Assignment # 1

SUBMITTED BY
ANAM RANA
2013-AG-689
COURSE : PY-714

ATOMIC ABSORPTION M.PHIL CHEMISTRY 3RD SEMESTER

SPECTROSCOPY

SUBMITTED TO : DR. YASIR JAMIL

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Atomic Absorption Spectroscopy

Introduction
Atomic Absorption Spectroscopy is an analytical technique used for the qualitative
and quantitative determination of the elements present in different samples like food,
nanomaterials, biomaterials, forensics, and industrial wastes (Farrukh, 2012).

Every element has a specific number of electrons associated with its nucleus. The normal
and most stable orbital configuration of an atom is known as the "ground state." If energy is
applied to an atom, the energy will be absorbed and an outer electron will be promoted to a
less stable configuration known as the "excited state." Since this state is unstable, the atom
will immediately return to the "ground state," releasing light energy.

In atomic absorption the "ground state" atom absorbs light energy of a specific wavelength
and it enters the "excited state as shown in fig. (a).

Figure a: Process involve in atomic absorption

(Analytical Methods for Atomic Absorption Spectroscopy, 1996)

Basic Principles of Atomic Absorption

The basic principles of atomic absorption spectroscopy can be expressed by three simple
statements:

I. All atoms can absorb light.

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II. The wavelength at which light is absorbed is specific for each element. The amount of
light absorbed at this wavelength will increase as the number of atoms of the selected
element in the light path increases, and is proportional to the concentration of
absorbing atoms.
III. The relationship between the amount of light absorbed and the concentration of the
analyte present in known standards can be used to determine unknown concentrations
by measuring the amount of light they absorb.

Figure b: G.Ma and G.W. Gonzales, http://www.cee.vt.edu

Types of atomic absorption spectroscopy

1. Flame atomic absorption spectroscopy

In flame atomic absorption spectroscopy the first stage is the treatment of the sample,
by dissolving it in a convenient matrix, and followed by the pneumatic nebulisation. In FAAS
the stage of atomization is performed in flame. The temperature of the flame is determined by
the fuel/oxidant coefficient. The optimum temperatures depend on the excitation and
ionization potentials of the analyte. The concentration of excited and non-excited atoms in the
flame is determined by the fuel/oxidant coefficient and varies in the different regions of the
flame (Willard et al., 1991).

2. Electrothermal atomic absorption spectroscopy

In the electrothermal atomic absorption spectroscopy the atomizing head replaces the
nebulising-burning part of the FAAS. The power source supplies the work current at the
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correct voltage of the atomizing head. The computer control of the atomizing chamber
ensures reproducibility in the heating conditions, establishing a suitable profile of
temperatures in the heating scale from environmental temperature to that of atomization so
that the successive stages of drying, calcination and carbonization the sample must go
through are those required. The working temperature and the duration of each stage of the
electrothermal process must be carefully selected taking into account the nature of the analyte
and the composition of the matrix of the sample. The control unit which measures and
controls the flow of an inert gas within the atomizing head is designed to avoid the
destruction of the graphite at high temperatures due to oxidation with the air. One variant of
the graphite oven is the carbon bar atomizer.

Main advantages

The main advantages of electrothermal atomic absorption are:

a. High sensitivity (absolute quantity of analyte of 10-8 to 10-11 g).

b. Small volumes of liquid samples (5–100 µL).
c. The possibility of analysing solid samples directly without pre-treatment and
d. Low noise level of the oven (Jamal Uddin, 2012).
3. Saturated atomic absorption spectroscopy

Saturated atomic absorption spectroscopy or Doppler-free spectroscopy is a set-up that

enables the precise determination of the transition frequency of an atom between its ground
state and an optically excited state. The accuracy to which these frequencies can be
determined is, ideally, limited only by the width of the excited state, which is the inverse of
the lifetime of this state. However, the samples of atomic gas that are used for that purpose
are generally at room temperature, where the measured frequency distribution is highly
broadened due to the Doppler Effect. Saturated absorption spectroscopy allows precise
spectroscopy of the atomic levels without having to cool the sample down to temperatures at
which the Doppler broadening is no longer relevant (which would be on the order of a few
millikelvins). It is also used to lock the frequency of a laser to the precise wavelength of an
atomic transmission in atomic physics experiments (Wikipedia).

