AAS, ICP-AES, ICP-MSAkhmad Sabarudin

Analytical Techniques forElemental 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

ICP-MS ICP-AES GF-AAS1 ppm

1 ppb

1 ppt

Mn

REEsMo

Cd10 ppt

100 ppt

10 ppb

100 ppb

PbMg Co

Cr NaBBr FeKCa

P

Cs U

Cu Zn

BaCa Mg

BiBe SrZn TiCdCr B Fe

Cu

AlPb

AgLi

AsNi

SeSb

KU Pd Sn

Zn

Cd Mg AgAl Cr MnCo As Cu

As Sn VTi SeHg

Ba Ca PbNi Sb Tl

LOD : Limit of Detection

LOD of each method

ICP-MS ICP-AES GF-AAS

Ranges 1 ppt 〜

100 ppb0.1 ppb 〜

10 ppm1 ppb 〜

100 ppb

Merit

Demerit

Detection mass emission absorbance

high sensitivity

multielement selective

multielement

damage fromhigh salinity

relatively lowsensitivity

high sensitivity

monoelement

Characteristics of instruments

Atomization in AAS, ICP-AES, ICP-MS

AAS

graphite tube (黒鉛炉 )

hollow cathode lamp（中空陰極ランプ）

GF-AAS

Light source

5 mm x 2.5 cm

flame

ICP-AESAr plasma（heating）

Atomic emission

Monochrometer（分光器）

Detector

Amplifier

Recorder

5000〜10000 K

Sample solution：aqueous soln.

ICP-torchIon lensesQuadropolemass filter

Sample soln.

AtomizationMass detection Plasma

ICP-MS

(Instrumentation)

A

B

A

B

Collision Unit

Ion

coun

ts

Application of ICP-MS (Some examples)Element m/z

Table 2 Analytical results for trace elements in several nitric acids by ICP-MS

Supplier A Supplier B

Ultraa/ Traceb/ng mL-1

Analc/ng mL-1

Extrad/ng mL-1

Ultraa/ng mL-1

Analc/ng mL-1

Li 7Be 9B 11Na 23Mg 24Al 27K 39Ca 43Sc 45Ti 49V 51Cr 52Mn 55Fe 57Co 59Ni 60Cu 63Zn 66Ga 69Ge 74As 75Se 82Rb 85Sr 88Y 89Zr 90Nb 93Mo 98Ru 102Rh 103Pd 106Ag 107Cd 114In 115Sn 118Sb 121Te 130Cs 133Ba 138La 139Ce 140Pr 141Nd 146Eu 151Sm 152Gd 157Tb 159Dy 163Ho 165Er 167Tm 169Yb 174Lu 175Hf 180Ta 181W 184Pt 195Au 197Hg 202Tl 205Pb 208Bi 209Th 232U 238

Extrad/ng mL-1

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.

