ATOMIC

SPECROSCOPY (AS)

Atomic Absorption Spectroscopy

Flame Atomic Emission Spectroscopy

ICP Atomic Emission Spectroscopy

 1
BASIC PRINCIPLE
ATOMIC ABSORPTION SPECTROSCOPY (AAS) is an

analytical technique that measures the concentrations of

elements. It makes use of the absorption of light

by these elements in order to measure their

concentration .
 - Atomic-absorption spectroscopy quantifies
the absorption of ground state atoms in
the gaseous state .
- The atoms absorb ultraviolet or visible light
and make transitions to higher electronic
energy levels . The analyte concentration
is determined from the amount of
absorption.
- Concentration measurements are usually
determined from a working curve after
calibrating the instrument with standards
of known concentration.

- Atomic absorption is a very common

technique for detecting metals and
metalloids in environmental samples.
Elements detectable by atomic absorption are highlighted in pink in this

periodic table
 The Atomic Absorption
Spectrometer
 Atomic absorption spectrometers have 4
principal components
1 - A light source ( usually a hollow cathode
lamp )
2 – An atom cell ( atomizer )
3 - A monochromator
4 - A detector , and read out device .
 Schematic Diagram of an Atomic
Absorption Spectrometer

Detector and
Light source atomizer
(hollow cathode Lamp ) monochromator readout device
 Atomic Absorption
Spectrophotometer
 1 – Light Source
 The light source is usually a hollow cathode
lamp of the element that is being measured . It
contains a tungsten anode and a hollow
cylindrical cathode made of the element to be
determined. These are sealed in a glass tube
filled with an inert gas (neon or argon ) . Each
element has its own unique lamp which must be
used for that analysis .
Hollow Cathode Lamp
Quartz window

Pyrex body

cathode

Anode

Cathode

Anode
 How it works

Applying a potential difference between the

anode and the cathode leads to the ionization of
some gas atoms .

These gaseous ions bombard the cathode and

eject metal atoms from the cathode in a process
called sputtering. Some sputtered atoms are in
excited states and emit radiation characteristic
of the metal as they fall back to the ground
state .
Scheme of a hollow cathode lamp
The shape of the cathode which is hollow
cylindrical concentrates the emitted radiation
into a beam which passes through a quartz
window all the way to the vaporized sample.

Since atoms of different elements absorb

characteristic wavelengths of light. Analyzing a
sample to see if it contains a particular element
means using light from that element .
For example with lead, a lamp containing lead
emits light from excited lead atoms that produce
the right mix of wavelengths to be absorbed by
any lead atoms from the sample .

A beam of the electromagnetic radiation emitted

from excited lead atoms is passed through the
vaporized sample. Some of the radiation is
absorbed by the lead atoms in the sample. The
greater the number of atoms there is in the
vapor , the more radiation is absorbed .
 2 – Atomizer

Elements to be analyzed needs to be in

atomic sate

Atomization is separation of particles into

individual molecules and breaking molecules
into atoms .This is done by exposing the
analyte to high temperatures in a flame or
graphite furnace .
The role of the atom cell is to primarily
dissolvate a liquid sample and then the solid
particles are vaporized into their free gaseous
ground state form . In this form atoms will be
available to absorb radiation emitted from the
light source and thus generate a measurable
signal proportional to concentration .

There are two types of atomization : Flame and

Graphite furnace atomization .

 Flame
 Flame AA can only analyze solutions , where
it uses a slot type burner to increase the
path length, and therefore to increase the total
absorbance .

Sample solutions are usually

introduced into a nebuliser by being sucked up a
capillary tube .In the nebuliser the sample is
dispersed into tiny droplets , which can be
readily broken down in the flame.
 FLAME ATOMIZERS

 Used in all Atomic Spectroscopic techniques

 Converts analyte into free atoms in the form of vapor phase

free atoms

 Heat is required

 Routes for sample introduction

Various flame atomization techniques
Types of Flames Used in Atomic Spectroscopy
Processes that take place in flame
 Effect of flame temperature on excited state population

# atoms in
Excited state
Boltz
mann
const Temperature
# atoms in
Ground state Energy
ant
difference

Statistical
factor
For Zn: N*/No = 10-15%
 Thus 99.998% of Na atoms are in the
ground state
 Atomic emission uses Excited atoms
 Atomic absorption uses Ground state atoms
Effect of flame temperature on excited state population
ATOMIZATION DEVICES

