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Solid/liquid
sample
Nebulisation
Solution
Sample
preparation
M X
+
Desolvation
Vaporisation
M(g) + X(g)
Sputtering, etc.
M+
Atoms in gas
phase
Ionisation
Molecules in
gas phase
MX(g)
Atomisation=
Dissociation
Excitation
Ions
ICP-MS and
other MS methods
(also: ICP-OES)
Adapted from www.spectroscopynow.com (Gary Hieftje)
Excited
Atoms
ICP-MS
Under vacuum
Detector
(e.g.
electron
multiplier)
nebuliser
Interface
Spray chamber
sample
http://www.cee.vt.edu/ewr/environmental/teach/smprimer/icpms/icpms.htm
ICP-MS instrumentation
Sampling cone
Collision cell
ICP Torch
Cones and
Ion Optics
Detector
(discrete
dynode)
Mass Analyser:
Quadrupole
Skimmer
cone
Mostly, singly
charged positive
ions are
generated (>90%
efficiency)
ICP torch
Time-of-Flight (rare)
HR (High-resolution): Uses magnetic sector mass
analyser
http://www.wcaslab.com/tech/
tbicpms.htm
http://las.perkinelmer.co.uk/content/TechnicalInfo/TCH_ICPMSThirtyMinuteGuide.pdf
Polyatomic interferences
in ICP-MS: Origins
Spectral interference:
caused by presence
of species with same
mass as analyte
Often derived from
compounds with Ar
Analyte
Interference
K+
38
Ar1H+
Ca+
40
Ar+
V+
35
Cl16O+
Cr+
40
Ar12C+
Fe+
40
Ar16O+
Cu+
23
Na40Ar+
As+
40
Ar35Cl+
Se+
40
Ar2+
39
40
51
52
56
63
75
80
Overcoming polyatomic
interferences:
Collision/reaction cells (CRC technology)
http://breeze.thermo.co
m/collisioncells/
(Webinar)
gas
31
O16O
16
N16O1H
14
N16O
15
32
30.95
31.00
Mass (u)
31.95
32.00
50
40
Zn: 4.1%
67
30
20
10
0
64
66
67
68
70
Isotope
Incubated overnight at 37C
with 40 mol equivalents of
67
Zn(II) (93% isotopic purity)
Measured isotopic ratios
Total S
Total Zn
Ratios:
66
Zn / 64Zn
0.657 0.0028 (n = 7)
67
Zn / 64Zn
4.17 0.025 (n = 7)
68
Zn / 64Zn
0.490 0.0037 (n = 7)
70
Zn / 64Zn
0.01325 0.00007 (n = 7)
As measured
Calculated for 3
exchanging Zn(II)
66/64
67/64
68/64
70/64
For each isotopic ratio, results agree best with the scenario for 3
exchanging zinc: Clear demonstration that only 3 out of 4 Zn exchange:
The protein has one zinc that is inert towards exchange
Caveat: Calibration ?
Laser ablation
Useful for surface analysis of solid samples
monitor camera
Laser
UV light
To ICP
Carrier gas in
sample
Cheap, simple
Small dynamic range
GFAAS about 100 times more sensitive than FAAS,
but also more challenging
Limited spectral interferences, good stability, low
matrix effects
http://pubs.acs.org/hotartcl/tcaw/99/oct/element.html
Synopsis:
Interferences in atomic
spectroscopy
Technique Type of
Method of Compensation
Interference
Flame
AAS
Ionization
Chemical
Physical
Ionization buffers
Releasing agent or nitrous oxide-acetylene
flame
Dilution, matrix matching, or method of
additions
Graphite
Furnace
AAS
Physical and
chemical
Molecular
absorption
Spectral
ICP-OES
Spectral
Matrix
ICP-MS
Spectral
Matrix
http://pubs.acs.org/hotartcl/tcaw/99/oct/table1.html