UNIT 11 APPLICATIONS OF AAS AND AES

Applications of AAS
and AES

Structure
11.1

Introduction
Objectives

11.2

Salient features of AAS and AES

Salient features of AAS
Salient features of AES
Comparison between AAS and AES

11.3
11.4

Sample Preparation
Applications of AAS
Biological Samples
Environmental Samples
Industrial Samples

11.5

Applications of AES
Biological Samples
Geological Samples
Environmental Samples
Industrial Samples

11.6
11.7
11.8

Summary
Terminal Questions
Answers

11.1 INTRODUCTION
In the preceding Units 9 and 10, you have studied about basic principles and
instrumental aspects of atomic absorption spectrophotometry (AAS) and atomic
emission spectrometry (AES) respectively. You would recall that atomic absorption
spectrophotometry concerns the absorption of radiation by the atomised analyte
element in the ground state; the atomisation being achieved by the thermal energy of
the flame or electrothermally in an electrical furnace. The wavelength(s) of the
radiation absorbed and the extent of the absorption form the basis of the qualitative
and quantitative determinations respectively. On the other hand atomic emission
spectrometry concerns the emission of radiation by the suitably excited atomic
vapours of the analyte; the atomisation as well as the excitation being achieved by any
of the numerous available energy sources such as flame arcs, sparks, or plasmas. Here,
the emitted radiation and its intensity form the basis for the qualitative and quantitative
applications of the technique. You have also learnt about flame emission
spectrophotometry (FES), another atomic emission technique, commonly called as
flame photometry in Unit 7. You would recall that it is a simple, rapid and inexpensive
method for routine analysis of alkali and alkaline earth metals like, sodium, potassium,
lithium, calcium and barium in environmental, clinical and biological samples
especially in biological fluids and tissues.
In this unit, we take up some of the important applications of atomic absorption
spectrophotometry and atomic emission spectrometry. We will begin the unit with
recalling the salient features of the two techniques and then take up the applications of
AAS and AES. In the next block you would learn about some miscellaneous
spectroscopic methods.

Objectives
After studying this unit, you will be able to:

outline the salient features of atomic absorption spectrophotometry and atomic

emission spectrometry,

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Atomic Spectroscopic
Methods-II

compare and contrast atomic absorption spectrophotometry and atomic emission

spectrometry,

enlist different areas of applicability of atomic absorption spectrophotometry

and atomic emission spectrometry,

discuss the merits and limitations of atomic absorption spectrophotometry and

atomic emission spectrometry,

describe some representative applications of atomic absorption

spectrophotometry and atomic emission spectrometry,

rationalise the complementary nature of atomic absorption spectrophotometry

and atomic emission spectrometry.

11.2

SALIENT FEATURES OF AAS and AES

You know that in atomic spectroscopy, the element present in a sample is converted to
gaseous atoms or elementary ions in a process called atomisation which may be
brought about by any of the available methods. The absorption of the radiation by the
vapourised atoms in the ground state, or emission or fluorescence emission of suitably
excited state forms the basis of different types of atomic spectroscopies. Collectively,
the atomic spectroscopic methods can be used for the qualitative and quantitative
determination of about 70 elements in a wide variety of samples of clinical, biological,
and environmental origin. You have learnt in details about AAS and AES in Units 7,9
and 10. Let us recollect the salient features of the AAS and AES methods before
taking up their applications.

11.2.1

58

Salient Features of AAS

AAS concerns the absorption of characteristic analyte radiation by the atomised

analyte element in the ground state. The wavelength(s) of the radiation absorbed
and the extent of the absorption form the basis of the qualitative and quantitative
determinations respectively.

In flame atomic absorption spectrophotometry, either an air-acetylene or a

nitrous oxide-acetylene flame is used to evaporate the solvent and dissociate the
sample into its component atoms.

It not an absolute method of analysis; the routine quantitative determinations

using AAS are based on calibration method. In addition, the internal standard
method and standard addition methods are also employed.

