Transcript Advances in Determinations of metals by ICPMS, from ultra-small

Advances in
Determinations of
metals by ICPMS,
from ultra-small
sampling to ultra-
trace analysis.
AES Department
Dr. Otto Herrmann
Teresa Switzer
May 11, 2009
Historical Background and Application
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1980’s atomic absorption – graphite furnace to low ppb and some fractional ppb
LATE 1980’S – introduction of ICPAES with routine 5 to 20 ppb – ultrasonic
nebulization to improve about 10x (overlap with graphite
- Pb in boiler water – Bruce
2000+ ICPMS with DRC– routine compromise conditions 0.1 ppb and
optimized to 0.01 ppb
- trace metals in moderator water; TIFAC at Darlington
- Gd precipitation and isotopic distribution in moderator
2009 next generation ICPMS – about 100x more sensitive and multiple sample
introduction methods
OPERATION AND MAINTENANCE
ICPMS#2 – with attachments
ICPMS-bare
ICPAES
AAS -GRAPHITE
AAS - FLAME
THE NEXT GENERATION STARTREK
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Varian 820-MS Instrument
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Design Features such as 90 degree mirror leading to superior sensitivity and
detection limits
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Interference reduction capabilities – new mechanism not fully characterized
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Isotope measurement as “radioanalytical” technique (direct -1500yr half-life;
indirect –neutron absorption capability B, Gd); non-active tracers
Laser Ablation- ICP-MS
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Use of technique as a semi-quantitative tool and quantitative tool (more
difficult)
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“non-destructive” analysis
HPLC and GC interfaces for speciation and matrix separation
Varian 820-MS
LA1
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LASER ABLATION
LASER ABLATION SAMPLING ATTACHMENT
NEW WAVE 266 NM LASER
LA2
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LASER ABLATION +/-
No sample digestion required – direct analysis of solid
material.
Relatively “non-destructive” analysis if sample cannot
be destroyed.
Interferences and contamination from sample
handling and digestion protocols are eliminated
BUT
Difficult to calibrate for accurate quantitation
(standards – both physical form and composition
critical)
Design special cells for large samples
LA3
Contamination via Handling – 5n Al
ICP
ICP
Goodfellow Goodfellow
B
Ba
Ca
Co
Cr
Cu
Fe
Mg
Mn
Mo
Nd
Ni
P
Pb
Sb
Sc
Si
Sn
V
Zn
Zr
ICP
Goodfellow
ICPMS
LA
Goodfellow Goodfellow
ZrN-old ZrN new drillTi new drillZrN-old NIL
<16
<30
<30
<0.2
0.04
<2
<2
<2
0.45
<4
36
2
<2
0.06
<6
<5
<5
<0.2
<6
<5
<5
7.08
29
<4
<2
26.9
0.87
150
46
21
151
13.1
<2
2
1
4.0
4.7
<2
<2
<2
4.25
0.59
<10
<6
<3
0.64
0.04
<10
<10
<10
7.25
<40
<40
<40
<20
0.80
<20
<20
<20
8.42
0.41
<44
0.31
0.04
0.03
<20
<20
<20
<20
0.14
<8
<8
<8
1.59
0.27
<10
<10
<10
<2
0.02
<2
11
<2
3.74
<6
0.80
0.13
LA4
High Purity Aluminum (5n) Analysis by LA-ICPMS
ppm
LA
LA
LA
Sample
09-01551-1
09-01551-2 09-01551-3
isotope
Goodfellow Ekain - China Giang&I -China
As75
<0.02
0.042
B11
0.039
0.037
Ca43
0.064
0.072
Ce140
0.645
0.220
Cu65
0.863
0.940
Fe57
13.080
21.408
Mg24
4.688
5.694
Mn55
0.585
1.012
Nd146
0.044
0.031
P31
0.798
1.121
Pb208
2.275
0.170
Sb121
0.039
0.025
Sc45
0.032
0.042
Si28
0.136
0.189
Si29
0.110
0.155
Sn118
0.267
0.428
V51
0.017
0.019
Zr90
0.127
0.040
TOTAL
23.809
31.645
5n=99.999% = <10 ppm impurities
<0.02
0.035
0.088
0.792
0.869
20.951
5.519
0.750
0.038
1.262
2.393
0.028
0.043
0.192
0.180
0.271
0.031
0.647
34.089
LA5
LASER ABLATION
Faults versus Bulk Analysis
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20um to 600 um spot size determined by application
Ablate in preset pattern – target vs. scan
BURN TRACK-20um
BURN
PENNY WITH TARGET
MARKING
Combined Techniques
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HPLC-ICPMS best known
- speciation (AS+3, AS+5, organo-As such as arsenobetaine);
EPA legislation tributyl tin
- matrix removal or species concentration
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GC-ICPMS – volatile species; Hg species; organometallics;
least familiar