INTRODUCTION

Atomic absorption spectroscopy (AAS) currently is the

most widely used of atomic spectroscopic techniques. AAS
is a quantitative method of elemental analysis that is
applicable to many metals and a few nonmetals. Atomic
Absorption Spectrophotometry is widely applied for the
analysis of samples, such as agriculture , clinical and
biochemistry, minerals, food , drugs , environmental
species and others . AAS deals with atoms , Fe2+ and Fe3+
will not be distinguished. ........................................
 PRINCIPLES OF AAS
In AA spectroscopy, as in all atomic spectroscopic methods,
the sample must be converted into an atomic vapor by a
process known as atomization. In this process, the sample is
volatilized and decomposed to produce atoms and perhaps
some ions in the gas phase. Several methods are used to
atomize samples. The two most important of these for AA
spectroscopy are flame and furnace atomization .
The radiation of a line source of the analyte , typically a hollow
cathode lamp, is directed through the flame containing the
gaseous analyte atoms . These ground state atoms absorb some
of the source radiation . The extend of this absorption will be
proportional to the number of the ground state atoms in the
flame i.e. the analyte’s concentration .
PRINCIPLES OFAAS … cont’d
 PRINCIPLES OF AAS … cont’d
Part of the energy of the incident radiation Po is absorbed. The
transmitted radiation P is given by
P = Poe - (ab) , A = log P0 / P = abc = - log T ( see Beer’s law unit 4 )
where a is the absorption coefficient of the analyte element and b is the
horizontal path length of the radiation through the flame and the others
as in Beer’s law. Atomic absorption is determined by the difference in
radiant power of the resonance line in the presence P and absence P0 of
analyte atoms in the flame. The width of the line emitted by the light
source must be narrower than the width of the absorption line of the
analyte in the flame.
 PRINCIPLES OF AAS … cont’d
Solution samples are usually brought into the flame by means of a
sprayer or nebulizer as mentioned in unit 7 and only 5% of the ground
state atoms are excited and used by FAES and the remaining 95% will
be used by AAS .
The use of a flame limits the excitation temperature reached by a
sample to a maximum of approximately 2600oC .For many
elements this is not a problem . Compounds of the alkali metals,
for example, and many of the heavy metals such as lead or
cadmium and transition metals like manganese or nickel are all
atomized with good efficiency in the flame , with typical detection
limits in the sub-ppm range.
 PRINCIPLES OF AAS … cont’d
However, there are a number of
refractory elements like V, Zr,
Mo and B which do not perform
well with a flame source. This is
because the maximum
temperature reached in the flame,
is insufficient to break down
compounds of these elements. As
a result, flame AAS sensitivity
for these elements is not as good
as other elemental analysis
techniques .
 PRINCIPLES OF AAS … cont’d
Evaporation
+ - + -
M X M X MX
Solution Mist Solid
Vapourisation

Thermal M (gas) Dissociation

*
M (g) MX
X (gas)
excitation Gas
Flame
emission Absorption of radiant
Measure for atomic
energy h
h absorption spectroscopy
Measure for
flame emission *
spectroscopy M (g)
o
Re-emit radiation at 90 Measure for atomic
(Atomic fluorescence) fluorescence spectroscopy

Process by which gaseous atoms are produced in flames

8
 INSTRUMENTATION

Every AA spectrometer must have the following components :

1- Radiation Source : which emits the sharp atomic lines of the
element to be determined is required ( line source ) . The most
widely used source is the hollow cathode lamp. These lamps are
designed to emit the atomic spectrum of the analyte .

a) Hollow Cathode Lamp ( HCL ) :

This lamp consists of a cylindrical metallic cathode (made from
the same element being analyzed) and tungsten anode sealed in
INSTRUMENTATION … cont’d

10
INSTRUMENTATION …. continued

a glass tube containing neon

or argon. When high
voltage is applied between
the anode and cathode, the
filler gas is ionized and
positive ions are accelerated
toward the cathode.
 Hollow Cathode Lamp (Cont’d)
They strike the cathode with enough energy to “sputter” metal atoms
from the cathode surface into the gas phase. The free atoms are
excited by collisions with high-energy electrons and then emit
photons to return to the ground state. This radiation has the same
frequency as that absorbed by analyte atoms in the flame .
(1) Ionization of the filler gas:
Ne + e- = Ne+ + 2e-
(2) Sputtering of the cathode element (M):
M(s) + Ne+ = M(g) + Ne
(3) Excitation of the cathode element (M)
M(g) + Ne+ = M*(g) + Ne
(4) Emission of radiation
M*(g)  (M(g) + h
Hollow Cathode Lamp (Cont’d)

The main disadvantage of HCL is that each element has it’s own
unique lamp because the cathode is made from the analyte . This can be
also considered an advantage due to less spectral interferences .

