Inductively Coupled Plasma

Mass Spectrometry

Dr. Lloyd Allen and Dr. Stuart Georgitis

LECO Corporation
3000 Lakeview Avenue
St. Joseph MI 49085
Principles of Operation
Spectrometer Componenets
Sample Introduction System
Sample Cell
Optical Bench
Detector
Recorder or Computer
The ICP-MS Spectrometer
ICP : Source of Ions
Atmospheric Argon based plasma
Operated from 2,500 to 8000 Kelvin to produce ions
Requires interface to vacuum bench
Mass Spectrometer : Mass Filter or Mass Analyzer
Quadrupole
High Resolution Double Focusing
Ion Trap
Time-of-Flight
The ICP-MS Spectrometer
(2)

Sample Forms Possible
Solids : Conductive and Non-Conductive
Liquids : Aqueous and Organic
Gases
Method Advantages
Very Low Noise = Very High Signal to Noise Ratio
excellent detection limits (ppt)
Isotopic Analysis
Few interferences compare to other atomic techniques
Speed
The ICP-MS Spectrometer
Qualitative Uses
Semi quantitation in the absence of standards, solids.
Concentration profiling
Isotopic Ratios = Dating, Finger Printing, Finger Pointing
Method Disadvantages
TDS : typically < 0.2%
High Sensitivity = Contamination during sample prep.
Sequential systems have elevated RSDs for Ratios
High resolution systems : Resolution > = < Sensitivity
Argide and Matrix Interferences

The Purpose of the Plasma
Desolvation : Drying Droplets
Vaporization : Particles to gas
Excitation : Emission
Atomization : Dissociation
Ionization : Electron Loss
e
-

Radial Emission
Med Energy Required

(NAZ) Mn Compromise
High Energy Required
Short Wavelengths
As, Se
Low Energy Required
Long Wavelengths
K, Cs, La,Li, Na, Sr
The Plasma of ICP
AES or MS
Frequency
27 Mhz
40 Mhz
Matching Network
Crystal Controlled
Free Running
Solid State
Mini-Torch or
Standard
ICP-MS Only

Secondary or Pinch
Discharge
Center Tapped
Interlaced Coils
Torch Shields

X, Y, Z Control

ICP-MS Components:
Interface
Ions must proceed from atmospheric
pressure to an area of reduced pressure
required for MS
Plasma 1st stage 2nd stage Analyzer stage
Atmospheric
Pressure
~ 1 torr 10
-4
torr 2 x 10
-6
torr
Mechanical Pump
(Interface)
Turbo Pump Turbo Pump
Mechanical Pump
(Backing)
The ICP-MS Interface
Sampler Cone
Skimmer Cone
Barrel Shock
Mach Disk
Supersonic
Jet
Zone of Silence
Torch & ICP
Sample
Ion lenses and
Mass Analyzer
The ICP-MS Interface
Torch & ICP
Sample
Sampler Cone
Skimmer Cone
Secondary Discharge
Oxides, Polyatomics,
secondary excitation
Velocity Consideration
4 eV, 100 amu ion 1964 m/s
14 eV, 100 amu ion 3674 m/s
A factor of 2 reduction in ions in extraction volume
0 50 100 150 200 250
1
2
3
4
5
6
7
8
9
10
11
12
E
n
e
r
g
y

(
e
V
)
Mass
Ion Energies for Shielded
Load Coil
Detection Limits (10s, 3 s)
Shielded vs. Top-grounded
0
10
20
30
40
50
60
70
80
90
100
Bi Pb Tl Ba In Co Al Mg Na Li
Element
D
e
t
e
c
t
i
o
n

L
i
m
i
t

(
p
p
t
)
TG
ST
ICP Sample Introduction
Systems
Solution Nebulizers
Concentric
High Efficiency C.
V-groove
Modified Liechte
Cross Flow
Burgener

Spray Chambers
Scotts
Cyclonics
Inert or glass
Ultrasonic Nebulizer
Membrane Desolvator
Direct Injection Nebulizer
Arc-Spark
ETV
Laser
Direct Insertion Nebulizer
Hydride Generator
Discrete Sampling

ICP-AES and ICP-MS
Inductively Coupled Plasma
Simultaneous Sequential
PMT
CID
CCD
PMT
PMTs
Magnetic Sector
Quadrupole
ICP-AES ICP-MS ICP-AES ICP-MS
Magnetic Sector
Time of Flight
Ion Trap
The Two Major Approaches to
ICP-MS Spectrometry
Sequential : Mass Filters
or
Simultaneous : Mass Analyzer
Quadrupole ICP-MS
A Sequential Mass Filter
All m/z
Values In
One m/z
Value Out
+
-
+
-
Separation Based on Stability of the m/z Value
in the RF and DC Fields on the Quadrupole Rods
Quadrupole ICP-MS
RF
1
, DC
1
RF
3
, DC
3
Time
1
Time
2
Sequential Analysis Limitations:
ICP-MS
Sample throughput > = < a function of the
number of m/z values measured

