ESS

Giornata ESS: 21 Giugno 2010 Università Roma Tre

ESS: impatto sulle Scienze della Terra e Ambientali ESS: impact on Earth and Environmental Sciences Romano Rinaldi Università di Perugia Dipartimento di Scienze della Terra [email protected]

1 Roma-3 Giornata ESS, 21 Giugno 2010

Foreword

• Only a few years ago, weather prediction was close to witch-doctor science; i.e.: Red sky at night, shepherd's delight. • Lately, thanks to global observation, powerful maths models and computers, weather prediction reliability went from 12-24 hours to 5-6 days. • The complexity of the problem is similar to that of the study of the inner Earth, although in this case, direct observation is not trivial. Models have to be built from observations gathered on the surface (minerals, rocks, geologic activities...) and experiments carried out on the materials involved, at conditions similar to those expected at depth. • Similar to weather forecast, Neutrons from ESS-type instruments can help bridge the prediction gap existing as regards Earth and Environmental phenomena such as, for instance, Earthquakes and Volcanic Eruptions. Only a few examples will be given here of the type of science ESS can help unravel in the fields of Earth and Environmental research. Much more info can be found in the ESS-SAC reports, in a recently published Book, and the 2 literature cited therein.

European Spallation Source (ESS) Project Scientific Advisory Committee (SAC) 2000-2002

Priority Research Theme: Earth and Environmental systems ESS contributions: • • • • •

• • • • •

In Situ high pressure\temperature studies, phase transitions, effect of chemical composition in geological materials and metamorphic reactions, distribution and migration of volatiles in upper and lower mantle. Core reactions. Structure and dynamics of hydrogen in minerals and in storage materials. Membrane materials, silicon and non-silicon based solar cells. Ion diffusion and exchange in minerals (in situ); ion diffusion in environmentally friendly batteries; membrane materials for fuel cells. In Situ characterization of rock anisotropy, stress and texture development. Characterization of surface reactions – weathering, toxic metal cycling, mineral processing, organic / inorganic interactions. Structure, formation, decomposition and dynamics of gas clathrates. Structure and reactions in clays and microporous materials. Local order in complex glasses and igneous melts. Minerals, glasses and ceramics for radionuclide encapsulation. Time resolved radiography / tomography of fluids and melts. Strategic ore minerals; structure, stability and surface properties. Mineral beneficiation and metal recycling. (Adapted from corresponding Fact Sheet - ESS-SAC Workshop, 2002)

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Versoix, near Geneva, March 20104

Storm, California Unplug and turn off your PC !

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Tsunami, Thailand

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Earthquake L’Aquila, April 6th, 2009

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Eyjafjallajoekull eruption April – May 2010

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Eyjafjallajoekull vs airlines

Earth Science and Environment: Importance of water in magmatic processes

Eyjafjallajoekull Ash spread extent April 2010

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Properties of neutrons relevant to Earth Sciences

• Generally low cross section (σ = 4πb2 with b = scattering length) -> high penetration power for most materials (in situ work) • High (incoherent) cross section and high coherent (negative) scattering length for Hydrogen (Z=1)  easier to “see” even in the presence of heavy atoms (also without D substitution) • Good contrast (different scattering lengths) for isoelectronic or quasiisoelectronic atoms (ions) - series: Cl- K+ Ca2+ Ti4+ (18 e-); O2- Na+ Mg2+ Al3+ Si4+ (10 e-); Mn, Fe, Co, Ni. All very common in natural minerals and materials. The same applies to isotopes (also H-D). • Near zero coherent scattering length for Vanadium (Z=23) with appreciable cross section for incoherent scattering (HT vessels + Zr). • High absorption cross section for Boron (Z=5), Cadmium (Z=48) and Gadolinium (Z=64), each with good characteristic as efficient shields for precision measurements. 12 (R. Rinaldi in: "Neutron Applications in Earth, Energy and Environmental Science”. Liang, Rinaldi & Schober Eds., Springer 2009, Ch.1)

Typical draw-backs of neutrons • Neutron fluxes are rather weak, needing large samples • A neutron beam is a large probe (several mm) as opposed to a micro-beam • Time required for data collection - in the range of days as opposed to hours • Activation decay may be long (for long exposures and wide energy spectrum)

The ESS aims to overcome most of these draw-backs (instrumental details were given in the previous talks)


Neutron scattering advantages in Earth & Enviro. Sci. Research •

Excellent data quality from in situ studies (HT-HP, reaction cells, etc.) hence model simulations on natural and man-made materials at “natural” conditions.

