COMMUNITY USER WORKSHOP ON PLANETARY LIBS …€¦ · Introduction to LIBS Sam Clegg Los Alamos...
Transcript of COMMUNITY USER WORKSHOP ON PLANETARY LIBS …€¦ · Introduction to LIBS Sam Clegg Los Alamos...
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COMMUNITY USER WORKSHOP ON PLANETARY LIBS (CHEMCAM) DATA
Introduction to LIBS
Sam Clegg
Los Alamos National Laboratory
16 Mar 2014 ChemCam Community Workshop 1
Lunar and Planetary Science Conference, March 16th, 2014
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Creating LIBS Sparks
16 Mar 2014 ChemCam Community Workshop 2
Introduction to LIBS
3”
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LIBS Spots and Dust Removal
16 Mar 2014 ChemCam Community Workshop 3
Introduction to LIBS
NASA/JPL-Caltech/MSSS/Honeybee Robotics/LANL/CNES
“Wernecke”
Sol 169
NASA/JPL-Caltech/LANL/IRAP/CNES/LPGNantes/IAS/CNRS/MSSS
ChemCam Dust Removal
Brushed Surface
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LIBS Sensitivities, ChemCam Configuration
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Introduction to LIBS
B** C** N** O** F Ne
Na* Mg*
Li** Be**
H** He
Al* Si* P** S** Cl** Ar
Ga Ge As** Se Br Kr
In Sn Sb Te I Xe
Tl Pb** Bi
Mn** Fe* Co Ni** Cu** Zn**
Ru Rh Pd Ag Cd**
Re Os Ir Pt Au Hg
K* Ca* Sc** Ti* V Cr**
Rb** Sr** Y Zr Nb Mo
Cs Ba** La Hf Ta W
5-100 ppm
100-1000 ppm
0.1-3%
Difficult
Approximate detection limits at Mars atmospheric pressure X* = Reported Oxides X** = To be reported
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Ca LIBS Spectrum-LANL Testbed
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Introduction to LIBS
• Not every NIST emission line is observed in a LIBS spectrum.
– http://physics.nist.gov/PhysRefData/ASD/lines_form.html
– Every LIBS line must be found in NIST
– Typically observe neutral and first ionized atoms, perhaps second ionization under ChemCam conditions.
• Must be Spectrally well calibrated! – Know the difference between vacuum vs. air (Earth or
Mars) calibration
– Closest NIST emission line is not good enough
• More details provided in the next few presentations
wavelength (nm)
260 280 300 320 340
Inte
nsity
(pho
tons/D
N)
-5.0e+12
0.0
5.0e+12
1.0e+13
1.5e+13
2.0e+13
2.5e+13
wavelength (nm)
380 400 420 440 460
Inte
nsity
(pho
tons/D
N)
-5e+12
0
5e+12
1e+13
2e+13
2e+13
3e+13
3e+13
wavelength (nm)
500 550 600 650 700 750 800 850 900
Inte
nsity
(pho
tons/D
N)
-4e+12
-2e+12
0
2e+12
4e+12
6e+12
8e+12
UV Region VIS Region
VNIR Region
Ca Spectrum Neutral Ca (I) Ionized Ca (II)
Ca Spectrum Neutral Ca (I) Ionized Ca (II)
Ca Spectrum Neutral Ca (I) Ionized Ca (II) O
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Raw ChemCam Spectrum – Jake_1
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Introduction to LIBS
Peak FWHM ~3 – 4 pixels
~1.5 nm
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Raw ChemCam Spectrum – Jake_1
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Introduction to LIBS
Peak FWHM ~3 – 4 pixels
~1.5 nm
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Raw ChemCam Spectrum – Jake_1
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Introduction to LIBS
Carefully Processed Spectra Lead to Quantitative Analysis Continuum Removal, Spectral Calibration, Distance Correction are Critical
Peak FWHM ~3 – 4 pixels
~1.5 nm
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ChemCam Spectra
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Introduction to LIBS
Fully Processed Spectra Ready for Quantitative Analysis Much can be Qualitatively Observed
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Chemical Matrix Effects Complicate Quantitative Analysis
10
Introduction to LIBS
Conventional Elemental Analysis Peak Area or Height vs.
Concentration Each Peak is Analyzed
Independently
Sample Elemental and Molecular Composition Influences: Laser-to-Sample Coupling Efficiency Chemical Reactions within the
Plasma Collisional Quenching
Chemical Matrix Effects Increase Scatter and Uncertainty
Chemical Matrix Effects Compensation Cal-Free LIBS Various Normalization
Si (288nm)
Elemental Concentration (Atomic Fraction)
0.16 0.18 0.20 0.22 0.24 0.26
Inte
gra
ted N
orm
aliz
ed
In
ten
sity (
arb
. u
nits)
0.002
0.004
0.006
0.008
0.010
0.012
0.014
0.016
0.018
0.020
b = -9.132e-3m = 0.087r ² = 0.700
Peak Area Analysis Method
Multivariate analyses are used to compensate for these matrix effects
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Quantitative Calibration
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Introduction to LIBS
3 m standoff distance
BHVO-2 DH 4912 Norite Swy-2
GBW 07105 JR-1 GYP A SGR-1
Igneous
NBS688 GBW 07113 GYP C VS MO7 Sedimentary
BIR-1 Ultramafic* GYP D UNS ZK Sulfur-rich
BCR-2 Umph* MHC1356* GUW GNA Rover cal
JA-1 Cadillac* MHC2319* M6 Haggerty*
* = from Dyar lab, all others from commercial sources
Ja2 VH-1* VZO106 GYP B
Ja3 MSHA* VZO114 MHC3828*
MO12 Moppin* NAu2-Hi-S UNS AK
MO14 BK-2 NAu2-Med-S GBW 07313
JB-2 BWQC1* NAu2-Lo-S GBW 07316
GSR-2 Trond* KGa2-Med-S SARM51
BE-N WMG* NBS-88b STSD-1
AGV-2 VH-49* JDo-1 STSD-3
JB-3 Grano Dike* GBW 07108 STSD-4
BT-2 Macusanite NBS 97a
GBW 07110 Picrite NBS 98a
GBW07104 Shergottite NAu2
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backup
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Introduction to LIBS
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Ca Electronic Energy Level Diagram
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Introduction to LIBS
Ca Electronic Energy Level DiagramsE
lectr
onic
Ene
rgy
(cm
-1)
0
2e+4
4e+4
6e+4
8e+4
1e+5
Ca I - Neutral Atoms
Upper States
Lower States
Ca II - Ionized Atoms (1e-)
Upper States
Lower States
3 States
3 States 2 States
2 States
Emission lines are produced as atoms relax from upper state to lower state. Lower state is not always the ground state.