4. Cold vapour atomic absorption spectroscopy

Atomic absorption spectrometry (AAS) in order to get maximum analytical
performance and measurement accuracy for mercury concentrations from 1 ppt (parts
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per trillion) to 100 ppm (parts per million). This so-called "cold vapour atomic
absorption spectroscopy" (CVAAS) is extremely sensitive for mercury determination
and has been used successfully over a period of many years. The cold vapour atomic
absorption technique is widely used for mercury trace analysis because of its simplicity,
robustness, and relative freedom from interferences. Excellent detection limits can be
achieved with our modern instruments.

In Cold vapour type spectroscopy the light source lamp, adjust the wavelength dial of
the spectroscope to the wavelength of the analytical line specified, and set at an appropriate
current value and a slit-width. Then, in the reduction vaporizing method, transfer the test
solution or the standard solution or control solution to the closed vessel, reduce to the element
by addition of a proper reducing agent, and vaporize. In the heat vaporizing method, vaporize
the sample by heating. Absorbance of the atomic vapour generated by these methods is
measured.

Instrumentation of atomic absorption spectroscopy

The basic instrumentation and function of the instrument is as follows:

(i) The radiation source (a hollow cathode or an EDL) emits a sharp line spectrum
characteristic of the analyte element.
(ii) The emission beam from the radiation source is modulated.
(iii) The modulated signal passes through the atomic vapour where the atoms of the
analyte absorb radiation of the line-like radiation source.
(iv) The desired spectral line (usually resonance line) is selected by the
monochromator.
(v) The isolated analyte line falls onto .the detector (a photomultiplier) where the light
signal is converted into the electric signal.
(vi) The modulated signal is amplified by a selective amplifier.
(vii) The signal is finally recorded by a readout device (a meter, strip chart recorder, or
through data processing to a digital display unit or printer) (Lajunen, 1992).

Single vs Double Beam Configurations

In a single-beam atomic absorption instrument the light source (hollow cathode lamp
or electrodeless discharge lamp) emits a spectrum specific to the element of which it is made,
which is focused through the sample cell into the monochromator. The light source must be
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electronically modulated or mechanically chopped to differentiate between the light from the
source and the emission from the sample cell.

Figure c: single-beam atomic absorption instrument

(Analytical Methods for Atomic Absorption Spectroscopy, 1996)

In a double-beam system the light from the source lamp is divided into a sample
beam, which is focused through the sample cell, and a reference beam, which is directed
around the sample cell. In a double-beam system, the readout represents the ratio of the
sample and reference beams. Therefore, fluctuations in source intensity do not become
fluctuations in instrument readout, and stability is enhanced.

Figure d: single-beam atomic absorption instrument

(Analytical Methods for Atomic Absorption Spectroscopy, 1996)

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Instrumentation

1) RADIATION SOURCE

The main sources used for atomic absorption are:

I. Hollow Cathode Lamp (HCL)

II. Electrode less Discharge Lamp (EDL

I. Hollow Cathode Lamp (HCL)

The hollow cathode lamp is an excellent, bright, stable line source for most elements.
The cathode is a hollowed-out cylinder constructed entirely or in part of the metal whose
spectrum is to be produced. The anode and cathode are sealed in a glass cylinder filled with
neon or argon. The glass cylinder has a quartz or UV glass window for optimum
transmittance of the emitted radiation. The optimum fill gas is selected that gives the best
lamp intensity while taking into consideration spectral interferences from either neon or
argon. A red glow is observed in lamps filled with neon, while argon filled lamps have a blue
glow. Hollow cathode lamps are available for more than 60 elements.

Figure e: Hollow cathode lamp

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The emission process is illustrated in Figure (f). When an electrical potential is

applied between the anode and cathode, some of the fill gas atoms are ionized. The positively
charged fill gas ions accelerate through the electrical field to collide with the negatively
charged cathode and dislodge individual metal atoms in a process called ‘‘sputtering’’.
Sputtered metal atoms are then excited to an emission state through a kinetic energy transfer
by impact with fill gas ions.

Figure f: emission process in HCL.