•

High scattering power, i.e. great sensitivity, for 1H and 2H (D2) – hydrous component in minerals, rocks and melts + other light elem. (Li, Be, B, C, N), also in the presence of heavy elements.

•

Good contrast for iso-electronic (or quasi-iso-) ions and Low-Z / High-Z atoms

•

Non-Z dependent scattering cross section, Diffraction data up to large scattering vectors Q (high spectral resolution, good* peak resol.). Low symmetry ok. Magnetic scattering ok - Complementarity with X-rays.

•

Fewer limitations as to size, thickness and shape of samples. Large samples (cm-dm scale) can be analysed totally undisturbed. Data collected are representative of the bulk object. Not limited to small portion or surface of the object. Surface features and properties can also be addressed.

•

Applicability to all kinds of materials (solid, liquid, glass etc.).

•

Fewer systematic effects such as preferred orientation or shape-dependent artefacts. Better statistics for coarser textures.

•

Simple apparatus (ToF-ND - similar to SR-ED) also for Imaging.

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Probing Earth's interior with Neutrons

Temperatures

Pressures

Depth

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INTRA PLATE ALK MAGMAS

IAB

OIB

MORB

O3

O3

O1 Si O1

O3

O2

O3 O3

M1

O1

O1 Si

O1 Si O1

M2

O2

O3

O3

M1

O3 O3

O2

O3

M1

O3

O3

O3

O1 Si O1

O3

O2

O3 M1

O3

O3

O3

Si O1

M1

O3

M2

M1

O3

O2

O2 O2

M2

O1 Si

M1

O3

SiO1 O1

O3 O3

O2 O2

M2

O3

M1

O3

O3

M1

O3O3

Si O1

O1 Si

O2

M2

O2

O3

M1

O2 O2

O3

O1 Si O1

M2 O3 O3

M1

O3

M2

O2

Si O1

O2

O3 O3

M1

O3

O3

O3 O2

M2

O1 Si

O2

O3

O3

O3 O2

O3

O2 O1 O2

O1

O1 O2

O2

O1 O5

O5

T2 O6

O6 O7

T1

M4

M1 O2

H

O4

A H

O4

M2 O4

M2 O1

O1 O2

O3

O2

In-situ studies of rock-forming minerals yield information on processes related to subduction and/or magmatic activity. From the left, structural models of: olivine, amphibole, pyroxene, mica, garnet; MORB = Mid-Ocean Ridge Basalt; IAB = Island Arc Basalt; OIB = Ocean Island Basalt (hot spots). [courtesy of R. Oberti]. 16

Earth Science and Environment:

Importance of water and volatile components in magmatic processes

Mount St. Helens May 18, 1980

Vesuvius 1944

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Schematic model for global water circulation. Arrows indicate directions of water or hydrogen movement. E. Ohtani IMA Keynote lecture Wed. Jul.26, 2006

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Paris-Edinburgh cell for HP(+HT) N-diffraction data collection

Electrical contact ring Insulating ceramic ring Graphite furnace cap Graphite furnace Sample (pressed pellet)

Metal foil for NRS Sample (pressed pellet) Pyrophyllite gasket Graphite furnace cap Insulating ceramic ring

18 mm

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Electrical contact ring

(SAT Redfern & RJ Harrison in: "Neutron Applications in Earth, Energy and Environmental Science”. Liang, Rinaldi & Schober Eds., Springer 2009, Ch.4)

Simultaneous high P/T cell

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Targeted P-T ranges at MLF, J-PARC (JSNS)

0

Temperature (℃) 2000 3000

0 25

MLF @ J-PARC

crust, upper mantle lower mantle core 100 Pressure (GPa)

geotherm 21

11 bar

ba 90r kbar Courtesy of Chris Tulk (SNS-ORNL)

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Volatile hosts in minerals: from stones that boil (zeolites) to ice that burns (gas hydrates) through hydrous and nominally anhydrous minerals (NAM’s)

Layer slab of the crystal structure of the synthetic zeolite RUB-18. Two neighbouring silanol groups are connected through strong hydrogen bridges. The neutron structure refinement reveals the proton as split position atom

Brucite Mg(OH)2 structure. Its HP behaviour investigated by neutrons shows stability over 9.5GP - good water carrier in depth. Deuterated samples are more compressible than hydrogenated ones - isotope fractionation with depth?.

phlogopite mica: octahedral layers between the two tetrahedral silicate layers with OH groups from [MgO6]-octahedra are shown with hydrogen spheres revealed by neutrons.