Transient Signals : very few isotopes analyzed
ETV
Chromatography
Single spot laser ablation
Can not obtain high precision isotope ratios
Small volume samples: v. few isotopes analyzed
Susceptible to cones plugging (TDS) by prolonged sample
contact


TOF ICP-MS Theory
Simultaneous Mass Spectra
KE = 1/2 mv
2
= zV m/z = 2V/v
2
m/z = (2Vt
2
)/(L
2
)
Velocity v = L / t
Flight Tube Length (L)
(+)
Accelerating
Voltage (V)
+
+
+ +
+ +
Repeated up to 30,000 times per second
Requirements of TOF-ICP-MS
Continuous ion beam requires modulation

Detector must respond to fast ion events (ns)

Data acquisition system must be able to handle TOF
speeds

Matrix ions must be removed to avoid detector
saturation
Right-angle/Orthogonal
Injection
Repeller
Acceleration
Field
Field-Free
Flight Region
Ion Lenses
Orthogonal TOF ICP-MS
Disadvantages
Transmission Efficiency at best 20%

Sensitivity/Resolution Tradeoff

Mass Dependent Optics in TOF due
to mass dependent energies

Orthogonal Transmission

Detector Plane
or
Ion Mirror
Original
Ion Packet
L= 0.5 to 0.75 m
23 mm dia.
ion detector
v
y
/ v
x y
x
Mass-Dependent Energies
Repeller
Acceleration
Field
Detector
Ion Mirror
Vsteer
Green - Pb
Red - Li
Ion beam
Orthogonal Mass Bias
0
256
M/Z
CTS
Low Mass Bias
Mid Mass Bias
High Mass Bias
Axial Mass Bias
0
256
M/Z
CTS
On-Axis Ion Injection Advantages
Improved Ion Transmission Efficiency

Reduced Mass Bias

Reduced Optical Maintenance

Reduced Instrument Footprint
Schematic Diagram of Axial TOF
ICP-MS
1 2 3
Acceleration
Extraction
Skimmer
Sampler
Detector
Ion Mirror
ICP Torch
Vacuum Stages
Flight Tube
Simultaneous Mass Spectra Modulation
(+)
+ +
+ +
Repeated up to 30,000 times per second
Accelerate to TOF Accelerate to TOF Accelerate to TOF
Reject
Reject Rejec
t
38 Micro S
38 Micro S
38 Micro S
Schematic Diagram of Axial TOF
ICP-MS
1 2 3
Einzel 2
X-Steering
Y-Steering
Acceleration
Repeller
Modulation
Extraction
Skimmer
Sampler
Third Stage Orifice
Detector
Energy Barrier
Gridded Ion Mirror
Flight Tube
ICP Torch
Ion Optic 1
Einzel 1
Ion Mirror
Ion Mirror
Acceleration
Field
Detector
Simultaneous Advantages
Transient Signals: complete multielement analysis

High precision isotope ratios : Simultaneous Reads
no additive noise when employing corrections
no sample introduction or plasma noise

Small volume samples: complete multielement analysis
minimum sample destruction
maximum spatial concentration profile capability

Sample throughput =delivery and rinse time primarily

Cone plugging via TDS exposure is minimized
Method Advantage :
TOF Means Speed
30,000 Full Mass Spectra per Second
U = Mach 115
Detection Limits
Are They Signal To Background ? Or Signal to Noise?
0
256
M/Z
CTS
Detection Limits
Are They Signal To Background ? Or Signal to Noise?
0
256
M/Z
CTS
TOF ICP-MS Detection Limits
(3s)
Element DL (ng/mL) Element DL (ng/mL)
Ba 0.002 Rb 0.004
Co 0.004 Rh 0.002
Cu 0.004 Sr 0.002
Dy 0.009 Ta 0.006
Er 0.008 Tb 0.001
Eu 0.003 Th 0.005
Gd 0.005 Tl 0.008
Ho 0.002 Tm 0.002
La 0.003 U 0.004
Lu 0.002 W 0.004
Nd 0.009 Y 0.003
Pr 0.002 Yb 0.005
Mn 0.003 V 0.003
Short Term Stability
Internal Standard Results
(20 min. 10 ppb)
% RSD % RSD Limit
V 1.04 0.31
V/Y 0.51 0.42
Ba 0.70 0.33
Ba/Tb 0.51 0.43
U 1.44 0.3
U/Bi 0.59 0.46
0
1000
S
i
g
n
a
l

(
c
p
s
)
0
6000
204 206 208
4
m/z
S
i
g
n
a
l

(
m
v
)
204 206 208
4
m/z
Dual-Mode Detection

1 ng/mL 100 ng/mL
A
n
a
l
o
g

S
i
g
n
a
l

(
m
V
)

I
o
n

C
o
u
n
t
i
n
g

S
i
g
n
a
l

(
c
p
s
)