Compounds of the alkali metals, some of the heavy metals such as lead or
cadmium and transition metals like manganese or nickel are all atomised with
good efficiency by flame However, a number of refractory elements like V, Zr,
Mo and B do not perform well with a flame source.

Graphite furnace atomic absorption spectrophotometry (GFAAS) in which the

atomisation is achieved electrothermally, is a much more sensitive method as
compared to flame AAS. The higher atom density and longer residence time in
the graphite tube improve furnace AAS detection limits by a factor of up to
1000 compared to flame AAS. The detection limits may extend to the sub-ppb
range.

GFAAS requires a very small sample size and does not require any sample
preparation; even solid samples can be analysed without dissolution.

The background absorption effects in GFAAS are managed by diluting the

sample or selecting another resonance wavelength line. In matrix modifier
method a reagent is added to the sample that may modify the matrix behaviour
and thereby tackle the problem of background.

Accuracy in AAS method is generally of the order of 0.5 5%; the precision
being 0.3 1% at absorbance larger than 0.1 or 0.2 for flame atomisation and
1 5% with electrothermal atomisation.

It is a robust technique that employs easy to use equipment and can achieve
good detection limits. As the turnaround time is small the cost of analysis per
sample is not much. However, lack of automation, and usage of flammable
gases are not desirable.

11.2.2

Salient Features of AES

In atomic emission spectrometry (AES) a reproducible and representative

amount of the sample is introduced into an atomization-excitation source
wherein it is converted into atomic vapours of the analyte in excited state. The
radiation emitted from these is characteristic of the constituents of the sample.

The AES is a versatile method due to the availability of a wide range of

atomization-excitation sources. Currently, plasma is the most used source. It is
high energy source which is an electrically neutral conducting gaseous mixture
having a significant concentration of cations and electrons.

The plasma can be sustained by supplying energy from a suitable external

source. Depending on the power sources employed, there are three different
types of plasmas. These are, the inductively coupled plasma (ICP), the direct
current plasma (DCP) and the microwave induced plasma (MIP). These plasmas
use radiofrequency, direct current and microwave radiation respectively as the
power sources.

As the energy of the plasma source is quite high, it ensures the excitation of the
atoms of all the elements present in the analyte which emit EM radiation
characteristic of different elements. Thus, it is a multielement technique.

Argon gas is commonly employed as plasma gas due to its inertness, simple
emission spectrum, moderately low thermal conductivity, and good natural
abundance.

Two types of spectrometers are used for ICP-AES. These are sequential
spectrometers and simultaneous spectrometers depending on whether the
emitted radiation is measured sequentially or simultaneously.

In ICP-AES the spectral interference due to the line-rich spectra of the hot
plasma source can be minimised by using high resolution spectrometers or using
an alternative analyte line. The background effects require the use of offline
background correction techniques, or by moving to an unaffected analyte line.
The matrix effects are generally handled by using internal standard method.

The ICP spectrometers are, however, relatively expensive to purchase and

difficult to operate as the user requires extensive training for the maintenance of
the instrument.

11.2.3

Applications of AAS
and AES

Comparison between AAS and AES

As has already been emphasised, AAS and AES have become the mainstay of the
analytical techniques for major, minor and trace element analysis in geological,
biological, environmental and industrial samples. Both the techniques can be used for
the determination of more than sixty elements, many of which can be determined at
1 ppm level. As regards their applicability, these two techniques are complementary to
each other though several points are common amongst them.
It must be kept in mind that only metals and metalloids can be determined by usual
flame methods like FAAS. This is because resonance lines for nonmetals fall in