23 (H. Gies in: "Neutron Applications in Earth, Energy and Environmental Science”. Liang, Rinaldi & Schober Eds., Springer 2009, Chapter 7)

katoite

hibschite [SiO4]-tetrahedron replaced by the [H4O4]-tetrahedron In the katoite-hibschite series of hydro-garnets laumontite with Ca-bonded water molecules (H. Gies in: "Neutron Applications in Earth, Energy and Environmental Science”. Liang, Rinaldi & Schober Eds., Springer 2009, Chapter 7)

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ambient pressure structure of Natrolite

high pressure structure of Natrolite

More water is retained by the zeolite at high pressure by slight rotation of framework units. Pressure release causes water release but water is retained in synthetic Ga natrolite. Neutron experiments in situ revealed mechanism. 25 (H. Gies in: "Neutron Applications in Earth, Energy and Environmental Science”. Liang, Rinaldi & Schober Eds., Springer 2009, Chapter 7)

Water in Minerals: Structural refinement of Al2SiO4(F,OH)2 (topaz) Crystal structure of topaz based on the neutron structure refinement viewed down [100], [010] and [001]. Thermal ellipsoid probability: 50%.

(010) Difference Fourier map clearly locates the H-position

(Gatta et al., 2008)

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Silicate melts The structure and dynamics of melts at the atomic scale can be studied by quasielastic neutron scattering (QNS). Combination of QNS experiments and molecular dynamics (MD) computer simulations provide the measurement of elastic structure factors as well as time-dependent density correlation functions for melts of different compositions. Molecular dynamics snapshot of the structure of (Na2O)3SiO2 at 2100 K at the density ρ = 2.2 g/cm3. The blue spheres represent the Na atoms. The Si–O network is drawn by yellow (Si) and red (O).

In situ studies at HT-HP unveil mass transport and rheological behaviour of melts.

27 (A. Meyer et al., in: "Neutron Applications in Earth, Energy and Environmental Science”. Liang, Rinaldi & Schober Eds., Springer 2009, Chapter 6)

Observation of Melt Dynamics Top: Neutron graphics of time evolution for two immiscible melts. Bottom: Finite difference calculations reproduce features of process Scale markers: 1cm

Dynamic neutron radiography can be used to observe processes in melts. These can be used as benchmarks for finite difference calculations Kahle A, Schmehling H, Winkler B (2003). Eur. J. Mineral, 15, 95

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Natural Gas Hydrates (clathrates)

Methane hydrate burning at RT (burning ice). Water is released by the combustion. 29 Roma-3 Giornata ESS, 21 Giugno 2010

Gas Hydrates (clathrates) Clathrate 51264 cavity

Cubic clathrate S1 network (Sp. Gr. Pm3n)

water oxygens at nodal points, CH4 inside cavity


This is also relevant to off-shore Louisiana oil spill, 2010 (unforeseen formation of gas hydrates has hampered attempts at tapping and stopping deep sea leak) – templating effect? 31

Questions: What are the stability limits? What is the composition (the so-called hydrate number)? Is there a compositional range with gas-rich and water-rich end-members?

Natural Gas Hydrates span at least three issues: hazard, resource, climate.

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Complex tectonics in the Alps through Neutron texture analysis

Quartz mylonites, Cimes-Blanches nappe, Western Alps (Froitzheim, Pleuger et al., Neutrons in Earth, Energy and Environment, Springer 2009, Ch. 10)

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Results: the dominant deformation during exhumation of the high-pressure rocks was shearing towards the North. The high-pressure rocks were exhumed in a framework of North-directed over-thrusting and only later affected by extensional shearing. 34 (Froitzheim, Pleuger et al., Neutrons in Earth, Energy and Environment, Springer 2009, Ch. 10)

Neutron REFLECTOMETRY in subsurface bacteria-promoted metal redox reactions

Electron transfer pathway in Dissimilatory Metal-Reducing Bacteria (DMRB) - Shewanella oneidensis MR-1 (Fe3, Mn4) Fe2O3

Environment LPS

OmcA

Outer Membrane

eMenaquinones

OmcA

MtrB Stc

NADH Dehydrogenase

MtrC

MtrA

e-

Periplasm

CymA

Inner Membrane Cytoplasm NADH

NAD+

Gram-negative bacterial cell

Outer membrane protein OmcA (C-type cytocrhome) is assumed to mediate electron transfer Shi et al., Journal of Bacteriology, 188:4705-4714, 2006 Weber et al., Nature Reviews Microbiology, 4(10), 752-764, 2006 Ross et al., Applied and Environmental Microbiology, 73:5797-5808, 2007

Courtesy of Liyuan Liang and Alex Johs (SNS-ORNL)

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Molecular shape of OmcA (a monomer in solution) by small angle x-ray scattering (SAXS) 100

