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New Frontiers in Stable Isotope Geoscience (in South
Australia)Galen P. Halverson
Geology & Geophysics, School of Earth & Environmental Sciences The University of Adelaide
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AcknowledgmentsARC-LIEF (2007)
CSIRO
Mike McLaughlin
Jason Kirby
John Foden
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Current and potential capability in stable isotope geochemistry at UA
•Light stable isotopes (C, N, O, S) by
conventional gas source mass spectrometry
•Non-traditional isotope systems via MC ICP-MS
•Fe, Zn, Cu
•Other methods
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Our Current Stable Isotope Facilities
Fisons Optima with an ISOCARB and Elemental Analyzer for analyses by Dual Inlet (DI) or Continuous Flow
(CF)
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EA (CF)EA (CF)
SulphidesBarite
δ34S
EA (CF)Organicsδ15N
Isocarb (DI)Carbonateδ18O
Isocarb (DI)EA (CF)
CarbonateOrganics
δ13C
MethodMaterialIsotope ratio
Current Capability
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Future Capability?
•δ18O on sulphates and organics (TC/EA)
•Simultaneous δ13C and δ18O on tooth enamel
•Simultaneous δ13C and δ15N measurements on
organics
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Ultra-Trace Element and Isotope Analysis Laboratory (Waite
Campus)
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The Finnigan Neptune High-Resolution Multi-Collector (MC
ICP-MS)
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New Wave 193 nm Excimer Laser
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Analysis by MC ICP-MS
Advantages•High precision
•High sample throughput
•Rapid switching between elements
Sample introduction via•Solution
•Laser Ablation
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Stable isotope fractionation is a function of relative mass difference
between isotopes
Johnson et al., 2004
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Likely stable isotope methods to be developed in
the early days:Fe, Zn, Cu, Mo
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Other likely methods to be developed:
Fe, Zn, Cu, Mo
Likely stable isotope methods to be developed in
the early days:
Mg, Si, Se, Hg …
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QuickTime™ and aTIFF (Uncompressed) decompressor
are needed to see this picture.
Analysis on a Neptune MC ICP-MS
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Isobaric Interferences:
54Fe: 40Ar14N56Fe: 40Ar16O
57Fe: 40Ar16O1H58Fe: 40Ar18O54Fe: 54Cr58Fe: 58Ni
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Analyses by high resolution MC-ICP-MS
M/ΔM = ~9000-11000Plateau: 180-220 ppm
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To correct for internal mass fractionation:
Use a standard-sample-standard bracketing
±Ni/Zn/Cu doping
Analytical uncertainty of ~0.02‰/amu
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Measuring multiple isotope ratios to monitor for untoward mass biases and interferences
y = 0.6774x + 0.0033
R2 = 0.9999
y = 0.6754x - 0.0004
R2 = 0.9997-1.0
-0.5
0.0
0.5
1.0
1.5
2.0
2.5
-1.0 0.0 1.0 2.0 3.0 4.0δ57Fe (‰ vs. IRMM-14)
6 M HCl leachBulk dissolution
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Expression of isotopic ratios:
δ57FeIRMM-14 (‰) =57Fesamp54Fesamp
57FeIRMM-1454FeIRMM-14
- 1( 1000
δ57FeIRMM-14= 3/2(δ56FeIGN + 0.09)
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Geochemical applications of iron isotopes:Igneous Petrology
Planetary Geology
As a biosignature?
Mn-Fe crusts and other seawater precipitates
Iron cycling in soils and groundwater
Iron cycling in sediments; origin of BIFs
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0 1 2 3 4 5-1
redoxtransformations
redoxtransformations
Δ57Fe (‰)
Δ57Fe (‰)
Fe(II)aq - Fe(III)aq
Fe(III)aq - Hematite
0 1 2 3 4 5-1
Fe(II)aq - FeS
Fe(II)aq - Fe(III) (oxy)hydroxide
-2-3-4-5
Fe(II)aq - Hematite
Fe(II)aq - FeCO3
Fe(II)aq - Fe(II)adsorbed
-3-4-5 -2
Fe(III) (oxy)hydroxide - Fe(II)aq (DIR)Fe(II)aq - Magnetite
Fe(II)aq - FeCO3
Fe(II)aq - Fe(III)-(hydr)oxideFe(II)aq - Ca0.15Fe0.85CO3
Experimentally determined fractionations
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Natural variationsin δ57Fe
Beard & Johnson (2004)
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Mantle and terrestrial igneous rocks cluster around 0‰
Large variation in chemical precipitates and black shales
Beard & Johnson (2004)
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→ Departures from 0‰ reflect redoxprocessing on the earth’s surface.