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Atomic Spectroscopic
Methods-II

vacuum UV region though some indirect methods have been developed for the same.
For example, chloride can be determined by precipitation with Ag+ and then either the
excess of Ag+ or the one which has already reacted is measured. Similarly phosphorus
(525.9 nm) and sulfur (383.7 nm) species exhibit sharp molecular band emission in the
Ar-H2 flame. Generally, AAS is considered as more sensitive technique at wavelengths
< 300 nm, whereas in visible region, AES is more advantageous. Some elements
exhibit maximum sensitivity using molecular band emissions.
As the source of radiation in AAS is a hollow cathode lamp which emits the
characteristic radiation of a given element, it is a unielemental technique. It is not
convenient to measure more than one element at a time by AAS as it is difficult to
incorporate more than a single source into the system. Each hollow cathode lamp
emits efficiently the spectrum of only one, two, or three elements at a time, measuring
additional elements requires substituting a new hollow cathode lamp. Though some
advances have been made in continuum source atomic absorption spectrophotometry
yet these arrangements are somewhat limited as sources extending into the ultraviolet
region of the spectrum are not widely available.
The basic principle of graphite furnace atomic absorption spectrophotometry
(GFAAS) is essentially the same as flame atomic absorption spectrophotometry, the
only difference being that the atomisation is achieved in a small, electrically heated
graphite tube, or cuvette, which is heated to a temperature up to 3000C to generate
the cloud of atoms. The higher atom density and longer residence time in the
electrothermal tube improve the detection limits by a factor of up to three orders of
magnitude as compared to flame AAS and we can go down to the sub-ppb range.
However, the use of graphite cuvettes, do not sort out the issue of determining
refractory elements.
It is essential that the AAS instrument should always be calibrated by preparing at
least four standard solutions over the concentration range of interest and measuring the
absorbance under the same experimental conditions. The correction, if necessary,
should be applied to the calibration plot. Sometimes, the method of standard addition
is used to compensate for chemical and other interferences.
In contrast to atomic absorption spectrophotometry, atomic emission spectrometry is
inherently a multielement method. Especially the high temperature of plasma ensures
effective atomisation and lead to intense atomic emission. The emission occurs from
all elements at the same time and is isotropic. The simultaneous multielement
determinations can be made simply by using a multichannel detection system.
Multichannel devices using two dimensional spectral dispersion along with two
dimensional arrays of detector elements offer extremely good sensitivity and low
noise.
More so at the operating high temperatures of ICP torch, even the most refractory
elements are atomised with high efficiency. As a result, detection limits for these
refractory elements can be of the orders of magnitude lower with ICP than with FAAS
techniques. These may be at the 1-10 parts per billion level. We can safely generalise
the order of detection limits of different techniques as GFAAS (sub-ppb) > ICP-AES
(1-10 ppb) > FAAS (sub-ppm).
Further, the dynamic range of the various techniques is also important, as it directly
affects the amount of dilution required in preparing solutions for analysis. If the
dynamic linear range is quite wide, we may use fewer standards. The dynamic ranges
of FAAS and GFAAS are of the order of only 102-103 only whereas the same for ICPAES the dynamic range spreads upto 106. This makes it a suitable technique that is
capable of measuring from trace to percent levels. A comparative account of the
characteristics of AAS and ICP-AES are briefly summarised in Table 11.1.

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Table 11.1: A comparative account of the characteristics of AAS and ICP-AES

Atomic Absorption Spectrophotometry

ICP-Atomic Emission Spectrometry

Primarily a single element technique; though

some instruments with multielement sources
are available.

Principally a rapid and multi-element

technique.

The flame constituents contribute to the

spectral, background and chemical
interferences.

Plasma is an optically thin emission source

and is relatively free from chemical
interferences.

The dynamic range is spread over three

orders of magnitude for FAAS and two
orders for GFAAS.

The dynamic range is large and extends over

a range of 4 to 6 orders of magnitude. It is
suitable for analytes from parts per billion to
99.9 per cent.

For AAS the detection limits are in the range

of ppm whereas these may go down to subppb level for GFAAS.

Detection limits are generally very low: 1 to

100 ng/g or g/L (parts per billion).

