AAS, ICP-AES, ICP-MS

Akhmad Sabarudin

Analytical Techniques for

Elemental Analysis
AAS - Atomic Absorption Spectrometry
ICP-OES - Inductively Coupled Plasma Optical Emission Spectrometry
=
Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES)
ICP-MS - Inductively Coupled Plasma Mass Spectrometry

LOD of each method

ICP-MS
1 ppm

10 ppb

100 ppt
10 ppt
1 ppt

GF-AAS

100 ppb

1 ppb

ICP-AES

Ca
K
Br Fe P
B
Cr Na
Cd Pb Cu Zn
Mg Co Mo
REEs Cs U

U
Al
Pb
Cr
Cd
Zn
Be
Ca
Ba

Pd
As
Ni
B
Cu
Ti
Bi
Mn

Sn
Se
Sb
Fe
Li
Ag
Sr
Mg

Hg
Ti
As
Ni
Ba
Co
Al
Cd

Se
Sn
Sb
Ca
As
Cr
Mg

V
Tl
Pb
Cu
Mn
Ag

Zn

LOD : Limit of Detection

Characteristics of instruments

Detection
Merit

ICP-MS

ICP-AES

mass

emission

absorbance

multielement

high sensitivity

high sensitivity
multielement

Demerit

Ranges

GF-AAS

selective

damage from
high salinity

relatively low
sensitivity

1 ppt
100 ppb

0.1 ppb
10 ppm

monoelement

1 ppb
100 ppb

Atomization
in AAS, ICP-AES, ICP-MS

AAS
GF-AAS
flame

5 mm x 2.5 cm

graphite tube ( )
Light source
hollow cathode lamp

ICP-AES
Ar plasmaheating
500010000 K
Atomic emission
Detector
Monochrometer

Sample solutionaqueous soln.

Recorder

Amplifier

ICP-MS
Quadropole
Ion lenses
mass filter

Mass detection

ICP-torch

Plasma

Atomization
Sample soln.

(Instrumentation)

Collision Unit

Ion counts

Application of ICP-MS (Some examples)

Table 2 Analytical results for trace elements in several nitric acids by ICP-MS
Supplier A
Element m/z

Impurities in nitric acid

60 elements

Anal.Sci., 19, 1561 (2003).

Li
Be
B
Na
Mg
Al
K
Ca
Sc
Ti
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
Ga
Ge
As
Se
Rb
Sr
Y
Zr
Nb
Mo
Ru
Rh
Pd
Ag
Cd
In
Sn
Sb
Te
Cs
Ba
La
Ce
Pr
Nd
Eu
Sm
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
Hf
Ta
W
Pt
Au
Hg
Tl
Pb
Bi
Th
U

7
9
11
23
24
27
39
43
45
49
51
52
55
57
59
60
63
66
69
74
75
82
85
88
89
90
93
98
102
103
106
107
114
115
118
121
130
133
138
139
140
141
146
151
152
157
159
163
165
167
169
174
175
180
181
184
195
197
202
205
208
209
232
238

Ultra a/
ng mL -1
0.000
0.000
0.57
0.026
0.073
0.027
0.033
0.66
0.002
0.03
0.15
0.018
0.050
0.001
0.004
0.039
0.24
0.21
0.007
0.000
0.013
0.028
0.006
0.003
0.007
0.001
0.005
1.08
0.002
0.001
0.008
0.11
0.019
0.001
0.023
0.003
0.012
0.000
0.012
0.005
0.12
0.008
0.000
0.001
0.001
0.000
0.005
0.000
0.000
0.000
0.002
0.000
0.000
0.001
0.000
0.000
0.001
0.003
0.000
0.000
0.002
0.001
0.000
0.000

Traceb/
ng mL-1
0.000
0.000
1.72
0.077
0.061
0.017
0.36
1.19
0.001
0.07
0.096
0.12
0.064
0.075
0.003
0.061
1.33
0.11
0.005
0.002
0.012
0.006
0.003
0.003
0.011
0.002
0.000
5.82
0.000
0.000
0.006
0.089
0.071
0.001
0.036
0.005
0.058
0.000
0.015
0.048
0.31
0.14
0.058
0.002
0.000
0.002
0.005
0.000
0.011
0.000
0.002
0.000
0.000
0.000
0.000
0.000
0.007
0.009
0.000
0.000
0.011
0.001
0.019
0.007

Anal c/
ng mL -1
0.001
0.000
1.16
0.094
0.066
0.012
0.34
0.88
0.003
0.03
0.17
0.036
0.060
0.043
0.015
0.033
0.12
0.14
0.007
0.001
0.007
0.048
0.004
0.004
0.011
0.001
0.005
41.7
0.004
0.000
0.044
408.7
0.53
0.002
0.031
0.010
0.47
0.001
0.014
0.078
3.99
0.061
4.05
0.008
0.010
0.013
0.020
0.042
0.000
0.000
0.006
0.000
0.004
0.000
0.000
0.26
0.010
0.008
2.4
0.009
0.098
0.010
0.057
0.000

