1 laser ablation. 2 laser ablation icp-ms cetac lsx 500 thermo finnigan element
TRANSCRIPT
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LASER ABLATION
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Laser Ablation ICP-MS
CETAC LSX 500CETAC LSX 500
Thermo Finnigan ElementThermo Finnigan Elementwww.cetac.com
www.thermo.com
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“Gold can be melted and recast and is therefore virtually untraceable”
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Watling et al., Spectrochim. Acta Part B 1994, 49B, 205-219.
DISTINGUISH GOLD SAMPLES BASED ON TRACE ELEMENTS?
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DEVELOPMENTS IN LASER ABLATION
GÜNTHER et al., ANAL. CHEM. 2003, 75, 341A; TrAC 2005, 24, 255. UV LASERS (266 , 213, 193 nm)HOMOGENIZED BEAM PROFILEHELIUM TRANSPORT GAS
FRACTIONATION1. VARIATION OF SIGNAL RATIO vs TIME AS DIG SINGLE PIT2. MEAS. SIGNAL RATIOS DIFFER FROM THOSE IN SAMPLE
SOLUTIONS:FLAT BOTTOM CRATERSVERTICAL SIDESSHORT PULSE (fs) LASER(RUSSO et al., ANAL. CHEM. 2002, 74, 70A).
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PARTICLE SIZE EFFECTS IN LASER ABLATION
GÜNTHER & GUILLONGJAAS 2002, 17, 831
AESCHLIMAN et al.JAAS 2003, 18, 1008
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Particles from Ablated Y2O3 Pellet
Track length velocity ~ 27 m/s
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Pressed pelletFernald soil blank
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SINGLE SPOT ABLATION
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FEMTOSECOND LASER ABLATION
RUSSO et al.JAAS 2002, 17, 1072.ANAL. CHEM. 2003, 75, 6184 2004, 76, 379.
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Femtosecond Laser Ablation
• Nanosecond laser ablation is partly a thermal process
• Differences in the vaporization properties of elements leads to elemental fractionation
• With femtosecond pulses, the ablation process occurs by a mechanism far less dependent on thermal effects. Melting is not observed with pulse widths < 1 ps.
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Crater Profiles
Crater profiles for 100 fs and 4 ns lasers after 50 pulses
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UV fs LASER ABLATIONINGO HORNUNIV. HANNOVER
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½WP1
½WP2
TP
SHG
THG
M3
ω
2ω
M4
M2
M1
½WP3
ω
3ω
3ω ω
3ω+4ω
2ω
M5
M6
M9
M12FHG
M7
M8 4ω
ω3ω
ω
fs-laser ablation system
785 nm 196 nm
Laser Optics
Sample cell
GasMC-ICP-MS
orICP-OES
RegenerativeAmplifier
Stretcher/Compressor
Seedlaser
Pumplaser
100fs=0.0000000000001sec.
By comparison, if traveling at the speed of light for 100 fs you would onlyjust cover about 30 m in distance.
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CALIBRATE LASER ABLATION?
COMPENSATE FOR MATRIX DEPENDENCEOF ABLATION PROCESS
MATCHED STANDARDS
MEAS. ANALYTE REL. TO MINOR ISOTOPEOF ELEMENT AT KNOWN CONCENTRATION
CALIBRATE REL. TO SOLUTION AEROSOL?BECKER JAAS 2001, 16, 602AESCHLIMAN JAAS 2003, 18, 872-877.
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pump
CETAC LASER ABLATION SYSTEM TSI PIEZOBALANCE
FINNIGAN
ICP-MS
ESI NEBULIZER
Nd:YAG laser (266 nm)
camera
translation stage
argon inlet
zoom lens
impactorelectrostatic precipitator
calibration solution
waste90%
10%
20%
80%
ICP
ESA
magnet
argon inlet
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0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
0 100 200 300 400 500 600 700
Time (s)
Sig
nal
(co
un
ts s-1
) / 1
06
60Ni+
51V+52Cr+
NIST STEEL
Solution
Ablatedsolid
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Calibration of LA-ICP-MS with Dried Solution Aerosols
• Simultaneous introduction of particles from a LA cell and desolvated aerosol particles from a micro-flow nebulizer
Stotal = Ssolid + Ssolution
= RX,solid TLAt[X]solid + RX,soln VTneb[X]soln
RX isotope-specific response factor (signal/ng X)
TLA transport from LA cell (ng solid/s)t time of ablation transient (s)
[X]solid concentration of isotope in solid (ng X/ng solid)V volume of solution injected to ICP (L)