Flame AAS is easy to set up and to use, and

requires minimal operator skills, the GFAAS
on the other hand is considerably more
difficult to operate.

It falls between these two AAS techniques;

however, it is a bit easier to master than
GFAAS.

FAS procedure cannot be automated

whereas it is possible to automate GFAAS.

ICP-AES measurements can be automated.

The accuracy is not very promising.

Good accuracy and precision (relative

standard deviation about 1 per cent).

The AAS determinations using flame are

rapid and precise and are applicable to about
67 elements.

It can be used for the determination of most

elements except Ar. In practice,
approximately 70 elements can be
determined.

Not suitable for the elements like, B, C, Ce,

La, Nb, Pr, S, P, Ti, Ta, V and Zr.

The elements that are difficult to be

determined by AAS, can be measured by
AES.

11.3

Applications of AAS
and AES

SAMPLE PREPARATION

All samples for determination by AAS or AES must be in solution form except for
spark source AES where solids especially metals and alloys with smooth surface can
be analysed directly. The detailed procedures for sample preparations have been
discussed in Section 9.7 and subsection 10.4.2 respectively for AAS and AES. You
would recall that in principle, the sample in solid, liquid or in the gas phase can be
analysed by flame AAS but in practice the sample is taken in the solution form. The
solution of the solids is generally prepared by wet dissolution method using a suitable
acid. The presence of organic solvents of low molar mass e.g. alcohols, ethers, ketones
and esters are found to enhance absorption peaks and hence increase sensitivity. A
microwave digestion system (MDS) offers more rapid and efficient decomposition of
complex matrices of geological and biological samples. It greatly reduces the operator
time to prepare samples for analysis. More so, it can be easily automated also.
On the other hand in ICP-AES, the solution preparation depends on the nature of the
sample and the concentration of elements to be determined. The solution for ICP
analysis can be prepared either by wet acid method or by direct attack method and
suitable precautions are taken as per the requirements of the plasma source.

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Atomic Spectroscopic
Methods-II

It must be noted that the possible contamination during dissolution and at the
workplace is the most important source of error in the analysis of trace elements and
must be avoided. Contamination may come from the air, from the skin of the subject/
sample collector, additives and reagents used in the analysis, as well as parts of
instrumentation including glass or plastic wares. Biological materials of human and
plant origin must be handled with extreme care because of sample inhomogeneity
especially for trace element analysis. Body fluids such as blood, viscera, urine, etc.
additionally need stabilization and homogenization so as to avoid occurrence of any
changes in their composition, prior to actual analysis. It is also advisable to keep the
total number of transfers to a minimum, and to use accessories made of non-wettable
and inert materials.

SAQ 1
What precautions should be observed while preparing samples for AAS and AES?
..
..
...
...

11.4

APPLICATIONS OF AAS

Atomic absorption spectrophotometry is now a routinely and widely employed

technique for trace and ultratrace analysis of complex matrices of geological,
biological, environmental or industrial origin. The atomic absorption methods using
flame are rapid and precise and are applicable to about 67 elements. Electrothermal
methods of analysis on the other hand are slower and less precise; however, these are
more sensitive and need much smaller samples. Let us take up some applications of
AAS in different areas. We begin with biological samples.

11.4.1

Serum is the supernatant

liquid of the clotted blood
and is separated by
centrifugation after
addition of anticoagulant
such as heparin.