ATOMIZATION :
A process of forming free atoms by heat
Atomizers are devices that carry out atomization:

Continuous
Non-continuous

Continuous: (Constant temperature with time)

Flame
Plasma

Non-Continuous: (temperature varies with time)

Electrothermal
Spark discharge
SAMPLE INTRODUCTION SYSTEMS

In continuous atomizers sample is constantly introduced in

form of droplets, dry aerosol, vapor

Nebulizer : A device for converting the solution into fine

spray or droplets

Continuous sample introduction is used with continuous

nebulizers in which a steady state atomic population is
produced. Sample is introduced in fixed or discrete amounts.

Discontinuous samplers are used with continuous atomizers

1- Discrete samples are introduced into atomizers in many
ways:
Electrothermal atomizers
a syringe is used
a transient signal is produced as temperature changes
with time and sample is consumed

2- Indirect insertion (Probe)

sample is introduced into a probe (carbon rod) and
mechanically moved into the atomization region
vapor cloud is transient because sample introduced is
limited
3-Flow Injection

The analyte is introduced into the carrier stream into a

nebulizer as mist

4-Hydride Generation

the volatile sample is stripped from the analyte

solution and carried out by a gas into the atomizer.
This strip is followed by chemically converting the
analyte to hydride vapor form.
5- With Arc Spark
Solids are employed

6- Laser Microbe Technique

A beam of laser is directed onto a small solid sample, gets
vaporized, atomized by relative heating. Either sample is
probed by encoding system or vapor produced is swept
into a second absorption or fluorescence
 Nebulization gas is always compressed, usually acts as the
oxidant; it is oxygen (O2) in flame and argon (Ar) in plasma

 Nebulization chambers produce smaller droplets and remove

or drain larger droplets called aerosol modifiers

 Aspiration rate is proportional to compressed gas pressure.

The pressure drops through capillary, here 1/4 capillary
diameters are recommended. This is inversely proportional to
viscocity of the solution

 Peristaltic and/or syringe pumps could be used

 Oxidant and fuel are usually brought into the nebulization
chamber through a separate port. They mix and pass the burner
head called premixed burner system.

 Add organic solvents to reduce the size of the drop

The Atomic Absorption Spectrometer
Sample Introduction System

Nebuliser

Capillary

Solution
 The fine mist of droplets is mixed with fuel
( acetylene ) , and oxidant ( nitrous oxide)
and burned.

The flame temperature is important

because it influences the distribution of
atoms. It can be manipulated by
oxidant and fuel ratio.
 Graphite Furnace
 The graphite furnace has several advantages over a flame. First it
accept solutions, slurries, or solid samples.

 Second it is a much more efficient atomizer than a flame and it can

directly accept very small absolute quantities of sample. It also
provides a reducing environment for easily oxidized elements.
Samples are placed directly in the graphite furnace and the furnace
is electrically heated in several steps to dry the sample, ash organic
matter, and vaporize the analyte atoms.

 It accommodates smaller samples but it’s a difficult operation,

because the high energy that is provided to atomize the sample
particles into ground state atoms might excite the atomized particles
into a higher energy level and thus lowering the precision .
 3- Monochromators

This is a very important part in an AA spectrometer. It is

used to separate out all of the thousands of lines.
Without a good monochromator, detection limits are
severely compromised.

A monochromator is used to select the specific

wavelength of light which is absorbed by the sample,
and to exclude other wavelengths. The selection of the
specific light allows the determination of the selected
element in the presence of others.
 4 - Detector and
Read out Device
The light selected by the monochromator is
directed onto a detector that is typically a
photomultiplier tube , whose function is to
convert the light signal into an electrical signal
proportional to the light intensity.

The processing of electrical signal is fulfilled by a

signal amplifier . The signal could be displayed
for readout , or further fed into a data station
for printout by the requested format.
 Calibration Curve
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 calculated
from the calibration curve
 Calibration Curve
A 1.0 -
b 0.9 -
S 0.8 - .
o 0.7 - .
r 0.6 - .
b 0.5 - . .
a 0.4 - .
n 0.3 - .
c 0.2 -
e 0.1 -

10 20 30 40 50 60 70 80 90 100
Concentration ( g/ml )
 Determining concentration from
Calibration Curve

A 1.0 - absorbance measured

b 0.9 -
S 0.8 - .
o 0.7 - .
r 0.6 - .
b 0.5 - . .
a 0.4 - .
n 0.3 - . concentration calculated
c 0.2 -
e 0.1 -

10 20 30 40 50 60 70 80 90 100
Concentration ( mg/l )
 Interferences
The concentration of the analyte element is
considered to be proportional to the ground
state atom population in the flame ,any factor
that affects the ground state atom population
can be classified as an interference .