The linewidth from the HCL is

relatively narrow (compared to
linewidths of atoms in the flame or
furnace i.e. absorption line ) because
of low pressure and lower temperature
in lamp (less Doppler broadening).
Hollow Cathode Lamp (Cont’d) Atomic absorption of a narrow
emission line from a source.

Atomic absorption of a narrow

emission line from a source. The
source lines in (a) are very narrow.
One line is isolated by a
monochromator. The line is
absorbed by the broader
absorption line of the analyte in
the flame (b) resulting in
reduction (c) of the source
radiation.
 Doppler broadening :
The linewidth of the source must be narrower than the linewidth of
the atomic absorption for Beer’s law to be obeyed .
The line bandwedth of radiation emitted or absorbed by a fast
moving atom decreases or increases as a result of the rapid motion
of the atoms . This is called Dopplerbroadening .

Collisional broadening :
Collisional , broadening arises from collisions of emitting or absorbing
species with other atoms or ions in the heated medium which leads to
deactivation of the excited state and thus broadening the spectral lines .
b- Electrodeless Discharge Lamps (EDL) :

Constructed from a sealed quartz tube containing an inert gas such as

argon and a small quantity of the metal analyte (or its salt).The lamp
does not contain an electrode but instead is energized by a field of
radio-frequency or microwave radiation. Radiant intensities greater
than HCL.The main drawbacks of EDL are their performance does
not appear to be as reliable as that of the HCL lamps (signal
instability) and they are only commercially available for some
elements.
C- Lasers:
They are intense enough to excite atoms to higher energy levels.
Why we don’t use continuum source in AAS ?

Atomic absorption bandwidths are so narrow, with an inherent

linewidth of 0.0001 nm. Due to Doppler effect and collisional
broadening,linewidths of atoms in a flame are typically 0.001 –
0.01 nm.The narrowest band of wavelengths that can be isolated
from a continuum with best monochromator is about 0.5 nm.
Therefore, we require a source having a linewidth of less than
0.01 nm . At a proper conditions, the bandwidth of emitted
radiation with hollow cathode lamp is even narrower than the
atomic absorption bandwidth.
 INSTRUMENTATION …cont’d
2- Nebulizer to transfer analyte solution into the flame atomizer.
By breaking the sample solution into small droplets. Most
(>99%) are collected as waste , only small fraction reach the
flame . The flame path is about 10 – 12 cm in AAS to
increase the absorption and consequently the sensitivity while
in FAES it is rounded .

premix burner
 INSTRUMENTATION …cont’d

3- Atomizer : to convert the analyte to ground state free atoms .

For this purpose we use either flame or graphite furnace or tube.

(a) Flame atomizer ( FAAS ) : In most cases air or nitrous

oxide – acetylene flames are used . Different flames can be
achieved using different mixtures of gases, depending on the
desired temperature and burning velocity. Some elements can
only be converted to atoms at high temperatures. Some metals
form oxides that do not re-dissociate into atoms. To inhibit their
formation, conditions of the flame may be modified to achieve a
reducing, non-oxidizing flame.
 INSTRUMENTATION …cont’d

Small changes in flame temperature have little effect in atomic

absorption but have significant effects in atomic emission
spectroscopy . The flame has been previously discussed in unit 7.
Other atomizers are graphite furnace and hydride generation
system will be discussed later .
ADVANTAGES AND DISADVANTAGES OF FLAME AAS
Advantages :
1- equipment relatively cheap .
2- easy to use (training easy compared to furnace) .
3- good precision .
4- cheap to run .
Disadvantages :
1- lack of sensitivity (compared to furnace) .
2- problems with refractory elements .
3- require large sample size .
4- sample must be in solution .
(b) Electrothermal Atomzer ( ETA ) :
The sample is contained in a heated, graphite
furnace.The furnace is heated by passing an electrical
current through it (thus, it is electro thermal). To
prevent oxidation of the furnace, it is sheathed in gas
(Ar usually) .There is no nebulization ,the sample is
introduced as a drop (usually 5-20 µL) or solid (rare).
The furnace goes through several steps .
- Drying (usually just above 110 deg. C.)
- Ashing (up to 1000 deg. C)
- Atomization (Up to 2000-3000 C)
Waste is blown out with a blast of Ar.
b) Electrothermal Atomzer : … cont’d

The light from the source (HCL) passes through the furnace
and absorption during the atomization step is recorded over
several seconds. This makes ETA more sensitive than flame
for most elements.
 Graphite cap Graphite holder

Sample
Cooling block inlet
Aperture
plate socket Seal
シール Graphite tube

Graphite tube

Eject arm Spring Fixing knob

 Easy switching between flame and furnace
Flame -> Furnace: All that is involved is to remove the burner
head, place the furnace unit, and fix it with the screw. No tools
are required.