Biological Samples

A wide range of the samples of biological origin are subjected to analytical procedures
for the determination of the elements present in them. These may include plant leaves,
fruits, vegetables, blood, urine, muscle tissue, hair, etc. The major difficulty in the
analysis of these materials is their complex nature. More so, these samples cannot be
analysed directly but require dry ashing followed by wet digestion with oxidising
acids such as HNO3 and HClO4 . In case of blood analysis, plasma or serum is
generally preferred because of the presence of significant amounts of clinically
significant elements in them.
i)

Determination of calcium in serum

A typical AAS determination of calcium in serum is carried out by calibration method

wherein, a calibration plot is obtained by measuring the absorption of characteristic
radiation (422.67 nm) for a series of standard solutions of calcium in a similar matrix.
An air-acetylene flame is used with a premix burner. The normal calcium content of
serum is generally about 100 ppm and it is determined by diluting the sample 1:20
with 1% SrCl2 solution. Thus, a typical sample would contain about 5 ppm of Ca.
Therefore, an equivalent amount of sodium and potassium are added to the standard
solutions. The plot is then used to determine the concentration of the given sample.
It needs to be mentioned that the effects of instrumental parameters and of phosphate
and aluminium ion on calcium absorption are to be suitably accounted for an effective
determination. Instrumental parameters such as burner height and fuel air ratio may be
studied to optimise the experimental conditions of flame height and fuel gas pressure.

62

Similarly the effect of organic solvent such as ethanol may also be studied. The effects
of interferants is borne by using 5 ppm each of phosphate, sodium and aluminium
solutions

Applications of AAS
and AES

In an alternative determination, using the method of standard addition a series of

calcium standards of 0, 2.5, 5, 7.5, 10 and 15 ppm are prepared from the 50 ppm stock
solution and SrCl2 is added to standards and the unknown to give a final concentration
of 1%. The standard addition absorbance calibration plot is then prepared and used for
the determination of the concentration of analyte sample.
ii)

Determination of cadmium

Cadmium is one of the most important toxic elements from the environmental point of
view. It occurs in nature mainly due to volcanic activity. It is used in plating of metals,
as stabiliser in polyvinyl chloride, pigments, Ni-Cd batteries and alloying. It is the
prime cause of itai-itai disease first observed in Japan. Cadmium along with lead has
been the most studied element with regard to human toxicology as it has no role in
human or plant nutrition. It is highly toxic even in trace amounts to the human body.
Total intake of cadmium in Germany, USA and most European countries is in the
range, 10-30 g/day whereas in contaminated areas of Japan, its intake is as high as
400 g/day. It is most likely to be ingested by tobacco smoking especially cigarettes.
Absorption of cadmium is higher in females than in males though its transport in the
intestinal tract is influenced by the presence of various food components such as
proteins and amino acids.
Cadmium in blood may be used as a biological monitoring measure for recent
occupational/environmental exposure. In addition, cadmium in urine may also be used
as a measure of biological monitoring for body burden where it reflects the total
accumulation of cadmium in the body. Typically it occurs at 1g/L in the blood of
healthy and nonexposed nonsmokers in various countries. Considering the
requirements of detection limit and contamination free sample handling, graphite
furnace atomic absorption spectrophotometry is the method of choice where the
detection limit is 0.04 g/L.
A typical determination of cadmium in blood involves de-proteination with nitric acid
followed by direct determination by GFAAS using source with 228.8 nm output. The
blood sample is collected in plastic collection tubes using vinyl gloves free of talc and
is stored at a temperature of 20 oC to 4 oC. All the laboratory ware is to be soaked in
diluted nitric acid and biodistilled quality water is used for dilution work. The
determination is preceded by the obtaining calibration curves using matrix adapted
calibration solutions. In simple words it means that the calibration solution contains all
the known components of the analyte sample. A multiple standard calibration is
preferred. Similarly, Cd could also be determined in urine, hair and other body tissues.
iii)

Quality control is usually

carried out by using
certified reference
materials from NIST
(USA) and NIES (Japan).