(Beaty and Jack ,1993)

Disadvantages

Hollow cathode lamps have a finite lifetime. Adsorption of fill gas atoms onto the
inner surfaces of the lamp is the primary cause for lamp failure. As fill gas pressure
decreases, the efficiency of sputtering and the excitation of sputtered metal atoms also
decreases, reducing the intensity of the lamp emission. To prolong hollow cathode lamp life,
some manufacturers produce lamps with larger internal volumes so that a greater supply of
fill gas at optimum pressure is available. The sputtering process may remove some of the
metal atoms from the vicinity of the cathode to be deposited elsewhere. Lamps for volatile
metals such as arsenic, selenium, and cadmium are more prone to rapid vaporization of the
cathode during use. While the loss of metal from the cathode at normal operating currents
(typically 5-25 milliamperes) usually does not affect lamp performance, fill gas atoms can be
entrapped during the metal deposition process which does affect lamp life. Lamps which are
operated at highly elevated currents may suffer reduced lamp life due to depletion of the
analyte element from the cathode.

Some cathode materials can slowly evolve hydrogen when heated. As the
concentration of hydrogen in the fill gas increases, a background continuum emission
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contaminates the purity of the line spectrum of the element, resulting in a reduction of atomic
absorption sensitivity and poor calibration linearity. To eliminate such problems, most
modern hollow cathode lamps have a tantalum ‘‘getter’’ on the anode which irreversibly
adsorbs evolved hydrogen as the lamp is operated.

Multi-element’’ lamp

The cathode of the hollow cathode lamp is usually constructed from a highly pure
metal resulting in a very pure emission spectrum of the cathode material. It is sometimes
possible, however, to construct a cathode or cathode insert from several metals. The resulting
‘‘multi-element’’ lamp may provide superior performance for a single element or, with some
combinations, may be used as a source for all of the elements contained in the cathode alloy.
However, not all metals may be used in combination with others because of metallurgical or
spectral limitations

II. Electrodeless discharge lamp (EDL).

For most elements, the hollow cathode lamp is a completely satisfactory source for
atomic absorption. In a few cases, however, the quality of the analysis is impaired by
limitations of the hollow cathode lamp. The primary cases involve the more volatile elements
where low intensity and short lamp life are a problem. The atomic absorption determination
of these elements can often be dramatically improved with the use of brighter, more stable
sources such as the ‘‘electrodeless discharge lamp’’.

Figure g : EDL electrodeless discharge lamp

(Dr. Deepak Bhanot Lab-Training.com)

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A small amount of the metal or salt of the element for which the source is to be used is
sealed inside a quartz bulb. This bulb is placed inside a small, self-contained RF generator or
‘‘driver’’. When power is applied to the driver, an RF field is created. The coupled energy
will vaporize and excite the atoms inside the bulb, causing them to emit their characteristic
spectrum. An accessory power supply is required to operate an EDL.Electrodeless discharge
lamp.

Concepts, Instrumentation and Techniques

Electrodeless discharge lamps are typically much more intense and, in some cases,
more sensitive than comparable hollow cathode lamps. They therefore offer the analytical
advantages of better precision and lower detection limits where an analysis is intensity
limited. In addition to providing superior performance, the useful lifetime of an EDL is
typically much greater than that of a hollow cathode lamp for the same element. It should be
noted, however, that the optical image for the EDL is considerably larger than that in a
hollow cathode lamp. As a result, the performance benefits of the EDL can only be observed
in instruments with optical systems designed to be compatible with the larger image.

Electrodeless discharge lamps are available for a wide variety of elements, including
antimony, arsenic, bismuth, cadmium, cesium, germanium, lead, mercury, phosphorus,
potassium, rubidium, selenium, tellurium, thallium, tin and zinc.

2) The atomic absorption atomizer

a) Flame AA
 Pre-Mix Burner System

The sample cell, or atomizer, of the spectrometer must

produce the ground state atoms necessary for atomic
absorption to occur. This involves the application of thermal
energy to break the bonds that hold atoms together as
molecules. While there are several alternatives, the most
routine and widely applied sample atomizer is the flame.

In ‘‘premix’’ design, sample solution is aspirated through a

nebulizer and sprayed as a fine aerosol into the mixing
chamber. Here the sample aerosol is mixed with fuel and
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oxidant gases and carried to the burner head, where combustion and sample atomization
occur.

Concepts, Instrumentation and Techniques

Fuel gas is introduced into the mixing chamber through the fuel inlet, and oxidant
enters through the nebulizer sidearm. Mixing of the fuel and oxidant in the burner chamber
eliminates the need to have combustible fuel/oxidant in the gas lines, a potential safety
hazard. In addition to the separate fuel and oxidant lines, it is advantageous to have an
auxiliary oxidant inlet directly into the mixing chamber. This allows the oxidant flow
adjustments to be made through the auxiliary line while the flow through the nebulizer
remains constant. Thus, for a burner system with an auxiliary oxidant line, the sample uptake
rate is independent of flame condition, and the need to readjust the nebulizer after every
oxidant flow adjustment is eliminated.

