Synchrotron Xray Microfluorescence Applications

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Synchrotron X-ray MicrofluorescenceApplications
Pascal Philippot Institut de Physique du Globe de
Paris (with Jean Cauzid, Julien Foriel,
Bénédicte Ménez)
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Fluid circulation in the Earths
Economic resources
Magmatism, Volcanism
Primary source of energy and organic matter
Global volatile cycles 80 of water store in
oceans
Origin of life?
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FLUID INCLUSIONS Direct testimony of fluid
processes during diagenesis, metamorphism
magmatism
Ore deposits
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Several generations of fluid inclusions generally
trapped in a same sample. Necessary to analyse
single fluid inclusions if information on the
history of hydrothermal processes is to be
solved.
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High resolution analytical techniques
Destructives LA-ICP-MS Multi-elementary (up
to 40 elements, no anions) LA-Optical Emission
Spectroscopy Adapted to light element (Li, B,
Na)
Non destructives Microthermometry
Salinity, density, chemical system Raman
Polyatomic species (CO2, CH4, N2, Cl) FTIR
Polyatomic species (oil) PIXE/PIGE
Multi-elementary (Zlt26) SR-XRF
Multi-elementary (Zgt16, including S, Cl, Br)
SR-XANES Element speciation
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High resolution analytical techniques

• - SR-XRF, SR-XANES can be performed conjointly
• Can also be coupled with SR-Raman and SR-IR
• Non-destructive versatile

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Synchrotron, versatile and non-destructive
environment
Fresnel Zone Plate Compound Refractive lens KB
Mirror
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Synchrotron Versatile and non-destructive
environment
2D and 3D imaging and high resolution in situ
analysis µ-fluorescence (chemical composition,
fluotomography) µ-diffraction (µ inclusions,
daughter crystals) µ-absorption (speciation,
structural environment at the atomic scale)
µ-infrared (organic compounds, anhydrous species)
Fluid inclusion
Microfossils
10 µm
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European Synchrotron Research FacilityID22,
Experimental set-up
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Experimental protocol on ID22 (2000)
Frenel Zone Plate (FZP) Compound Refractive Lens
(CRL)
Imaging of a single fluid inclusion using the CCD
camera
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X-ray microprobe set-up at ID22 (2006)

• ? Non-destructive, in situ analysis
• ? High spatial resolution (µm)
• Multi-elementary analysis (S, Pb)
• Element speciation and imaging
• Detection limits 1 ppm (Zgt Ca) to
• 100 ppm (S, Cl)

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2006
2000
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Quantification procedure
Concentration f(d, h)
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Theoretical model

d
h

• Known

• Calculated

• Measured

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Fluid inclusion model
d exp ?

d opt
d exp ?
h opt
El Line E(keV) Area StdDe Si Ka
1.740 13017 135 Cl Ka 2.622 294
61 Ar Ka 2.957 4789 94
Ca Ka 3.691 8736 111 Fe Ka
6.399 1844 68 Cu Ka 8.041
605 58 Br Ka 11.908
17405 141 Sr Ka 14.142 20802 154
h exp
Homogeneous fluid Homogeneous matrix Absorption
of the host mineral and fluid known
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3 X-ray spectra obtained on two different fluid
inclusions (red and blue) and on host quartz
(white). The different peak intensities reflect
different absorption by the host mineral of the
fluorescent X-ray beam as well as different
compositions
Foriel et al., 2004
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Increasing signal/background ratio using a He
Chamber
Today He chamber implemented on different
beamlines
Before
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He chamber Effects CRL vs KB mirror focusing
devices ambiant air vs He atmosphere on
absorption of fluorescent X-ray
Courtesy of Rémi Toucoulou
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• Quantification procedures (d and h)
• Optical measurements
• Ka/Kb methods
• Transmission measurements
• Tomography reconstruction
• or a combination of these

• Calibration procedures
• External standard (capillaries or synthetic fluid
  inclusions)
• Internal standard (e.g. Cl from microthermometry)
• Standardless procedure

SXRF analyis well adapted for the analysis of
dilute and homogeneous systems Analysis of anions
(S, Cl, Br) in situ
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d ? Microscope or Ka/Kb h
(Philippot et al., 1998, 2001)
Arsenic distribution (147 ppm), Brusson deposit
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d ? Microscope or Ka/Kb h ? Microscope or
Transmission measurements
Cauzid et al. (2004)
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Calibration