Factors that may affect the ability of the

instrument to read this parameter can also be
classified as an interference .
 The different interferences that are encountered in atomic absorption
spectroscopy are :

- Absorption of Source Radiation : Element other than the one of

interest may absorb the wavelength being used.

- Ionization Interference : the formation of ions rather than

atoms causes lower absorption of radiation .This problem is
overcome by adding ionization suppressors.

- Self Absorption : the atoms of the same kind that are absorbing
radiation will absorb more at the center of the line than at the
wings ,and thus resulting in the change of shape of the line as
well as its intensity .
- Back ground Absorption of Source Radiation :
This is caused by the presence of a particle from
incomplete atomization .This problem is overcome by
increasing the flame temperature .

- Transport Interference :
Rate of aspiration, nebulization, or transport of the
sample ( e g viscosity, surface tension, vapor
pressure , and density ) .
 2
Atomic Emission
Spectroscopy
Atomic emission spectroscopy is also an analytical
technique that is used to measure the
concentrations of elements in samples .

It uses quantitative measurement of the emission

from excited atoms to determine analyte
concentration .
The analyte atoms are promoted to a higher energy
level by the sufficient energy that is provided by the
high temperature of the atomization sources .

The excited atoms decay back to lower levels by

emitting light . Emissions are passed through
monochromators or filters prior to detection by
photomultiplier tubes.
The instrumentation of atomic emission
spectroscopy is the same as that of atomic
absorption ,but without the presence of a
radiation source .

In atomic Emission the sample is atomized

and the analyte atoms are excited to
higher energy levels all in the atomizer .
Schematic Diagram of an Atomic
Emission spectrometer
The source of energy in Atomic Emission could be a flame
like the one used in atomic absorption ,or an inductively
coupled plasma ( ICP ) .

- The flame ( 1700 – 3150 oC ) is most useful for

elements with relatively low excitation energies like
sodium potassium and calcium .

- The ICP ( 6000 – 8000 oC) has a very high

temperature and is useful for elements of high
excitation energies .
 INDUCTIVELY COUPLED PLASMA
(ICP)

Plasma is a type of electrical discharge

Plasma is any type of matter that contains an appreciable 

amount of less than 1% of electrons and +ve ions in equal
numbers + atoms + neutral molecules
 Plasma has 2 characteristics:
i- can conduct electricity
II- affected by magnetic fields

Plasma is highly energetic ionized gases usually inert, 

recently reactive oxygen is used.

ICP is the state-of-the-art plasma

Other plasmas include direct current plasma (DCP) and 

microwave induced plasma (MIP)
ADVANTAGES OF THE ICP

High degree of selectivity

Ability to overcome depressive interference effects

Capable of exciting several elements not excitable by 

ordinary flames

Higher sensitive than Flame Photometry

Simpler to operate than Arc Spark methods

Higher degree of sensitivity than Arc Spark 

Lacks electrodes which gives freedom from contamination 

and extremely low background.
GENERAL CHARACTERISTICS OF THE ICP

Up to 70 elements can be analyzed at concentrations below 1

ppm

(Fig 1))
THE ICP DISCHARGE
(Fig 2)
The argon gas is directed through a torch consists of 3 
concentric tubes made of quartz

A copper coil called the Load Coil surrounds the top 

end of the torch and connected to a Radio Frequency
Generator (RF)

When RF power (700 – 1500 Watts) is applied to the 

load coil, an alternating current moves back and forth
within the coil or oscillates at a rate corresponding to the
frequency of the generator (27 – 40 MHz). This RF
oscillation causes the RF electric and magnetic fields to
be set up in the area at the top of the torch.
 With Argon gas being swirled through the torch, a spark is 
applied to the gas causing some electrons to strip out from their
Argon atoms

These electrons are then caught up in the magnetic field and 

accelerated by them.