Only a portion of the sample solution introduced into the burner chamber by the nebulizer is
used for analysis. The finest droplets of sample mist, or aerosol, are carried with the
combustion gases to the burner head, where atomization takes place. The excess sample is
removed from the premix chamber through a drain. The drain uses a liquid trap to prevent
combustion gases from escaping through the drain line. The inside of the burner chamber is
coated with a wettable inert plastic material to provide free drainage of excess sample and
prevent burner chamber ‘‘memory.’’ A free draining burner chamber rapidly reaches
equilibrium, usually requiring less than two seconds for the absorbance to respond fully to
sample changes.

 Impact Devices

The sample aerosol is composed of variously sized droplets as it is sprayed into the mixing
chamber. Upon entering the flame, the water in these droplets is vaporized. The remaining
solid material must likewise be vaporized, and chemical bonds must be broken to create free
ground state atoms. Where the initial droplet size is large, the sample vaporization and
atomization process is more difficult to complete in the short time in which the sample is
exposed to the flame. Incomplete sample vaporization and atomization will lead to increased
susceptibility to analytical interferences. Impact devices are used to reduce droplet size
further and to cause remaining larger droplets to be deflected from the gas stream and
removed from the burner through the drain.
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Types

Two types of impact device are used typically

Impact beads

Flow spoilers.

Impact bead systems are normally used to improve nebulization efficiency, the percentage
of sample solution converted to smaller droplets. The impact bead is normally a spherical
bead made of glass, silica or ceramic. Glass or quartz impact beads may be less corrosion
resistant and may cause more contamination problems than more chemically inert ceramic
beads.

The impact bead is positioned directly in the nebulizer spray as it exits the nebulizer. The
sample spray contacts the impact bead at high speed, causing some of the larger droplets to
be broken up into smaller droplets. The design and positioning of the impact bead are critical
in determining how well it will work. Properly designed impact bead systems will improve
nebulization efficiency and remove many of the remaining large droplets from the spray.
However, poorly designed or positioned impact beads may have little or no effect on
nebulization efficiency and may be very inefficient at removing larger droplets from the
spray. The increased population of large droplets in the aerosol may create undesirable
effects, including poorer precision and increased interferences. Additionally, burner systems
using an impact bead may exhibit memory problems with high concentration solutions or
solutions with high dissolved solids content.

The quality of an impact bead system can frequently be determined by the increase in
sensitivity it provides for selected elements. A poorly designed system will provide improved
sensitivity for easily atomized elements simply because more sample is transported to the
flame and less to the drain. However, there normally will be little or no improvement in
sensitivity for the less easily atomized elements. A properly designed impact bead system
will provide improved nebulization efficiency and improved sensitivity for all elements.

Flow spoilers normally do not improve nebulization efficiency. The primary use of a flow
spoiler is to remove the remaining large droplets from the sample aerosol. The flow spoilers
used in atomic absorption burner systems normally are placed between the nebulizer and the
burner head. They typically have three or more large vanes constructed from or coated with a
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corrosion resistant material. Smaller droplets are transported through the open areas between
the vanes while larger droplets contact the vanes and are removed from the aerosol.

For routine atomic absorption analyses where maximum sensitivity is not required, use of an
efficient flow spoiler alone will provide the required analytical stability and freedom from
interference. A burner system optimized for maximum sensitivity and performance should
include both a high nebulization efficiency ceramic impact bead and an efficient flow spoiler.

 Nebulizers, Burner Heads and Mounting Systems

Several important factors enter into the nebulizer portion of the burner system. In order to
provide efficient nebulization for all types of sample solution, the nebulizer should be
adjustable. Stainless steel has been the most common material used for construction of the
nebulizer. Stainless steel has the advantage of durability and low cost but has the
disadvantage of being susceptible to corrosion from samples with a high content of acid or
other corrosive reagents. For such cases, nebulizers constructed of a corrosion resistant
material, such as an inert plastic, platinum alloys or tantalum should be used.

Burner heads typically are constructed of stainless steel or titanium. All-titanium heads are
preferred as they provide extreme resistance to heat and corrosion.

