Principles, Instrumentation and

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

Figure 8.4. Three types of spectroscopy

Atomic Spectroscopy

Different atomic spectroscopy systems

HCL
FLAME
MONOCHROMATOR
Figure 1. Simplified drawing of a Flame AA system.

HCL

GRAPHITE TUBE

MONOCHROMATOR

DETECTOR

DETECTOR

Figure 2. Simplified drawing of a Graphite Furnace AA system.

PLASMA

MONOCHROMATOR

DETECTOR

Figure 3. Simplified drawing of a basic ICP system.

Atomic Spectroscopy

Figure 6. Processes Occurring in Flame.

Atomic Spectroscopy

Atomic Spectroscopy

Flame and Flameless Atomic Absorption
Quantitation and Qualification of Atomic Spectroscopy

Beer-Lamberts Law is the basis for the quantificatitative determination

A = abc
A is the absorbance
a is the absorption coefficient
b is the length of the path light
c is the concentration of the absorbing species

Atomic Spectroscopy
Instruments for Atomic Spectroscopy
Flame and Flameless Atomic Absorption

Basic instrument components:

Atomic Spectroscopy

Flame and Flameless Atomic Absorption

Basic instrument components:

1. Light source: hollow cathode lamp (HCL)

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

Flame and Flameless Atomic Absorption

Basic instrument components:

2. Nebulizer and atomizer:

Atomic Spectroscopy

Flame and Flameless Atomic Absorption

Basic instrument components:

2. Monochromator
lenses
mirrors
gratings
prisms
.

Atomic Spectroscopy
Flame and Flameless Atomic Absorption

Basic instrument components:

3. Detector:

Figure 1. Detectors used in atomic spectroscopy traditional phototube, photomultiplier tube

Atomic Spectroscopy

Cold Vapor Atomic Absorption (CVAA) Spectroscopy for Hg

Free Hg atoms exist at room temperature, no requirement for heating
Sample may contain Hg0, Hg22+ or Hg2+
Reduction with a strong reducing agent (e.g. SnCl2 or NaBH4)

Atomic Spectroscopy

Hydride Generation Atomic Absorption (HGAA) Spectroscopy

AsH3 and SeH3 generated by reaction samples containing As and Se with
NaBH4
Allso used for Pb, Sn, Bi, Sb, Te, Ge, Se determination

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

Inductively Coupled Plasma Atomic Emission (ICP-OES)

Plasma torch inner tube contains the sample

aerosol and Ar support gas

Radio frequency generator produces a

magnetic field which sets up an oscillating
current in the ions and electrons of the support
gas (Ar)

Produces high temperatures (up to 10,000 K)

Figure 2. Inductively coupled plasma torch

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

Low detection limit is essential for trace analysis

Without low level capability sample pre-concentration is required

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.

scattering of the radiation source due to matrix impurities

e.g. Refractory oxides formed by Ti, Zr, and W due to atomization of high
concentration solutions. Use a blank.

Atomic Spectroscopy

Comparison of Interferences and Other Considerations

BACKGROUND CORRECTION METHODS
Continuum Deuterium Source Background Correction
common background correction technique in FAAS
significant at lower wavelength range (180nm-420nm)

Figure 1. D2 Lamp Background Correction Schematic

Atomic Spectroscopy

Comparison of Interferences and Other Considerations
BACKGROUND CORRECTION METHODS
Zeeman Background Correction
Mainly used in GFAAS

Figure 2. Zeeman Background Correction Schematic

Atomic Spectroscopy

Comparison of Interferences and Other Considerations
BACKGROUND CORRECTION METHODS
Zeeman Background Correction

Figure 3. Zeeman splitting of an atom in a magnetic field

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

Comparison of Interferences and Other Considerations

MATRIX INTERFERENCES
a physical interference and can either suppress or enhance absorbance
signal of analyte.
Causes:
1. Differences in viscosity and surface tension.
2. Preparation in different solvents.
3. Measurement at different temperatures.
4. High concentration of dissolved salts or acid (sample)
5. Presence of organic species.
6. Different aspiration and atomization rate in flame.

Atomic Spectroscopy

Comparison of Interferences and Other Considerations
Other Considerations
Sample throughput, cost, ease of use, availability of proven methodology

Single-element (FAAS and GFAA) vs. multi-element (ICP-OES/MS)

Single:
o Change of lamp
o Run time ~1 min

Multi:
o 10-40 elements per minute

2010 by DBS

Atomic Spectroscopy

Comparison of Interferences and Other Considerations

Other Considerations
Cost:

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

Summary of Atomic Spectroscopy

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.