Remove the burner head.

Fit the furnace.

Fit the burner head.

Remove the furnace.

Advantages and disadvantages of electrothermal atomization
Advantages :
1- Very sensitive for many elements (10-14 g compared to
10-10 g for flame ) .
2- Small sample size .
3- Less chemical interferences due to very high temperature .
4- Direct analysis of solid samples ( rare ) .
5- less physical interferences because there is no nebulization .
Advantages and disadvantages of electrothermal
atomization .. Cont’d
Disadvantages
1- poor precision 5 – 10% compared to 1% for the flame .
2- high ionization interferences due to high temperature.
2- Expensive to purchase and run (argon, tubes) .
3- Requires background correction .
4- Requires a high degree of operator skill (compared to
flame AAS) .
5- The linearity range is relatively narrow .
 NSTRUMENTATION …. Cont’d

4- Monochromators :
The operation and sensitivity of the atomic absorption spectrometer
depends on the spectral band width of the resonance line emitted by
the line source (the hollow cathode lamp).The function of the
monochromator is to isolate the resonance line from other lines close
to it in the source spectrum and from background continua and
molecular emissions originating in the flame . Hollow cathode lamps
emit a number of lines, in the case of multi-element lamps, the
number can be quite large and it is necessary to isolate the line of
interest.A prism or a grating can be used for this purpose . These also
have been previously discussed in unit 3 .
 INSTRUMENTATION …. Cont’d

5- The detector is normally a

photomultiplier tube, which produces
an electrical current which is amplified Light Photocathode
and processed by the instrument e-
electronics to produce a signal which Dynode
can be further processed to produce an Dynode
instrument readout directly in Dynode
concentration units .
The photomultiplier tube has been Current
investigated in unit 3 .
Therefor we will limit our
investigation to the components that
have not been discussed before .
AAS INTERFERENCES

What do we mean with interference ?

Any factor that affects the ground state population of the
analyte element in the atomizer . In other words any
increase or decrease in the signal obtained from the analyte
as a result of the presence of some other component in the
sample or in the atomizer .
Also factor that may affect the ability of the instrument to read
this parameter . There are five important types of
interferences :
A) Spectral interferences:
This refers to overlap of analyte line with lines originating from
other elements in the sample or with lines or bands due to the
flame or furnace .e.g. flame background emission . The
presence of Al and V in the same solution will interfere with
each other :
308.216 nm Al
308.211 nm V
Solution:
Use a different line (which may be less sensitive) or
Separate these elements .

33
Background correction
Background signal arises from absorption, emission, or scatter by
everything in the sample besides analyte ((the matrix), as well as
by the flame, the furnace, or the plasma.
Background correction methods :
1- Beam chopping
In order to eliminate the unwanted emissions from the atomizer,
the light source is modulated by a chopper which is located
between the hollow cathode lamp and the atomizer . The amplifier
which modifies the signal from the photomultiplier is tuned in to
the same frequency .
(Alternatively, the hollow cathode lamp may be modulated by
applying an AC voltage at say 50 Hz .
A beam chopper for subtracting the signal
due to flame background emission. Resulting
square-wave signal.
 2- Using continuum source : The difference between absorbance
measured with the hollow cathode and absorbance measured with
the continuum source is the absorbance due to analyte.
B ) Chemical Interferences :
Elements that form very stable compounds are said to be
refractory because they are not completely atomized at the
temperature of the flame or furnace.
Solution
Use a higher flame temperature (nitrous oxide/acetylene)
Use a release agent
Use protective chelation
For example in the determination of calcium in the presence of
sulfate or phosphate , the ground state calcium atoms will be
reduced due to formation of thermally stable difficult to atomize
compounds :
3Ca2+ + 2PO43- = Ca3(PO4)2
(stable compound)
This can be solved by either adding a release agent to free Ca from
the stable compound e.g. LaCl3
2LaCl3 + Ca3(PO4)2 = 3CaCl2 + 2La(PO4)
CaCl2 readily dissociates
Or by adding chelating agent such as EDTA :
Ca3(PO4)2 + 3EDTA = 3Ca(EDTA) + 2PO43-
Ca(EDTA) dissociates readily .
38
C ) Ionization Interferences :
M(g)  M+(g) + e-
A problem in the analysis of very low excitation potential metals
such as alkali metal and particularly at higher temperatures.
These metals are most extensively ionized in flames.
At 2450 K , sodium is 5% ionized.
Potassium is 33% ionized under the same conditions.
Ionized atoms emit radiation different from the radiation emitted
by the excited atoms . Therefore the analytical signal from the
ground state atoms ( atomic absorption ) is reduced.
To reduce the ionization interferences we add an ionization
suppressor which is easily ionized element such as Cs e.g. adding
Cs when analysing Na or K. Cs is more readily ionized than either Na
or K.This produces a high concentration of electrons in the flame and
reduce the ionization of Na or K according to Le Châtelier's principle.
[M  ][e - ]
K
[M ]
[M  ][e - ]
[M ] 
K