Supplier B
Extra d/
ng mL-1

Ultraa/
ng mL -1

Analc/
ng mL-1

Extra d/
ng mL -1

0.001
0.000
0.82
0.47
0.28
0.031
0.63
0.78
0.002
0.02
0.087
0.036
0.24
0.048
0.005
0.127
0.32
0.18
0.006
0.001
0.006
0.004
0.002
0.021
0.007
0.001
0.001
1.09
0.000
0.000
0.008
0.17
0.015
0.003
0.059
0.010
0.015
0.000
0.027
0.29
0.12
0.000
0.000
0.010
0.010
0.008
0.002
0.000
0.000
0.000
0.002
0.000
0.004
0.004
0.000
0.039
0.002
0.023
0.014
0.000
0.065
0.009
0.038
0.008

0.000
0.000
0.55
0.030
0.030
0.006
0.025
0.57
0.001
0.04
0.065
0.014
0.054
0.006
0.003
0.000
0.04
0.062
0.004
0.001
0.003
0.022
0.000
0.001
0.004
0.003
0.002
0.60
0.000
0.000
0.009
0.98
0.011
0.000
0.002
0.001
0.008
0.000
0.003
0.005
0.060
0.006
0.000
0.002
0.001
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.004
0.000
0.000
0.000
0.000
0.001
0.006
0.000
0.034
0.000
0.000
0.008

0.001
0.000
0.27
0.075
0.044
0.005
0.31
0.44
0.001
0.05
0.062
0.030
0.065
0.037
0.001
0.010
0.05
0.11
0.004
0.002
0.005
0.022
0.001
0.002
0.000
0.001
0.000
0.97
0.000
0.000
0.006
0.064
0.015
0.000
0.170
0.008
0.015
0.000
0.012
0.005
0.12
0.004
0.12
0.006
0.000
0.004
0.005
0.014
0.004
0.000
0.002
0.000
0.000
0.000
0.000
0.000
0.002
0.002
0.002
0.000
0.018
0.002
0.000
0.008

0.001
0.000
0.41
0.073
0.036
0.008
0.020
0.49
0.001
0.01
0.080
0.024
0.066
0.050
0.002
0.005
0.02
0.037
0.003
0.002
0.003
0.016
0.001
0.002
0.000
0.000
0.001
1.12
0.000
0.000
0.008
3.12
0.016
0.001
0.043
0.002
0.010
0.000
0.005
0.065
0.24
0.000
0.058
0.000
0.021
0.000
0.020
0.000
0.004
0.000
0.002
0.004
0.002
0.000
0.000
0.000
0.002
0.002
0.010
0.000
0.006
0.000
0.019
0.000

a. Ultrapure reagent grade. b. For trace metal analysis. c. Analytical reagent grade. d. Extrapure reagent grade.
Concentration in 0.1 M nitric acid solution diluted with ultrapure water from concentrated nitric acid reagents.

Solid samples

Acid digestion apparatus: microwave system

Plug
Safety Disk
Seal
Screw Cap
Supporting Vessel
Pressure vessel (TFM)
Liner
Bomb Jacket
Vessel Base Plate

Microwave sample preparation system

MULTIWAVE (Anton Paar GmbH)

Analytical results of peach leaves

Element
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu

Mass number Measured value

(mg/Kg)
139
140
141
146
147
151
157
159
163
165
167
169
172
175

8.99
9.88
1.21
6.76
0.926
0.142
1.15
0.0890
0.305
0.0553
0.170
0.0143
0.112
0.0117

Certified value
(mg/Kg)
(9)
(10)
(7)
(1)
(0.17)
(1)

Analytical results for REEs in NIES No.2 sediment sample

Element m/z
Y
La
Ce
Pr
Nd
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu

89
139
140
141
146
147
151
157
159
163
165
167
169
172
175

Direct*1
(g g-1 )
11.7
8.06
14.2
1.66
6.72
1.30
0.43
1.27
0.20
1.31
0.29
0.81
0.11
0.80
0.11

0.19
0.25
0.79
0.07
0.20
0.02
0.01
0.01
0.00
0.04
0.00
0.06
0.01
0.03
0.01

Column*1
(g g-1)

Column*2

Column*3

(g g -1)

(g g-1)

10.4 1.3
7.21 0.90
13.5 1.7
1.63 0.22
6.15 0.87
1.17 0.16
0.43 0.05
1.25 0.23
0.19 0.09
1.21 0.17
0.29 0.05
0.76 0.10
0.10 0.03
0.79 0.12
0.11 0.03

0.53
0.04
0.69
0.03
0.18
0.03
0.01
0.03
0.02
0.03
0.01
0.03
0.01
0.03
0.01

9.45
7.06
13.2
1.69
6.02
1.19
0.48
1.21
0.20
1.23
0.32
0.81
0.12
0.80
0.10

*1 : 0.2 g sample with HNO3 (5 ml) + HF (1 ml) (2500-fold dilution, n=3).

*2 : 0.2 g sample with HNO3 (5 ml) + HF (1 ml) + HCl (1 ml) (2500-fold dilution).
*3 : 0.2 g sample with HNO3 (5 ml) + HF (1 ml) + H2SO4 (1 ml) (2500-fold dilution).