

Time resolved IR reflectivity at U2A (NSLS) for temperature calibration (to 8 GPa)

[Dolan et al., to be published]

X-ray diffraction of shock compressed simple metals to 20 GPa at HPCAT (APS)

WSU powder gun

[Gupta et al., to be published]

Dynamic compression: first synchrotron measurements

Time resolved IR reflectivity at U2A (NSLS) for temperature calibration (to 8 GPa)

X-ray diffraction of shock compressed simple metals to 20 GPa at HPCAT (APS)

Simulated coherent diffractive imaging of shock front (50 nm resolution)

Polycrystals/fluids? Higher P-T conditions? Dedicated beamlines?

Future prospects:
time-resolved diffraction; single shot diffraction (at 1012 photons/pulse); in situ 3D characterization, chemical characterization, and imaging of defects/dislocations

Materials studies with shocks and isentropic compression techniques

- Hydrogen and Helium at TPa - Fast Ramp Wave Loading - Core electron chemistry - Rigidity at TPa conditions - Going beyond the EOS - Wave-velocities in super-giant planets - Gigabar Pressures

Combined static/ dynamic compression Ultra-fast diagnostics

Continued advances in static high P-T techniques

0.25 c t

Large CVD diamonds

[Meng et al., PNAS (2008)]

25 mm 100 c t

Prototype CVD diamond production reactor at Carnegie

Multiple diamonds growing (MSU

Smart diamond anvil devices

[Struzhkin, Cuk, Shen, Rotundu, Greene to be published]

[Vohra and Weir (2002)]

Shinji MATSUI http://www.nanonet.go.jp/english/mailmag/2006/files/086a1.jpg

Optical and X-ray applications of CVD diamond

High quality CVD single-crystal diamond as large as 18 mm and 15 carats have been produced.

Stokes and anti-Stokes stimulated Raman spectra of ~670-m SC-CVD diamond with picosecond laser pumping at 0.53207 m and 1.06415 m wavelengths. X-ray lenses fabricated from polycrystalline CVD diamond. Single crystal material is needed for improved optical and mechanical properties.

X-ray topography of measured at APS (above) and synchrotron IR absorption at NSLS.

380 m

[Evans-Lutterrodt & Isakovic, to be published]

Carnegie Institution

The Deep Carbon Cycle The Deep Carbon Cycle

We need fundamental advances in understanding Earths deep carbon cycle:

Where is the deep carbon & how

much is there? How does carbon move between reservoirs? Is there a deep source of organics? What is the nature and extent of deep microbial life?

The Deep Carbon Cycle The Deep Carbon Cycle

The Deep Carbon Observatory
To tackle fundamental needs and opportunities in five interrelated aspects of deep carbon cycle research: - Carbon reservoirs - Carbon fluxes - Abiotic organic synthesis - Deep microbial life - Interactions between the deep and surface carbon cycles Major international academic/government/industrial collaboration Proposal to be submitted in April 2009 to the A. P. Sloan Foundation (~$25 M/five years)

The Deep Carbon Cycle The Deep Carbon Cycle

The Deep Carbon Observatory
Deep Carbon Observatory DECIMAL4 SIDEC5 High-resolution Mass Spectrometer Ultra-Carbon Microscope STEM Integrated ToF/SIMS/ Raman/FIB Advanced Carbon Spectroscopy High P-T Instrumentation Computational Facilities DECADE1 CINDEE2 DEOSS3

DECADE: Deep Earth Carbon Abundance and Distribution Experiment CINDEE: Carbon IN Deep Earth Experiment DEOSS: Deep Earth Organic Synthesis and Stability DECIMAL: Deep Earth Carbon Interface with Microbial Activity Limits SIDEC: Surface Interface with Deep Earth Carbon

CONCLUSIONS AND PERSPECTIVES

1. Numerous new tools are coming on line that will allow us to tackle a broad range of problems in high-pressure geoscience. 2. These tools span a range of scales, from benchtop devices to major national facilities. 3. There is potential impacts beyond geoscience to the fields that span the physical and biological sciences. 4. The new Deep Carbon initiative represents a new opportunity for this community.

Extreme pressures and temperatures

Carnegie Institution