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Techniques in Atomic
Absorption/Emission
Spectroscopy
JOSE G. INTANO, JR.
Overview
Introduction to the Principles of Atomic Spectroscopy
Instrumentation in Atomic Spectroscopy
Selection of the Proper Atomic Spectroscopic Technique
Atomic Spectroscopy
technique for determining the elemental composition of an
analyte by its electromagnetic or mass spectrum
atomic emission, atomic absorption, and atomic fluorescence
understanding of the atom and the atomic process involved
Atomic Spectroscopy
Atomic Spectroscopy
HCL
FLAME
MONOCHROMATOR
Figure 1. Simplified drawing of a Flame AA system.
HCL
GRAPHITE TUBE
MONOCHROMATOR
DETECTOR
DETECTOR
PLASMA
MONOCHROMATOR
DETECTOR
Atomic Spectroscopy
Atomic Spectroscopy
Atomic Spectroscopy
Flame and Flameless Atomic Absorption
Quantitation and Qualification of Atomic Spectroscopy
Atomic Spectroscopy
Instruments for Atomic Spectroscopy
Flame and Flameless Atomic Absorption
Atomic Spectroscopy
Figure 2-4. Hollow cathode lamp process, where Ar+ is a positively-charged Ar ion, Mo
is a sputtered, ground-state metal atom, M* is an excited-state metal atom, and is
emitted radiation at a wavelength characteristic for the sputtered metal.
Atomic Spectroscopy
Atomic Spectroscopy
Flame and Flameless Atomic Absorption
Atomic Spectroscopy
Flame and Flameless Atomic Absorption
Atomic Spectroscopy
Atomic Spectroscopy
Atomic Spectroscopy
Inductively Coupled Plasma Atomic Emission (ICP-OES)
2010 by DBS
Atomic Spectroscopy
Inductively Coupled Plasma Atomic Emission (ICP-OES)
Sample is nebulized and entrained in the flow of plasma support gas (Ar)
Source: http://www.cee.vt.edu/ewr/environmental/teach/smprimer/icpms/icpms.htm
Atomic Spectroscopy
Atomic Spectroscopy
Selection of the Proper Atomic Spectroscopic Techniques
Important factors:
o Detection limit
o Working range
o Sample throughput
o Cost
o Interferences
o Ease of use
o Availability of
proven methodology
Atomic Spectroscopy
Comparison of Detection Limits and Working Range
Figure 6. Typical detection limit ranges for the major atomic spectroscopy techniques.
Atomic Spectroscopy
Comparison of Detection Limits and Working Range
Ideal working range minimizes analytical effort and potential errors
Figure 7. Typical analytical working ranges for the major atomic spectroscopy techniques.
Atomic Spectroscopy
Comparison of Interferences and Other Considerations
Interference
4 types:
(i) spectral,
(ii) chemical,
(iii) ionization,
(iv) physical/matrix
Atomic Spectroscopy
Comparison of Interferences and Other Considerations
SPECTRAL INTERFERENCES
caused by radiation overlap of absorption line/emission line
e. g. Vanadium line is 3082.11 A and Aluminium is at 3082.15 A. Choose a
different Aluminium line at 3092.7 A.
Atomic Spectroscopy
Atomic Spectroscopy
Comparison of Interferences and Other Considerations
BACKGROUND CORRECTION METHODS
Zeeman Background Correction
Mainly used in GFAAS
Atomic Spectroscopy
Comparison of Interferences and Other Considerations
BACKGROUND CORRECTION METHODS
Zeeman Background Correction
Atomic Spectroscopy
Comparison of Interferences and Other Considerations
CHEMICAL INTERFERENCES
REFRACTORY COMPOUND FORMATION
compounds that cannot be broken down in flame
e.g. Ca signal is depressed due to formation of Ca sulfate or Ca phosphate
e.g. Mg signal is depressed in the presence of Al. Al forms heat stable
compound with Mg.
Atomic Spectroscopy
Comparison of Interferences and Other Considerations
CHEMICAL INTERFERENCES
SOLUTION FOR REFRACTORY COMPOUND FORMATION
Use of Hotter flame
Use of Releasing agents such as chlorides La and Sr.
Use of Protective agent such as EDTA and 8-Hydroxyquinolone
Atomic Spectroscopy
Comparison of Interferences and Other Considerations
IONIZATION INTERFERENCES
affects Group 1 and 2 elements (Ba, Ca, Sr, Na, K)
Solution: Use of Low Temperature Flame or Use of Ionization Buffer
Ionization buffer/suppressor/suppressant prevents analyte ionization
e.g. Addition of a 0.1% KCl soln to blank, standard, and sample.
Atomic Spectroscopy
Atomic Spectroscopy
Comparison of Interferences and Other Considerations
Other Considerations
Sample throughput, cost, ease of use, availability of proven methodology
Single:
o Change of lamp
o Run time ~1 min
Multi:
o 10-40 elements per minute
2010 by DBS
Atomic Spectroscopy
Atomic Spectroscopy
Comparison of Interferences and Other Considerations
Other Considerations
ICP-OES and ICP-MS are multi-element techniques favored when there is a
large number of samples and cost is not a concern
Atomic Spectroscopy
Comparison of Interferences and Other Considerations
Other Considerations
ICP-OES has become the dominant instrument for routine analysis of metals
Compared to FAAS:
o Lower interferences (due to higher temperatures)
o Spectra for most elements can be recorded simultaneously under the
same conditions
o Higher temperature allows compounds (e.g. metal oxides) to be
measured
o Determination of non metals (e.g. Cl, Br, I, S)
2010 by DBS
References
Csuros, M. and Csuros, C. (2002) Environmental Sampling and Analysis for Metals.
CRC press, Boca Raton, Fl.
Tatro, M.E. (2000) Optical Emission Inductively Coupled Plasma in Environmental
Analysis. Encyclopedia of Analytical Chemistry, Edited by Meyers, R.A. John Wiley
& Sons, West Sussex, UK.
http://delloyd.50megs.com/moreinfo/AAinterferences.html
http://lab-training.com/2013/05/08/background-correction-in-atomic-absorptionspectroscopy/
Thermo Elemental (2001). AAS, GFAAS, ICP or ICP-MS? Which technique should I
use? An elementary overview of elemental analysis.