Determination of lead

As you know, lead is another highly toxic element which is an environmental

contaminant. It enters into biological systems like plants and animals and reaches
blood, urine, teeth, bones, hair, plant and animal tissues, etc. These materials need to
be analytically assessed for the amount of lead so that its damage potential can be
ascertained. From the viewpoint of occupational and environmental toxicology the
determination of lead in blood is the most important since the concentration of lead in
whole blood is considered to be the best indicator of current lead exposure in humans.
It enters into human blood because of inhalation of polluted air, food and water though
these are less relevant for assessing health hazards for humans than the amount of lead
actually absorbed.
In a typical lead determination, after adding heparin, a natural anticoagulant, the blood
is treated with trichloroacetic acid to precipitate proteins. These are then separated by

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Atomic Spectroscopic
Methods-II

centrifugation. In order to avoid interferences, lead is extracted in an organic solvent

methyl isobutylketone (MIBK) after adding ammonium pyrrolidinedithiocarbamate
(APDC) at pH 3. The lead is extracted as Pb (APCO)2. The organic phase is then
aspirated into air-acetylene flame for the determination of lead. The detection limit of
lead in blood is 0.1 g/mL. Most values of lead in blood are in the range 0.3 0.4
g/mL with 0.6 g/mL as the upper limit. It is essential that internal and external
quality control should be used for the determination of lead in blood.
iv)

Zinc in plant leaves

Zinc is an essential nutrient in plants and remains distributed in all parts of the plant.
About 1g dried plant leaves are grounded with pestle and mortar and dry ashed in
silica crucible at 500C. The ash is then dissolved in acid and final solution is prepared
to 0.1 M HCl. The solution is then directly aspirated into an air-acetylene flame of
AAS. A blank is also prepared in exactly similar manner.

11.4.2

Environmental Samples

Air, soil and water are three components of environment where determination of toxic
contaminant is of extreme importance. Analysis of particulate matter in air from
industrial establishments is the most representative study of environmental samples by
atomic spectrometry.
i)

Analysis of airborne particulate matter

In the analysis of airborne particulate matter, the choice of sample collection location
and collection procedure is very important. For example samples may be collected
from surrounding areas of a factory emitting harmful gases affecting workers health
adversely or a residential colony located near industrial establishment where toxic
pollutants may travel and thus affect general public. A measured volume of air is
collected on a cellulose acetate membrane filter using air sampler. Weighed amount of
particulate matter is scratched out of the filter paper or the filter paper itself may be
dry ashed in a low temperature furnace so as to avoid loss of volatile elements. The
particulate matter or ash is then dissolved using acid digestion method and heating on
hot plate. The final solution is prepared in dilute HCl and making up final volume to a
fixed volume. Appropriate hollow cathode lamps are selected depending on the
elements to be determined and respective standard solutions are prepared. Calibration
plots should be drawn for each element to be determined and the test solution is
aspirated. Thus concentration of desired elements in air dust particulate matter may be
determined. Results are usually reported in terms of g/m3 of air.
ii)

Mercury in air/water

Metallic mercury is important as it forms amalgam with other metals. Its alloy with
silver was earlier used by dentists for dental filling though it is no longer so because of
toxicological effects known since many years. Mercury in air is collected by bubbling
air through an acidic KMnO4 solution where volatile elemental mercury is trapped by
oxidising it to Hg2+. The excess permanganate is reduced with hydroxylamine, and the
collected mercury (or mercury in a water sample) is then reduced to the element by
SnCl2 according to following equations.
5Hg0 + 2MnO 4 + 16H+

6MnO4 + 5NH2OH + 13H+

Hg2+ + SnCl2 + 2Cl

5Hg2+ + 2Mn2+ + 8H2O

6Mn2+ + 5NO3 + 14H2O
Hg0 + SnCl4

As elemental mercury has appreciable vapour pressure at room temperature, and by

bubbling argon through the solution, mercury vapour is swept into a quartz ended cell
where its atomic absorption is measured at 253.6 nm using mercury line. A calibration
curve should be prepared before the sample is run. At least two blanks should also be
64

prepared in the same manner, omitting the addition of mercury. The measured
absorbance is corrected for the blanks and the amount of mercury is determined from
the calibration curve.