• Internal standard
• Calibration using an element of known
  concentration present in the inclusion (CL from
  microthermometry)
• External standard
• Calibration using an element of known
  concentration (e.g. Cl from seawater) measured in
  microcapillaries or from crush leach (when only
  one fluid inclusion population)
• Concentration of Cl in the inclusion calculated
• Standardless
• Calibration of the experimental set up (d and h
  carefully evaluated and solid angle of detector
  measure)

(Ménez et al., 2002 Cauzid et al., 2005)
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Concentration estimates
Emerald deposit, Columbia
(Ménez et al., 2002)
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Concentration estimates
Mole Granite tin deposit, Australia
(Cauzid et al.,2005)
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Element distribution in a single fluid inclusion
Count
19000
16620
14250
11870
9500
7125
4750
2375
0
50 µm
Count
1120
980
840
700
560
420
280
140
0
Count
195300
170900
146500
Emerald deposit, Columbia
122100
97670
73250
48830
(Ménez et al., 2002)
24420
0
0
20
40
60
80
0
20
40
60
80
distance (µm)
distance (µm)
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Emerald deposit, Columbia
Homogeneous distribution
Fe
Zn
Fe
Partitioning in the vapor phase ?
Br
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Homogeneous elemental distribution
(Foriel et al., 2003)
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Heterogeneous elemental distribution
(Foriel et al., 2003)
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Highly-localized elemental distribution
solid phase
(Foriel et al., 2003)
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Summary of element distribution in a single
fluid inclusion
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Fluorescence tomographyElemental partitionning
between lowand high density fluids
vapor phase
liquid phase
Cauzid et al., 2007
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Fluorescence tomographyElemental partitionning
between lowand high density fluids
Cauzid et al., 2007
vapor phase
liquid phase
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Geological applications

• Early Archean oceans and hydrothermal systems
• Foriel et al. (2004) ESPL 228, 451-463
• Source and compositions of epithermal ore fluids
  Thébaud et al., (2006)
• Speciation and element partitioning of
  Mesothermal ore fluids
• Cauzid et al., (2007)

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Deep-sea hydrothermal vents as potential
analogues for early life development on Earth

• ? Composition of Archaean seawater
• and hydrothermal fluids
• Imaging sulfur-metabolizing skills in
• individual fossil and living microbial filaments

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Early habitat of life and primitive environments
Atmosphere CO2, CH4, O2 ?

• Ocean SO42-, pH, halogens, salinity ?

Microbial life Metabolism, diversity?
Archaean samples from the Pilbara Craton Western
Australia
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Dresser Formation _at_ North Pole (3.5Ga),
Warrawoona Group, Australia
Van Kranendonk et al., 2006
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PILBARA DRILLING PROJECT Fresh, unaltered
diamond drillcores collected under the water table
Drilling late August 2004
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Intra- and inter-pillow quartz segregation
Foriel et al., (2004)
Hydrothermal fluid vs seawater infiltration
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Intrapillow quartz segregation near the seafloor
Foriel et al., (2004)
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Crush-leach results
In strong excess
Equivalent to seawater
Foriel et al., (2004)
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SR-µXRF results
(Foriel et al., 2004)
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Homogeneously distributed species
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Foriel et al., 2004 Philippot et al., 2005
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Sulfur analysis
 seawater 
S, ppm
Fe fluid
Br/Cl
Foriel et al., 2004
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Volcanoclastic terrigenous sediments
Life
Cl/Br 274 ?
Organic matter?
Present day value
Cl/Br 274 Global Earth
2-
SO lt 8 mM Poorly oxygenated atmosphere?
4
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Deep-sea hydrothermal vents as potential
analogues for early life development on Earth
Most microorganisms at the fluid-seawater
interface are thought to be chemolithoautotrophs
oxidising reduced forms of sulfur (H2S) and iron
or producing filamentous sulfur. Members of the
epsilon subdivision of the Proteobacteria appear
to predominate.
Imaging sulfur-metabolizing skills in individual
fossil and living microbial filaments
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Living microbial filaments
Micro-colonisers exposed for 15 days to a vent
emission from Lucky Strike site (Mid-Atlantic
Ridge).
Almost exclusively colonised by e-proteobacteria
likely located at the fluid-seawater interface.
(Lopez-Garcia et al., Env. Microbiol, 2003).
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Microfossil filaments
Filamentous microfossils collected from a
fragment of an inactive siliceous hydrothermal
chimney at 1815South of the East Pacific
Rise (1993 NAUDUR cruise Fouquet et al., 1994)
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Objective
One of the less ambiguous relic testimony of
microbial activity during the Archaean
Ancient fossil system (3.2 Ga) Sulfur Spring,
Pilbara  Morphological  microfossil 
Living Microbial filament MAR, Lucky Strike
Modern microfossil East Pacific Rise
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Micro-SXRF analysis showing the trace element
composition at the scale of individual fossil and
microbial filaments
EPR microfossil
MAR microbial filament
Philippot et al., 2002, ESRF Highlights Foriel et
al., GCA 2003
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Trace metal distribution in a single
fossil Filament of the East Pacific Rise, PIXE
analysis
Fe
Cu
Zn
Cl
Ca
Metabolic activities using or generating metal
sulfides
External contamination (seawater?)
Foriel et al., GCA 2003
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Micro-XANES analysis showing the redox
distribution of sulfur (sulfate, sulfites,
SH-radicals and minor sulfides) at the scale of
individual microfossil and microbial filaments
SH-radicals
Sulfites
Sulfates
Philippot et al., 2002, ESRF Highlights Foriel et
al., GCA 2003
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Synchrotron-microinfrared analysis showing the
presence of CH-radicals in the living (MAR) and
fossil (EPR) filaments and of amides in the
living microbial filaments
Foriel et al., GCA 2004
Collaboration Paul Dumas
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Meso to epithermal ore deposits