Different burner head geometries are required for various flame or sample conditions. A ten-
centimeter single-slot burner head is recommended for air-acetylene flames. A special five-
centimeter burner head with a narrower slot is required when a nitrous oxide-acetylene flame
is to be used. Burner heads also are available for special purposes, such as use with solutions
that have exceptionally high dissolved solids contents.

In addition to the flame, there are several options for atomic absorption atomizers Most of
these options require removal of the premix burner system and replacement by an alternate
atomizer in the spectrometer sample compartment. Since these alternate atomizers offer
complementary and extended analytical capabilities, it is likely that the analyst will want to
alternate between the use of flame AA and one or more of the other systems. A ‘‘quick
change’’ atomizer mount is an important item to facilitate convenient changeover from one
device to another without the use of tools. In addition to convenience, a ‘‘quick change’’
mount may reduce or eliminate entirely the need for realignment of the atomizer when it is
replaced in the sample compartment (Beaty and Jack, 1993).

b) Other means of sample vaporization

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Cathode Sputtering:

The principle of the hollow cathode tube, production of a vapour of atoms by cathodic
sputtering, has been employed by Gatehouse and Walsh for sample vaporization. The sample
is introduced into a vacuum chamber and is made the cathode which produces a cloud of
activated atoms. The light of a separate hollow cathode tube is passed through this vapor and
absorption is measured in a spectrophotometer. The method is said to yield reproducible
results, and a straight working curve was obtained with silver.

Flameless Crucibles

L’vov (1961) developed a flameless furnace applicable for atomic absorption spectroscopy.
A tube-shaped graphite crucible is inserted into a chamber, fitted at both ends with quartz
windows. A carbon electrode is installed in the middle of the graphite tube and another one
outside. Solid samples weighing less than 0.1 mg are placed at the tip of the electrode inside
the tube and the chamber is closed, evacuated, and filled with argon at low pressure. The
graphite crucible is heated electrically to 2000°C. Then an arc is struck between the carbon
electrodes whereby the small sample is suddenly evaporated and an atomic vapor is created
inside the graphite crucible. The concentration of a metaI in the vapor is dependent upon the
total amount present originally in the sample placed on the carbon electrode. The beam of an
appropriate hollow cathode tube is passed through the long axis of the graphite tube and
absorption is measured by a spectrophotometer. It is stated that no interference could be
found for any of the elements tested, that reproducibility was excellent, and that only 3
minutes were required for one determination.

Capacitor Discharge Lamp

Nelson and Kuebler (1983) described a modified capacitor discharge lamp into which
samples could be introduced for vaporization. The single, intense light pulse of these lamps
results in flash heating of the samples to several thousand degrees Celsius, by which a dense
cloud of atomic vapor is produced that persists for a few thousandths of a second. By
spectrographic means the authors were able to record the absorption spectra of about 20
metals including copper, iron, lead, calcium, magnesium, and zinc.

Cool Vapor

Mercury, the only metallic element with significant volatility at room temperature, has been
conventionally determined for many years by atomic absorption spectrometry, as the mercury
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vapor detector (WZO) is based on this principle (Zettner 1964). Lindstrom (1959) used a
flame to volatilize the mercury in the liquid sample, but determined its concentration in the
exhaust gases with the mercury vapor meter after cooling and purification in a filter that
removed particulate matter. The method is said to be capable of detecting 0.1 µg % of
mercury in the original liquid sample.

3) OPTICAL CONSIDERATIONS
 Photometers
The portion of an atomic absorption spectrometer’s optical system which conveys the light
from the source to the monochromator is referred to as the photometer

.Light from the source must be focused on the sample cell and directed to the
monochromator, where the wavelengths of light are dispersed and the analytical line of
interest is focused onto the detector. Some energy is lost at each optical surface along the
way. Front-surfaced, highly reflective, mirrors can be used to control the focus of the source
lamp and the field of view of the light detector precisely and with minimal light loss.
Alternately, focusing can be accomplished by refraction instead of reflection by using a lens
system. Since the focal length of a lens varies with wavelength, additional optics (which may
further reduce energy throughput) or complex optical adjustments must be used to obtain

Figure h: optical considerations of AAS ((Beaty and Jack, 1993)

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proper focus over the full spectral range for atomic absorption. Particular care must be taken
in the monochromator to avoid excessive light loss

Grating

Wavelength dispersion is accomplished with a grating, a reflective surface ruled with many
fine parallel lines very close together. Reflection from this ruled surface generates an
interference phenomenon known as diffraction, in which different wavelengths of light
diverge from the grating at different angles. Light from the source enters the monochromator
at the entrance slit and is directed to the grating where dispersion takes place. The diverging
wavelengths of light are directed toward the exit slit. By adjusting the angle of the grating, a
selected emission line from the source can be allowed to pass through the exit slit and fall
onto the detector. All other lines are blocked from exiting.