Adding energy to the electrons by the use of the coil in this 

manner is called “Inductively Coupling”

These high-energy electrons in turn collide with other Argon 

atoms, stripping off still more electrons
This collisional ionization of Argon continues in a chain 
reaction thus breaking down the gas into a Plasma consisting of
Argon atoms, electrons, and Argon ions know as “ICP”
discharge

This ICP discharge is sustained

This ICP discharge appears as intense, brilliant, white and 

tear-drop shaped (Fig 3)
(Fig 4)

Explains what happens to aerosol samples introduced into the

plasma
(Fig 5)

Explains advantage of the plasma with repect to stability,

high temperature suurounding the sample for long time
(2 milliseconds) thus resulting into lack of matrix
interferences.
General Information

Used for Qualitative Analysis

Used for Quantitative Analysis

Detection limit is in ppb range

Not possible to determine: H, N, O, C or Ar in trace levels 

as they are used in solvents and plasma

Not possible to determine F, Cl and noble gases at trace 

levels as they require high excitation energy

Not used for determining radioactive elements

 Upper limit for linear calibration is 10000 – 1000000 times 
the detection limits for a particular emission line

Only 2 standard solutions are required for the calibration 

plot as linearity is infinite

ICP has a multi-elemental capability for analysis

INSTRUMENTATION
Similar to an atomic absorption spectrometer ,the
monochromator is simply a wavelength selector
that separates all different wave lengths and
select the desired one .

The selected wave length is passed on to a

detector that converts the light signal into an
electrical signal .
 Comparison Between Atomic
Absorption and Emission
Spectroscopy
Absorption Emission

- Measure trace metal - Measure trace metal

concentrations in concentrations in
complex matrices . complex matrices .

- Atomic absorption - Atomic emission depends

depends upon the upon the number of
number of ground state excited atoms .
atoms .
- It measures the - It measures the
radiation absorbed by radiation emitted by
the ground state atoms. the excited atoms .
- Presence of a light
source ( HCL ) . - Absence of the light
source .
- The temperature in
the atomizer is adjusted - The temperature in the
to atomize the analyte atomizer is big enough
atoms in the ground to atomize the analyte
state only. atoms and excite them
to a higher energy level.
 3
AAS APPLICATIONS
The 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, and petrol.
- Pharmaceuticals. In some pharmaceutical
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.
- 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.
- Mining: 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 .

- Trace elements in food analysis

- Trace element analysis of cosmetics
- Trace element analysis of hair
 Paper 1
Determination of lead in dialysis
concentrates using FI – HG AAS
- Dialysis is a medical treatment that is given to patients with
abnormal function of the kidney .
- Washing the kidney from the various trace elements that the
kidney itself should have done .

- One of the elements that is present in a dialysis concentrate is -

lead ,which is very toxic and become fatal if it exceeds the level of
380 กg / l in our body .

- In order to determine the pb concentration in a dialysis -

concentrate, a flow injection hydride generation atomic
absorption spectroscopy was proposed .
- The hydride generation is very applicable since its is a
reducing agent and for some metals with high
oxidation state the atomization energy is high ,so the
hydride simply reduces the oxidation sate and thus the
atomization energy .
- Lead hydride is usually unstable but in an acidic medium
of Hcl with the presence of a mild oxidant k3 Fe (CN )6
it showed high precision and freedom from
interferences .
- Sample is injected in an HCl , k3 Fe (CN ) 6 carrier
solution and then combined with with NaBH4 to mix
in the mixing coil .

- An Argon gas carrier is used to sweep out the lead

hydride carrier all the way to the atomizer .
- Comparison was done with an electro thermal AAS ,and
the results were close but in FI HG AAS interference
was absent .
- Finally FI HG AAS showed to be easy ,simple ,and low
cost compared to ICP ; and it is applicable to all
hydride standards .
 paper 2
Online separation for the speciation of
mercury in natural waters by flow injection
Atomic Absorption Spectrometry ratio

- Nowadays methyl mercury is considered as the

most toxic mercury compound .

- In this application separation of inorganic

mercury Hg + from methyl mercury CH3Hg+
will be performed in an ion exchanger in a FIA
apparatus ,and then followed by detection of
CH3Hg+ in an atomic absorption spectrometer .
- An ion exchanger is used to take out the Hg+
since at pH < 10 Hg+ is completely anionic
(HgCl)4-2 while CH3HgCl remains neutral .
- The left CH3Hgcl is detected by an atomic
absorption Spectrometer .
- This application is very interesting because it
used AAS , and FIA techniques to do both
separation and detection .