• Porphyry-copper deposit (gt450C)
• Epithermal (100-400C)
• Evolution of fluid composition and speciation as
  a function
• of temperature (how does it works?)

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Boiling processes
High density liquid inclusion
Low density vapor phase
Phase separation (liquid, vapor, solid)
Trapping of high density and low density fluids
Temperature
Supercritical fluid
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Cu-speciation in vapor and liquid fluid
inclusions from the Yankee Lode deposit, Mole
Granite, Australia

• Density model in the system H2O-NaCl-KCl-HCl
• accounts for vapor-brine distribution patterns of
  a
• wide range of elements except Cu and Au
• Partitioning in vapor of Cu and Au requires
  formation of other stable complexes
• (reduced sulfur? Lowenstern, 1991 Heinrich
  1992..)

Pokrovski et al., 2005
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• Why Mole Granite?
• Plenty of data using different techniques /
  control on our analytical results and cross
  laboratory constraints
• PIXE (Heinrich et al., 1992)
• LA-ICP-MS (Audédat et al., 1998, 2000)
• XANES (Mavrogenes et al., 2002)
• Heterogeneous system to test quantification
  procedure, tomography reconstruction, and in situ
  element mapping of dissolution processes using a
  micro furnace
• S, Cl and Cu analysis in situ
• Observation of Cu-Cl and Cu-S complexes forming
  in vapor and liquid inclusion upon heating

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HT immiscible brine and vapor inclusions
Chip analyzed here from same sample Courtesy of
Christoph Heinrich
Audédat et al., 1998
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2D X-ray fluorescence mapping (room T)
Liquid inclusion Depth 3 µm
10 µm
Cl Not dissolved
S dissolved In part?
Cu Dissolved
Cauzid et al., 2007
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2D X-ray fluorescence mapping (room T)
Vapor inclusion Depth 3 µm
10 µm
S Not dissolved Not H2S!
Cl Dissolved
Mn
Fe
Cu Not dissolved Not a Cu-Cl complex
Zn
As
Br
Pb
Cauzid et al., 2007
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Element partitoning betweenliquid and vapor
inclusions
Cu
large error on S estimates
Audédat et al., 1998 Heinrich et al., 1999
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Microfurnace for in situ solubility and
speciation analysis of immiscible liquid and
vapor fluid inclusions
a

fluid inc.
host mineral
ß
detector
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Heating runs of liquid inclusion2D X-ray
fluorescence mapping
Inclusion depth 20 µm Heated during more then
24h prior to dissolution!
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Heating runs of vapor inclusion 2D X-ray
fluorescence mapping
Inclusion depth 20 µm Heated during more then
24h prior to dissolution!
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Heating runs of liquid inclusion, micro-XANES
measurements
25C
334C
450C
Fe
Cu
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Heating runs of vapor inclusion, micro-XANES
measurements
Cu
XANES
S
Cl
depth
3 µm
25C
Cu(H2O)6
20 µm
450C
CuCl2 or CuClH2O
20 µm
500C
20 µm
Cu(S,Cl)?
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Micro-XANES in-situ measurements
Fulton et al, 2000 XANES
Cauzid et al., 2007
Mavrogenes et al., 2002