KAA 502:

Atomic Spectroscopy

Atomic absorption spectrometry

Part II

ChM Dr. Noorfatimah Yahaya

Advanced Medical And Dental Institute
Universiti Sains Malaysia
noorfatimah@usm.my
High sensitivity sampling systems
Limitation to flame AA sensitivity
• The need for trace metal analyses
• Sampling process determines the process of creating ground state
atoms
• Nebulization process draws sample solution 3-8 mL/min limits the
sample introduction rate
• Premix burner design – wasteful of sample
• Sample introduced into the flame is resident in the light path for
only short time.
By improving the sampling efficiency and/or constraining analyte atoms to the
light path for a longer period of time, greater absorption can be achieved.
 The cold vapor mercury technique
• In this technique, mercury is chemically reduced to the free atomic state by
reacting the sample with strong reducing agent. For eg: stannous chloride or
sodium borohydride
• The volatile free mercury is transferred from the reaction flask by bubbling
air or argon.
• Mercury atoms are carried in the gas stream through tubing connected to
an absorption cell.
 The cold vapor mercury technique
• Mercury atoms pass into the sampling cell, measured, and absorbance rises
indicating the increasing concentration of mercury atoms in the light path.
• Highest absorbance observed will be taken as the analytical signal.
• The absorbance will rise until an eq is achieved in the system.
• This absorbance is used for quantitation.
• This technique can be automated using flow injection analysis.
 The cold vapor mercury technique
Advantages:
1. Improved sensitivity is achieved
2. 100% sampling efficiency
3. The detection limit for mercury by this cold vapor technique is
approximately 0.02 ug/L
4. Very large sample volume can be used

Limitation:
Limited to mercury
 Hydride generation technique
• Relatively similar to cold vapor mercury systems.
• Samples are reacted in an external system with a reducing agent (Eg: sodium
borohydride)
• Unlike the mercury technique, gaseous reaction products are not free
analyte atoms, but volatile hydrides. The molecular species are not capable of
causing AA. How to dissociate the hydride gas into free atoms?
• The hydride gas is dissociated in the heated cell into free atoms.
• Atomic absorption rises and falls as the atoms are created and then escape
from the absorption cell.
• Maximum absorbance, or peak height, or the integrated peak area is taken as
analytical signal.
Hydride generation technique
 Hydride generation technique
Advantages:
1. Elements determinable by this technique include As, Bi, Ge, Pb, Sb, Se, Sn,Te
2. LODs at sub ug/L can be achieved
3. Higher sampling efficiency
4. Also used to eliminate matrix interferences
5. Less expensive use manual operation, expensive and advanced uses flow injection
automated system
Limitation:
1. Restricted to elements listed above
2. Results depend very much on number of parameters
3. Formation of analyte hydrides is also suppressed by a number of common matrix
components, prone to chemical interference.
 Graphite furnace atomic absorption
• Most advanced and widely used high sensitivity sampling technique.
• In this techniques, a tube of graphite is located in the sample compartment
of AA spectrometer with the light path passing through it.
 Graphite furnace atomic absorption
Advantages
1. Detection limits in the ng/L range
2. Sample is atomized in a very short time, concentrating the available atoms in
the heated cell.
3. Small sample volumes compensated by long atom residence times in the
light path, provide LODs similar to those of much large samples.
4. Easily automated.
5. Wide applicability in variety of matrices.
Graphite furnace atomic
absorption (GFAAS)
 Graphite furnace applications

1. The term ‘characteristic mass’ is used to measure sensitivity in graphite

furnace rather than concentration.
2. Sensitivity of GF makes it obvious choice for trace metal analysis.
3. Possible to analyze complex matrices.
4. Microliter sample size.
 Components of the graphite furnace
system

1. ATOMIZER
2. THE POWER SUPPLY
3. THE PROGRAMMER
 The graphite furnace atomizer

A basic graphite furnace is comprised of:

1. Graphite tube
2. Electrical contacts
3. Enclosed water cooled housing
4. Insert purge gas control
Introduction to graphite furnace atomic
absorption

Longitudinally-heated graphite furnace atomizer.

 Introduction to graphite furnace atomic
absorption
• The electrical contacts at each end
of the tube must be cooled.
• As a result, temperature gradient
along the length of the tube. This
cause vaporized atoms and
molecules to condense as they
diffuse to the cooler tube end.
• This may contribute to interferences.
Transversely-heated Graphite Furnace
 The graphite furnace power supply and
programmer

The power supply and programmer perform the following functions:

1. Electrical power control
2. Temperature program control
3. Gas flow control
4. Spectrometer function control
 Summary of a graphite furnace analysis
1. Graphite furnace analysis consists of measuring and dispensing a known
volume of sample into the furnace.
2. Sample is subjected to a multi-step temperature program.
3. When the temperature increased to the point at which the atomization
occurs, the atomic absorption measurement is made.
4. Variables under operator control include the volume of sample placed into
the furnace and heating parameters for each step.
5. These parameters include:
a)Temperature: final temperature during step
b) Ramp time: time for temperature increase
c) Hold time: time for maintaining final temperature
d) Internal gas: gas type and flow rate
 Summary of a graphite furnace analysis