The angle of dispersion at the grating can be controlled by the density of lines on the grating.
Higher dispersion will result from greater line density, i.e., more lines/mm. High dispersion is
important to good energy efficiency of the monochromator.

Another factor affecting the optical efficiency of the monochromator is the blaze angle of the
grating, whether it is mechanically ruled or holographically generated. A grating can be
constructed for a blaze at any desired wavelength by controlling the angle of cut during
ruling. The farther removed a given wavelength of light is from the wavelength for which a
grating is blazed, the greater will be the extent of monochromator light loss at that
wavelength.

4) Detectors

Once the proper atomic resonance line has been isolated by the spectrometer, the detector and
its associated electronics are used to measure the intensity of the atomic absorption or
emission. The detector universally used is the photomultiplier tube. This has high sensitivity,
a wide dynamic range and can be used across the complete wavelength range required for
atomic absorption analysis.

The photomultiplier tube is a vacuum tube that produces an electrical signal which is
proportional to the intensity of the light which reaches the device. Light admitted through a
window in the photomultiplier tube falls directly onto a photosensitive material–the
photocathode. The cathode is coated with a material which emits electrons whenever it is
illuminated. The higher the intensity of the incident light–the greater the number of electrons
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emitted. The electrons emitted are accelerated towards an adjacent electrode, maintained at a
positive electrical potential with respect to the cathode. This is called a dynode. When each
electron reaches the dynode, it liberates a number of secondary electrons which are in turn
attracted to another dynode, emitting even more electrons. This is the multiplier process that
gives the photomultiplier its name. A dynode chain of between 9 to 16 stages is usually fitted
inside the PMT, causing an increase in the electron current generated at the cathode. As many
as 108 secondary electrons may be collected as the result of a single photon striking the
photocathode.

The electrical current measured at the anode is then used as a relative measure of the intensity
of the radiation reaching the PMT. Thus the light intensities which are obtained in atomic
spectroscopy lead to an electric current of useful magnitude which can be further amplified to
provide the required quantitative measurement.

The major advantage of the PMT over other detection devices are that it can be used to
measure light over the complete wavelength range of analytical interest, it can amplify very
weak incident light levels and it has a wide dynamic range.

Atomic absorption and beer’s law

In the atomic absorption light at the resonance wavelength of initial intensity, I o, is
focused on the flame cell containing ground state atoms. The initial light intensity is
decreased by an amount determined by the atom concentration in the flame cell. The light is
then directed onto the detector where the reduced intensity, I, is measured. The amount of
light absorbed is determined by comparing I to Io.

Several related terms are used to define the amount of light absorption which has taken place.
The ‘‘transmittance’’ is defined as the ratio of the final intensity to the initial intensity.

T = I/Io

Transmittance is an indication of the fraction of initial light which passes through the flame
cell to fall on the detector. The ‘‘percent transmission’’ is simply the transmittance expressed
in percentage terms.

%T = 100 x I/Io
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The ‘‘percent absorption’’ is the complement of percent transmission defining the percentage
of the initial light intensity which is absorbed in the flame.

%A = 100 - %T

These terms are easy to visualize on a physical basis. The fourth term, ‘‘absorbance’’, is
purely a mathematical quantity.

A = log (Io/I)

Absorbance is the most convenient term for characterizing light absorption in absorption
spectrophotometry, as this quantity follows a linear relationship with concentration. Beer’s
Law defines this relationship:

A = abc

Where ‘‘A’’ is the absorbance; ‘‘a’’ is the absorption coefficient, a constant which is
characteristic of the absorbing species at a specific wavelength; ‘‘b’’ is the length of the light
path intercepted by the absorption species in the absorption cell; and ‘‘c’’ is the concentration
of the absorbing species. This equation simply states that the absorbance is directly
proportional to the concentration of the absorbing species for a given set of instrumental
conditions.