Tneb nebulizer efficiency
[X]soln isotopic concentration in solution standard (ng X/L)
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NIST 612 Glass (13 Elements, 5 Replicates)
• Particle transport from the LA cell was measured using a piezoelectric microbalance• Each replicate was generated by firing 50 laser shots per localized spot on the sample• A two-point calibration plot for each replicate was prepared and an average calculated• All elements were measured in medium resolution (R = m/m = 4000)
CONCENTRATION (ppm) MEASURED CERTIFIED Relative Diff. (%)
Mn (55Mn+) 40.8 7.9 (39.6) 3.0Fe (56Fe+) 51.6 6.1 51 1.2Co (59Co+) 36.0 4.7 (35.5) 1.4Ni (60Ni+) 39.2 4.7 38.8 1.0Cu (63Cu+) 38.5 6.7 (37.7) 2.1Ba (138Ba+) 41.6 5.5 (41) 1.5Nd (146Nd+) 36.2 2.6 (36) 0.56Sm (147Sm+) 39.5 4.7 (39) 1.3Eu (151Eu+) 36.5 4.7 (36) 1.4Dy (161Dy+) 35.1 2.5 (35) 0.29Er (166Er+) 39.3 4.2 (39) 0.77Tl (205Tl+) 15.8 1.6 (15.7) 0.64Pb (208Pb+) 39.2 5.8 38.57 1.6
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NIST 1264a Steel (8 Elements)
• 266 nm QUAD. Nd:YAG LASER, CETAC LSX-100• AVG. 30 SPOTS, TWO-POINT STD. ADDNS.• 50 SHOTS PER SPOT, MED. RES.• PARTICLE TRANSPORT MEAS. WITH MICROBALANCE
CONCENTRATION (wt %)MEAS. CERT. (INFO)
V (51V+) 0.119 0.029 0.106 Cr (52Cr+) 0.073 0.012 0.066 Co (59Co+) 0.156 0.017 0.150 Ni (60Ni+) 0.143 0.017 0.142 Cu (63Cu+) 0.248 0.040 0.250 W (184W+) 0.107 0.027 0.102 Pb (208Pb+) 0.056 0.055 0.024 Bi (209Bi+) 0.0016 0.0032 (0.0009)
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NIST 1264a Steel (8 Elements)
• 193 nm ArF LASER• AVG. 3 SPOTS, TWO-POINT STD. ADDNS.• 50 SHOTS PER SPOT, MED. RES.• PARTICLE TRANSPORT MEAS. WITH MICROBALANCE
CONCENTRATION (wt %)MEAS. CERT. (INFO)
V (51V+) 0.115 0.011 0.106 Cr (52Cr+) 0.078 0.036 0.066 Co (59Co+) 0.137 0.035 0.150 Ni (60Ni+) 0.139 0.108 0.142 Cu (63Cu+) 0.277 0.201 0.250 W (184W+) 0.108 0.013 0.102 Pb (208Pb+) 0.021 0.004 0.024 Bi (209Bi+) 0.0006 0.0001 (0.0009)
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Multivariate Analysisin LA-ICP-MS
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Laser Ablation of NIST 1224 Steel
0
500000
1000000
1500000
2000000
2500000
100 150 200 250 300 350 400
Time (s)
Sign
al (
coun
ts/s
)
53Cr
59Co
60Ni
65Cu
98Mo
184Wstart laserablation
end laserablation
signal fromargon blank
65Cu+
59Co+60Ni+
98Mo+
184W+
53Cr+
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STEEL SAMPLES
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Principal Component Analysis
• Eigenvector decomposition of covariance matrix• Matlab toolbox developed by Eigenvector
Research, Inc.• “Traditionally” applied to IR spectra• Used to extract reduced dimension “factors” that
describe trends and similarities/dissimilarities in data from multi-component spectra
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1 2 3 4 5 6 7 8 90.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
Comparison of Stainless Steel Washers from the Same Bag(16 Elements)
95% C.I.
99% C.I.
Q R
esid
ual
Sample Number
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1 2 3 4 5 6 7 8 90
2
4
6
8
10
12
Comparison of Two Stainless Steel Washers from the Same Box(19 elements)
99% C.I.
Q R
esid
ual
Sample Number
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Chemometric Comparison of Seven Carbon Steels(25 Isotope Model)
-8
-7
-6
-5
-4
-3
-2
-1
0
1
2
3
4
5
6
7
8
9
-10 -9 -8 -7 -6 -5 -4 -3 -2 -1 0 1 2 3 4
Principal Component 3
Pri
nci
pal
Com
pon
ent
2
NIST 1224
NIST 1227
NIST 1263a
NIST 1264a_1
NIST 1264a_2
pipe
bar
plate
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0 2 4 6 8 100
2
4
6
8
10
12
95% C.I.
99% C.I.
Comparison of SRM 139 and 139b to 139a(20 Elements)
Q R
esid
ual
Replicate
SRM139b SRM139
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1 2 3 4 5 6 7 8 90.1
1
10
Comparison of Two Strands from a Single Copper Wire(7 Elements)
95% C.I.
99% C.I.
Q R
esid
ual
Sample Number
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1 2 3 4 5 61E-3
0.01
0.1
1
10
Copper Wire ComparisonQ
Res
idua
l
Model Wire
Wire 1 Wire 2 Wire 3 Wire 4 Wire 5 Wire 6 99% C.I.