Steps in graphite furnace program:

1) Drying
2) Pyrolysis
3) Cool down (optional)
4) Atomization
5) Clean out
6) Cool down

Graphite furnace temperature program

 Sample size

• For very low concentrations, the maximum volume of analyte can be used,
while for higher concentrations, sample volume can be reduced
• Smaller sample size can be used where the sample is limited and
background absorption is excessively large.
• Convenient sample volume for most of analysis is 20 uL. Sample volumes up
to 100 uL can be used depending on the tube and sample.
• When larger volumes are required, for improved detection limits, multiple
injections can be used with drying and pyrolysis steps between each injection
to increase the effective sample size.
• Use of autosampler is strongly recommended.
 Measuring the graphite furnace AA signal

• Peak height measurement

• Peak area measurement
 Measuring the graphite furnace AA signal
Peak height measurement
• Peak height depend on the analyte
concentration in the sample, and is also
affected by other factors.
• It measures the maximum atom population
which occurred in the furnace during
atomization.
• If matrix components in the sample affect
the rate of atom formation, the maximum
atom population and the peak heigh are also
affected. Effect of matrix on peak height and area.
 Measuring the graphite furnace AA signal

Peak area measurement

• Provides capability to integrate absorbance during entire atomization
period, resulted in signal equal to integrated peak area, that is area under
the peak signal.

• If the temperature in the furnace is constant during the measurement

process, the peak area will represent a count of all atoms present in the
sample aliquot, regardless of whether the atoms were generated early or
late in the atomization process.
Measuring the graphite furnace AA signal
 Interferences and the graphite furnace

• Spectral interferences – resulting from light absorption by

molecules or by atoms other than analyte element
• Non-spectral interferences – affect the production or the
availability of analyte atoms which create the measured
atomic absorption
 Spectral interferences
Emission interference
• Occurs when ‘black body’ radiation (the intense light
emitted by the hot graphite tube or platform) reaches the
instrument’s light detector, the photomultiplier tube (PMT)

Black body radiation spectrum

 Spectral interferences
Background absorption

• Most severe spectral interference

• Non-specific light at the analyte wavelength caused by
matrix components
• Background absorption is broad band, covering tens or
hundreds of nm.
 Background reduction techniques

• During pyrolysis, matrix components are volatilized from the

sample.
• If this 100% efficient, if all the matrix could be driven off during
pyrolysis, thus there will be no background absorption.
• However, analyte must not be lost during pyrolysis.
• Thus, pyrolysis temperature and the effectiveness of this
pyrolysis step in matrix removal limited by temperature which
analyte atoms are lost.
 Matrix modification

• A reagent called ‘matrix modifier’ is added to the sample.

• Is used to generate ‘increased matrix volatility’ or
‘decreased analyte volatility’.
Matrix modification
 Background reduction techniques

• Varying the sample volume is also effective, when

sensitivity is not limited.
• Modification of atomization step.
• Use different absorption wavelength where one exists and
sensitivity requirements will allow.
 Background reduction techniques

Automatic instrumental background correction

1. Continuum source
2. Zeeman effect

Interpolated Background correction

[AA] = [AA+BG] – [BG]
 Non-spectral interferences

• Result when diverse components in the sample matrix inhibit

the formation of free analyte atoms.
Mº + Xº MX
Mº = free analyte atoms
Xº = diverse matrix component atoms
 Non-spectral interferences

• Method of standard addition (consideration of matrix effects)

• The graphite furnace tube surface
• The L’vov platform
• Matrix modification
• Maximum power atomization
• Peak area measurement
 Non-spectral interferences
Graphite furnace tube surface
• Nature of graphite surface – carbide formation. Number of elements tend to
form nonvolatile carbides by interaction with graphite surface.
Solution?
More dense graphite surface is used.
Pyrolytically coated graphite tube offers a more dense, impermeable surface
than uncoated tube.
Uncoated tubes – porous, allowing sample solution to soak into structure of
graphite during drying. Atomic vapor contact with hot graphite tube wall at
atomization interact with porous surface more readily to produce analyte
carbides, thus decreasing the population of free atom.
Pyrolytic coating graphite tube also increase lifetime of the tube.
 Non-spectral interferences
The L’vov platform

• The ultimate goal to control nonspectral interference

- To delay the appearance of analyte in the furnace
atmosphere until the furnace has reached the actual
temperature set for the atomization step of the furnace
program
Non-spectral interferences
The L’vov platform
 Non-spectral interferences
Matrix modification

• For enhancing the ability to remove matrix materials from

samples, during pretreatment step.
• By adding matrix modifier which stabilizes the analyte, the
appearance temperature, for example, the temperature at which
the analyte absorption signal first appears, will increases.
• This delays the release of the analyte into the furnace.
 Non-spectral interferences
Maximum power atomization

• Rapid heating, or maximum power atomization, increases

the temperature of the tube atmosphere more rapidly, and
analyte is volatilized into a hotter environment.
• As a result, more energy is available to atomize the sample
resulting in an increase in free atoms and enhanced
sensitivity.
 Non-spectral interferences
Peak area measurement

• Depends not the maximum concentration of atoms, but is

a measure of the total number of atoms passing through
the light path during the atomization process.