Ionization interferences can be minimized by lowering the atomizer’s

temperature ..
D ) Self-absorption Interferences :
It is a process observed when a HCL lamp is operated at high
currents where sputtering of a large number of atoms takes place.
Most atoms do not get enough excitation energy in this process
and thus absorb emitted radiation from other excited atoms within
the lamp causing lower sensitivity and negative deviation in the
calibration curve with the increasing concentration .This can be
overcome by using only the lamp current suitable to the analyte .
Also the ground state atoms in the outside cool parts of the flame
can absorb the emission from the excited atoms in the hot meddle
of the flame for the same elements resulting in reducing intensity
in FAES and also FAAS . This can be reduced by reducing the
length of the flame as in the following figure and avoiding high
concentration .
E) Physical interference

Spray efficiency fluctuations due to difference in physical properties

e.g. viscosity , density and surface tension between the standards and
sample . In other words The amount of sample reaching the flame
and the droplet’s size are dependent on the physical properties of the
solution .
To avoid differences in the amount of sample and standard reaching
the flame, it is necessary that the physical properties of both be
matched as closely as possible . Example analysis of blood .
The increased signal In presence of ethanol is due to lower surface
tension in presence of ethanol which produces smaller droplets.
SENSITIVITY :
the concentration of an element which will reduce the
transmission by 1% .

 P   99 
Abs  - log 0   - log   0.00436
P   100 
This corresponds to an absorption of 0.00436

DETECTION LIMIT :
The concentration of an element that gives a signal
equal to three times the blank signal .
APPLICATIONS
A calibration curve is used to determine the unknown
concentration of an element in a solution. The instrument is
calibrated using several solutions of known concentrations.
The absorbance of each known solution is measured and
then a calibration curve of concentration vs absorbance is
plotted.
The sample solution is fed into the instrument, and the
absorbance of the element in this solution is measured .The
unknown concentration of the element is then founded from
the calibration curve
APPLICATIONS …. Cont’d
Standard addition method can also be used instead of the
calibration method if necessary .
There are many applications for atomic absorption:
- Clinical analysis : Analyzing metals in biological fluids such as
blood and urine.
- Environmental analysis : Monitoring our environment – e g finding
out the levels of various elements in rivers, seawater, drinking water,
air, soil , and petrol.
- Pharmaceuticals. Analysis of drugs .
- manufacturing processes, minute quantities of a catalyst used in
the process (usually a metal) are sometimes present in the final
product. By using AAS the amount of catalyst present can be
determined. Analysis of trace elements in food and in cosmetics .
- Industry : Many raw materials are examined and AAS is widely
used to check that the major elements are present and that toxic
impurities are lower than specified – e g in concrete, where calcium
is a major constituent,
the lead level should be low because it is toxic . By using AAS the
amount of metals such as gold in rocks can be determined to see
whether it is worth mining the rocks to extract the gold .
AAS vs ICP
The basic difference between the two techniques is that AAS
relies upon an atomic absorption process while ICP is an
atomic/ionic emission spectroscopic technique. The next
essential difference is the means by which the atomic or ionic
species are generated. A combustion flame or graphite furnace is
typically used for AAS while ICP-AES uses a plasma.
The typical maximum temperature for an air/acetylene flame is
2300 °C while for nitrous oxide acetylene, it is 2 900 °C.
Temperatures as high as 10 000 K can be reached in an argon
plasma.
Non metals such as sulfur, nitrogen, carbon, and the halogens
(e.g. I, Cl, Br) can only be determined by ICP.
Detection limits
‫على الراغبين في االستماع الى محاضرة عن موضوع هذه الوحدة باللغة العربية‬
: ‫الضغط على كل من الروابط التالية‬
Part 31 : Atomic Absorption Spectrometry
Part 32 : Atomic Absorption Spectrometry
Part 33 : Atomic Absorption Spectrometry
Part 34 : Atomic Absorption Spectrometry
Part 35 : Atomic Absorption Spectrometry
Part 36 : Atomic Absorption Spectrometry
Part 37 : Atomic Absorption Spectrometry
Part 38 : Atomic Absorption Spectrometry
1 ‫محاضرة باللغة االنجليزية‬
2 ‫محاضرة باللغة االنجليزية‬