Saturation
10
-3
10
-2
10
-1
10
0
10
1
10
2
10
3
10
4
10
0
10
1
10
2
10
3
10
4
10
5
10
6
10
7
209
Bi
Concentration (ppb)
C
o
u
n
t
i
n
g

S
i
g
n
a
l

(
c
p
s
)
10
-3
10
-2
10
-1
10
0
10
1
10
2
10
3
10
4
A
n
a
l
o
g

S
i
g
n
a
l
Dynamic Range

Correlation Coefficient
Counting Analog
Co 0.9993 1.0000
In 0.9994 0.9999
Cs 0.9994 1.0000
Ba 0.9999 0.9997
Bi 1.0000 1.0000
U 0.9991 0.9999
Dynamic Range (Counting and
Analog)
1E-3 0.01 0.1 1 10 100 1000 10000 100000
0.1
1
10
100
1000
10000
100000
1000000
R=0.99954
B
i
s
m
u
t
h

R
e
l
a
t
i
v
e

S
i
g
n
a
l

A
r
e
a
Concentration (ppb)
LECO Patented Ion
Counting/Analog Detection
Scheme
ETP
AF831H
20 dB
gain switching
pre-amp
100 MHz Ion Counter
500 MHz
flash A/D
Windowed Buffer
Dual Accumulator
VME
Bus
High Data Throughput
Data throughput from ICP-MS up to
750 Mbytes/sec
reduction is necessary for practical
analysis


Buffer retains 2000, 2 ns bins from
each spectra


Individual spectra are summed and
the data transferred to the host
computer

Max bandpass 0.75 Mbytes/sec


TOF-MS
500 MHz A/D, 100 MHz Counter
30 kHz Spectral Rate
Buffer
Accumulation
Mass Mapping
Summation
Throughput
(Mbytes/sec)
750
0.75
120
13
Mass Mapping
Mass
68 69 70
40
Ar
14
N
2
68
Zn (impurity)
70
Ge
139
La
(2+)
69
Ga
2 ppb Ga/Ge, 500 ppb La
Time Bins
Bin Summation
255 Summed to 1
Figures of Merit and Applications
Spectral resolution and matrix deflection

Detection limits and speed of analysis

Multielement transient signal analysis

Isotope ratios and internal standards

Solid sample analysis by LA
Quadrupole Resolution
Low M/Z High M/Z
0.3 AMU 1.0 AMU
TOF Resolution
Low M/Z High M/Z
Unit Mass Baseline Resolved
1.0 AMU at Greatest Mass
< 0.3 AMU at Least Mass
with No Sacrifice in Sensitivity
TOF Resolution
Low M/Z High M/Z
Lower Mass Resolving Power
66 67 68 69 70 71 72 73 74 75 76 77
40
Ar
14
N
2
68
Zn (impurity)
76
Ge
74
Ge
73
Ge
72
Ge
71
Ga
70
Ge
139
La
2+
69
Ga
2 ppb Ga/Ge, 500 ppb La
2 ppb Ga/Ge
Mass
Resolving Power at High
Mass
204 205 206 207 208 209 210
R
50%
= 1270
R
10%
= 475
S
i
g
n
a
l
Mass
50 ppt Pb, Bi
Resolution
Selected Spectral Regions Expanded
58 60 62 64
65
Cu
+
64
Zn
+
63
Cu
+
62
Ni
+
61
Ni
+
60
Ni
+
134 135 136 137 138
59
Co
+
58
Ni
+
138
Ba
+
137
Ba
+
136
Ba
+
135
Ba
+
134
Ba
+
m/z
202 204 206 208
208
Pb
+
207
Pb
+
206
Pb
+
205
Tl
+
204
Pb
+
203
Tl
+
Quadrupole ICP-MS
Matrix Filter
RF
1
, DC
1
RF
3
, DC
3
Time
1
Time
2
TOF and High Matrix
Low M/Z High M/Z
Coulombic Repulsion During Flight
TIME
+
+ +
+
TOF and High Matrix
Low M/Z High M/Z
Selectable Matrix Removal
Flight Tube
T.R.I.P.
Transverse Rejected Ion
Pulse
Acceleration
Repeller
Modulation
8 12 16 20
0
1
2
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
R
e
l
a
t
i
v
e

I
n
t
e
n
s
i
t
y

(
m
V
)
Flight Time (sec)
8 12 16 20
Flight Time (sec)
Background Species Deflection
(T.R.I.P.)
NO
+
Ar
+
Ar
+
NO
+
O
+
, OH
+
ICP-MS Speed Quadrupole vs TOF
* Theoretical 0.3 sec. dwell time, 5 replicates, 60 sec. rinse time
** 3 points/peak, 10 s quadrupole settle time
EPA 200.8
(Analytes, Interference Corrections, Internal Standards)
0.0
100.0
200.0
300.0
400.0
500.0
600.0
1 11 21 31 41 51 61 71 81 91
Number of m/z Values Measured
T
i
m
e

(
s
e
c
o
n
d
s
)
Quadrupole**
TOFMS