0.000 0.000 0.001 0.001 0.000 0.001 0.0010.000 0.000 0.000 0.000 0.000 0.000 0.0000.57 1.72 1.16 0.82 0.55 0.27 0.410.026 0.077 0.094 0.47 0.030 0.075 0.0730.073 0.061 0.066 0.28 0.030 0.044 0.0360.027 0.017 0.012 0.031 0.006 0.005 0.0080.033 0.36 0.34 0.63 0.025 0.31 0.0200.66 1.19 0.88 0.78 0.57 0.44 0.490.002 0.001 0.003 0.002 0.001 0.001 0.0010.03 0.07 0.03 0.02 0.04 0.05 0.010.15 0.096 0.17 0.087 0.065 0.062 0.0800.018 0.12 0.036 0.036 0.014 0.030 0.0240.050 0.064 0.060 0.24 0.054 0.065 0.0660.001 0.075 0.043 0.048 0.006 0.037 0.0500.004 0.003 0.015 0.005 0.003 0.001 0.0020.039 0.061 0.033 0.127 0.000 0.010 0.0050.24 1.33 0.12 0.32 0.04 0.05 0.020.21 0.11 0.14 0.18 0.062 0.11 0.0370.007 0.005 0.007 0.006 0.004 0.004 0.0030.000 0.002 0.001 0.001 0.001 0.002 0.0020.013 0.012 0.007 0.006 0.003 0.005 0.0030.028 0.006 0.048 0.004 0.022 0.022 0.0160.006 0.003 0.004 0.002 0.000 0.001 0.0010.003 0.003 0.004 0.021 0.001 0.002 0.0020.007 0.011 0.011 0.007 0.004 0.000 0.0000.001 0.002 0.001 0.001 0.003 0.001 0.0000.005 0.000 0.005 0.001 0.002 0.000 0.0011.08 5.82 41.7 1.09 0.60 0.97 1.120.002 0.000 0.004 0.000 0.000 0.000 0.0000.001 0.000 0.000 0.000 0.000 0.000 0.0000.008 0.006 0.044 0.008 0.009 0.006 0.0080.11 0.089 408.7 0.17 0.98 0.064 3.120.019 0.071 0.53 0.015 0.011 0.015 0.0160.001 0.001 0.002 0.003 0.000 0.000 0.0010.023 0.036 0.031 0.059 0.002 0.170 0.0430.003 0.005 0.010 0.010 0.001 0.008 0.0020.012 0.058 0.47 0.015 0.008 0.015 0.0100.000 0.000 0.001 0.000 0.000 0.000 0.0000.012 0.015 0.014 0.027 0.003 0.012 0.0050.005 0.048 0.078 0.29 0.005 0.005 0.0650.12 0.31 3.99 0.12 0.060 0.12 0.240.008 0.14 0.061 0.000 0.006 0.004 0.0000.000 0.058 4.05 0.000 0.000 0.12 0.0580.001 0.002 0.008 0.010 0.002 0.006 0.0000.001 0.000 0.010 0.010 0.001 0.000 0.0210.000 0.002 0.013 0.008 0.000 0.004 0.0000.005 0.005 0.020 0.002 0.000 0.005 0.0200.000 0.000 0.042 0.000 0.000 0.014 0.0000.000 0.011 0.000 0.000 0.000 0.004 0.0040.000 0.000 0.000 0.000 0.000 0.000 0.0000.002 0.002 0.006 0.002 0.000 0.002 0.0020.000 0.000 0.000 0.000 0.000 0.000 0.0040.000 0.000 0.004 0.004 0.004 0.000 0.0020.001 0.000 0.000 0.004 0.000 0.000 0.0000.000 0.000 0.000 0.000 0.000 0.000 0.0000.000 0.000 0.26 0.039 0.000 0.000 0.0000.001 0.007 0.010 0.002 0.000 0.002 0.0020.003 0.009 0.008 0.023 0.001 0.002 0.0020.000 0.000 2.4 0.014 0.006 0.002 0.0100.000 0.000 0.009 0.000 0.000 0.000 0.0000.002 0.011 0.098 0.065 0.034 0.018 0.0060.001 0.001 0.010 0.009 0.000 0.002 0.0000.000 0.019 0.057 0.038 0.000 0.000 0.0190.000 0.007 0.000 0.008 0.008 0.008 0.000

ng mL-1

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

60 elements

Impurities in nitric acid

Solid samples

Plug Safety Disk Seal Screw Cap

Liner Bomb Jacket Vessel Base Plate

Supporting Vessel Pressure vessel (TFM)

Microwave sample preparation systemMULTIWAVE (Anton Paar GmbH)

Acid digestion apparatus: microwave system

Element Mass number Measured value Certified value (mg/Kg) (mg/Kg)

La CePr NdSmEuGdTb DyHo ErTmYbLu

139140141146147151157159163165167169172175

8.999.881.216.760.9260.1421.150.08900.3050.05530.1700.01430.1120.0117

(9)(10)

(7)(1)

(0.17)(1)

Analytical results of peach leaves

Analytical results for REEs in NIES No.2 sediment sample

*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).

Element m/z Direct*1

(μg g-1) Column*1

(μg g-1)Column*2

(μg g-1)Column*3

(μg g-1)

Y 89 0.53±11.7 0.19 ±10.4 1.3 9.45La 139 0.04±8.06 0.25 ±7.21 0.90 7.06Ce 140 0.69±14.2 0.79 ±13.5 1.7 13.2Pr 141 0.03±1.66 0.07 ±1.63 0.22 1.69Nd 146 0.18±6.72 0.20 ±6.15 0.87 6.02Sm 147 0.03±1.30 0.02 ±1.17 0.16 1.19Eu 151 0.01±0.43 0.01 ±0.43 0.05 0.48Gd 157 0.03±1.27 0.01 ±1.25 0.23 1.21Tb 159 0.02±0.20 0.00 ±0.19 0.09 0.20Dy 163 0.03±1.31 0.04 ±1.21 0.17 1.23Ho 165 0.01±0.29 0.00 ±0.29 0.05 0.32Er 167 0.03±0.81 0.06 ±0.76 0.10 0.81Tm 169 0.01±0.11 0.01 ±0.10 0.03 0.12Yb 172 0.03±0.80 0.03 ±0.79 0.12 0.80Lu 175 0.01±0.11 0.01 ±0.11 0.03 0.10