RG = 30.6 ± 0.2 Å

log I(q)

2

10

oxidized

6 4

0.0

2.0e-4 4.0e-4 6.0e-4 8.0e-4 1.0e-3 2

-2

q [Å ]

2

0.20

P(r) [a.u.]

ln I(q)

6 4

0.15 0.10 Dmax = 96 Å

0.05

1 6 4

0.10

0.20 q [Å ] -1

0.30

20

40 60 r [Å]

80

90º

34 Å

90º

20 Å

Roma-3 Giornata ESS, 21 Giugno 2010

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Courtesy of Liyuan Liang and Alex Johs (SNS-ORNL)

Neutron Reflectometry 1

1

10

-6

10

-6

10

8x10

0

0

log Reflectivity

-2

-1

Fe2O3

-6

4x10

10

-6

10

2x10

Si

-3

SiO2

-6

10

air

0x10

0

100

-4

10

200 z [Å]

300

400

-5

-7

10

-2

Fe2O3

-6

4x10

-6

10

2x10

Si

-3

-6

10

SiO2

D2O OmcA + D2O

0x10

0

100

-4

10

200 z [Å]

300

400

-5

10 10

-6

6x10 -2

-2

-1

10

log Reflectivity

Nb [Å ]

6x10

Nb [Å ]

10

-6

-6

8x10

10 layer Si SiO2 Fe2O3 air

0.00

Nb [Å-2] 2.07·10-6 3.80·10-6 6.60·10-6 0

d [Å] 10 112 -

 [Å]

-6

10

3 5 40 -

-7

10 0.05

0.10

0.15 -1

Q [Å ]

Thickness of protein monolayer: 33Å 164 ng/cm2 83 nm2/OmcA

0.20

0.25

0.30

 ki

 [Å-2] 2.07·10-6 3.80·10-6 6.60·10-6 4.64·10-6 6.35·10-6

layer Si SiO2 Fe2O3 Protein D2O

0.00

d [Å] 10 112 33 -

0.05

 [Å] 3 5 40 50 -

0.10

 Q [A kr

QZ

-1

0.15

0.20

]

Si

q

q

 kt

SiO2 Fe2O3 Protein/D2O D2O

“Characterization of the Decaheme c-type Cytochrome OmcA in Solution and on Hematite Surfaces by Small Angle X-ray Scattering and Neutron Reflectometry”, A. Johs, L. Shi, T. Droubay, J.F. Ankner, and L. Liang, Biophys. J., 2010, in press Courtesy of Liyuan Liang and Alex Johs (SNS-ORNL)

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Neutron Radiography and Tomography: non-destructive imaging to map water distribution around plant roots in-situ

Radiography (2d, scale of root system, fast, realtime monitoring of water)

Tomography (3d, high resolution, small scale, detailed information)

1.5 cm

100 mm

15 cm

27 mm

15 cm

q

0.35 0.3 0.2

θ

0.15 0.1 0

Results: the presence of rhizosphere mucilage with higher water-holding capacity than the bulk soil facilitates 38 the root uptake of water especially as soil dries out. Ahmad Moradi, A. Carminati, P. Vontobel, E.Lehmann, S. E. Oswald - NMI3 Gen. Ass.bly BCN May, 2010

IMPACT OF ESS Similar to weather forecast development, Neutrons experiments at the ESS will help bridge the prediction gap existing as regards natural phenomena and related environmental outcomes (and hazards)

The impact of the ESS on Earth and Environmental Sciences will be quite extraordinary


For more information…

Published Jan. 2009

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esss (European Spallation Source, Scandinavia) ESSS Director Colin Carlyle at esss stand - ICNS Knoxville TN, May’09 (apples have always played an important role in Physics)

Building of new European Neutron Source soon to begin in Lund (Sweden) Italy ought to be involved with instrument building and scientific proposals 41 Roma-3 Giornata ESS, 21 Giugno 2010

Summary of typical applications of neutrons in Earth and Environmental Sciences

●

In situ studies of minerals (HP/T–LT- hydrous comp),

fluids and fluids/rocks interactions (also cements and concretes) + porosity and related processes.

• Phase transitions and reactions / processes of alteration (also in depth – in situ). • Stress and strain and partition among mineral phases of the material (natural or man-made).

• Fundamental properties of minerals (e.g. phonon density of states - also in situ) by INS to model thermodynamical properties and inner conditions in the Earth. • Applicability to solids, glasses, melts, liquids.

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Giornata ESS: 21 Giugno 2010 Università Roma Tre

THANKS Romano Rinaldi


Observations and modelling !

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Remember: Eyjafjallajoekull !