Beard & Johnson (2004)
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Iron isotope data on Precambrian sediments
(Johnson et al., 2008)
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Application of iron isotopes to Neoproterozoic syn-glacial iron-
formationRapitan Group BIF in northwestern Canada
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Zn isotopes: 64Zn, 66Zn, 67Zn, 68Zn, 70Zn
δ66Zn(‰): 66Zn/64Zn vs. JMC 3-0749L
Natural variations: (-1‰< δ66Zn <1.3‰)
Applications:
•Seawater composition and evolution (bioproductivity)
(Carbonates; Manganese nodules)
•Zn ores
•Tracing Zn sources
•Biological uptake
•Soil processing
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δ66Zn variation in deep sea carbonates over the past 180,000 years (Pichat et al., 2003)
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Natural variationsin δ66Zn in geological materials.
Wilkinson et al. (2005)
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δ66Zn variations in different parts of the Irish Midlands hydrothermal sphalerite ore system
Wilkinson et al.
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Negative fractionation during incorporation of Zn into sphalerite?
Wilkinson et al.
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Plants may generate large Zn fractionations:
Enrichment during Zn adsorption
Progressive depletion from roots to leaves (Weiss et al., 2005)
Viers et al. (2007)
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Cu isotope fractionation:
• Large fractionation due to multiple oxidation states of Cu
• 3‰ fractionation associated with oxidation of Cu-sulphides (at surface temperatures)
• -3 to -4‰ fractionation associated with reduction of aqueous Cu(II) to Cu(I)
• Positive fractionation during Cu absorption (e.g. onto iron oxyhydroxides)
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Cu isotopes: 63Cu, 65Cu
δ65Cu(‰): 65Cu/63Cu vs. SRM 976
Large fractionations:-3‰< δ65Cu <2.5‰
Applications:
•Cu ores•Biological uptake•Soil processing
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Natural variations in Cu Isotopes
Ehrlich et al. (2004)
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Distribution in δ65Cu in hydrothermal and weathered ore deposits
Larson et al.
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Cu isotope fractionation:
•Large fractionation due to multiple oxidation states of Cu•Significant enrichment (3‰) associated with oxidation of Cu-sulphides (at surface temperatures)•Significant depletion (-3 to -4‰) associated with reduction of aqueous Cu(II) to Cu(I)•Positive fractionation during Cu adsorption (e.g. onto iron oxyhydroxides)
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Iron isotopes via in situ LA-MC ICP-MS:
•Better than 0.35‰/amu precision
•Matrix-matched bracketing standard not necessary
•Variety of Fe phases (Fe-sulphides, hematite, goethite, siderite)
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Other/future applications
•In situ Lu-Hf (e.g. zircons)•In situ Sr isotopes•Pb isotopes•Mo isotopes (palaeoredox)•Mg isotopes (weathering, dolomitisation)•Bo isotopes (in situ, solution)•U series dating (in situ, solution)
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CONCLUSIONS:
•Non-traditional stable isotope geochemistry has huge potential in a broad range of applications
•Still in the early days (very little known about sources of fractionation)
•Will have the analytical facilities to make these measurements
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CONCLUSIONS:
•Non-traditional stable isotope geochemistry has huge potential in a broad range of applications
•Still in the early days (very little known about sources of fractionation)
•Will have the analytical facilities to make these measurements
CAVEAT:
Need the people, resources, and scientific problems to realise the potential of stable isotope geochemistry in South Australia