This directly proportional behaviour between absorbance and concentration is observed in

atomic absorption. When the absorbances of standard solutions containing known
concentrations of analyte are measured and the absorbance data are plotted against
concentration, a calibration relationship similar to that in Figure( i ) is established.

After such a calibration is established, the absorbance of solutions of unknown concentrations

may be measured and the concentration determined from the calibration curve. In modern
instrumentation, the calibration can be made within the
instrument to provide a direct readout of unknown
concentrations. Since the advent of microcomputers,
accurate calibration, even in the nonlinear region, is
simple (Beaty and Jack, 1993).Characteristic
Concentration
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The ‘‘characteristic concentration’’ (sometimes called ‘‘sensitivity’’) is a convention

for defining the magnitude of the absorbance signal which will be produced

by a given concentration of analyte. Figure i: calibration curve

Detection limit

The detection limit is defined by the IUPAC as the concentration which will give an
absorbance signal three times the magnitude of the baseline noise.

The term ‘‘detection limit’’ incorporates a consideration of both signal size and baseline
noise to give an indication of the lowest concentration of an element which can be measured.

Recent applications of atomic absorption spectroscopy

1) Interference free and fast determination of manganese(II), iron(III) and

copper(II) ions in different real samples by flame atomic absorption
spectroscopy after column graphene oxide-based solid phase extraction.

A solid phase extraction (SPE) and flame atomic absorption spectroscopy (FAAS) for the
determination of Mn(II), Fe(III) and Cu(II) ions with a graphene oxide (GO) packed column
and 1-Phenyl-3-(2-thienylmethyl)thiourea (PTT) as chelating reagent was studied. In
theoretical part, the PM6 semi-empirical and PBE density functional theory methods were
used for investigation of adsorption mechanism of the complexes on GO sheet. The
calculated thermochemistry of the complexation reactions was reported. Based on quantum
theory of atoms in molecules (QTAIM) analysis, the nature of the metal/ligand bonding was
discussed. Extraction efficiency and the effects of parameters such as flow rate, pH, type and
the least amount of acid for stripping of understudied ions from the modified column and
break through volume were examined. The preconcentration factor was 280 (for 1400 mL of
sample solution and flow rate of 10 mL min − 1) and detection limit of the proposed method
was found in the range of 0.06–0.49 μg L− 1. The developed method was successfully applied
to the determination of Mn(II), Fe(III) and Cu(II) ions in leaves of spinach, honey, hair, blood
and various water samples( Pourjavid et al., 2016).

2) Quantitative Estimation of Lead (Pb) and Cadmium (Cd) Content in Commonly

Used Cosmeceuticals Using Atomic Absorption Spectroscopy

Background: Humans are exposed continuously to a large number of chemicals from various
sources and via multiple routes. One of the most common sources is the use of
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cosmeceuticals like lipsticks and sunscreen which contain significant amount of heavy metals
like Lead (Pb) and Cadmium (Cd).

Introduction: The present study was undertaken with an objective to investigate the content of
heavy metals especially Pb and cadmium Cd from commonly used brands of cosmetic
products (lipsticks and sunscreen creams) in India.

Methods: Sixty samples of lipsticks (5 colors in 6 brands) and sunscreen creams (3 colors in
10 brands) were chosen for the present investigation, procured from cosmetic shop centre,
Moradabad (India). The Pb and Cd concentrations of the formulations were analyzed using
atomic absorption spectroscopy.

Result: The results indicated that the concentrations of Pb and Cd in the lipstick samples were
within the range of 0.12– 4.9 μg/g and 3.48–46.38 μg/g, respectively. In sunscreen creams,
the concentration of Pb and Cd were found to be in the range of 0.96–4.50 μg/g and 9.54–
22.41 μg/g respectively. The observed concentrations of the heavy metals in the lipsticks
samples were lower than that of the sunscreen creams.

Conclusion: The significant difference between the average of Pb content in the different
brands of the sunscreen creams and the lipsticks was recorded. Therefore, the frequent use of
such cosmetics may culminate enhanced absorption of heavy metals, especially Pb and Cd, in
the body through absorption of cosmetics over skin surface as well as by swallowing of
lipsticks during its application. Pb and Cd as heavy metal may be harmful, if these are present
in cosmeceuticals in excess quantity. Therefore, attempts must be made to familiarize the
cosmetic users and the public about the harmful consequences of heavy metal present in
cosmetics (Mishra et al., 2016).
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