Applications of AAS
and AES

Similarly, the water sample from tap, river, or other sources can be analysed. Tap
water should contain around 1 ppb or less mercury. In such determinations the water
samples and the standards should be run in a similar manner. As in the case of air
samples, the correction should be made for the reagent blank as its magnitude will
generally govern the detection limit of the procedure. Extreme care must be taken to
minimise reagent and glassware contamination. From the calibration graph the
quantity and concentration of mercury in the sample is determined.
iii)

Trace element contamination in soil

In order to determine toxic contaminants in soil samples, the representative samples

are collected from surface of the soil, and also at some depth. These are then passed
through a sieve to make it uniform sample and is stored in separate containers to avoid
cross contamination. In order to determine all the contaminants, the sample is prepared
by treating a weighed amount of soil with 1:1 nitric acid and making appropriate
solution. Metal contents such as Ni, Cu, Zn, Cd, Pb, etc. are then determined by using
appropriate hollow cathode lamp and air-acetylene flame. It is essential that the
standard solutions for each element are prepared in appropriate concentration range
and their respective calibration plots are obtained.

11.4.3

Industrial Samples

Quality control of finished products of steel industry and other products such as alloys
requires accurate analysis. For such an analysis an alloy or steel is be dissolved in acid
(HCl, HNO3, HClO4 or a mixture of these) and a solution is prepared for analysis by
AAS. Care must be taken to eliminate excess of acid. A typical example is described
in following lines.
i)

Determination of molybdenum in steel

Weighed amount of sample is dissolved in aqua regia and finally in dil HCl. Final
volume is made up to fixed volume in a volumetric flask by adding doubly distilled
water. Molybdenum can be determined in acetylene-air or acetylene-N2O flame
selecting a wavelength of 313.26 nm. Let us take up an example.
Example
0.32 g stainless steel sample was dissolved in nitric acid and the resulting solution was
made to 100 cm3 with water. Five standards and the sample solution were aspirated
into flame for the determination of nickel. The following observations were made.
Concentration of Nickel (ppm)

Absorbance

0.126

0.250

0.374

0.500

10

0.626

Sample

0.226

Calculate the percentage of nickel in steel sample.

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Atomic Spectroscopic
Methods-II

Solution
Let us prepare the calibration plot by taking the concentration on X-axis and
absorbance on Y-axis, as shown below

According to the calibration plot the sample concentration is found to be 3.612 ppm. It
corresponds to 1.12%.
ii)

Tin in canned fruit juice

Availability of fruit juice in tinned cans is becoming increasingly common though it is

also marketed in cartons. As tin is likely to be leached in acidic medium of juice the
contents of the can get contaminated. Hence its determination is quite important to
ascertain the contamination, if any. Sn can be determined successfully by graphite
furnace atomic absorption spectrophotometry (GFAAS). In a typical determination,
the juice solution is prepared in dil HCl and boiled till it becomes clear. In case the
solution is still turbid or colloidal then it is centrifuged and only supernatant is taken
for analysis. As the concentration of Sn in juice is likely to be very low, standards are
prepared in the concentration range 25-100 ppb together with acid as blank. The
measurement is made at a wavelength of 224.6 nm.

SAQ 2
Enlist some important applications of AAS in the area of environmental analysis.
..
..
...
...

11.5

APPLICATIONS OF AES

Emission spectroscopy is widely used for qualitative as well as quantitative analysis

because of high sensitivity and the possible simultaneous excitation of many elements,
notably metals and metalloids. AES is especially suited for rapid survey analysis of
the elemental contents in small samples at level of 10g/g or less. It is essential to
construct an analytical curve with known standards. Often the ratio of analyte
emission intensity to the emission intensity of a second element contained in, or added
to the sample is used. This internal standard method improves the precision of
analysis.
ICP-AES is used widely for determining trace metals in environmental samples such
as drinking water, industrial waste water and ground water supplies and so also for
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determining trace metals in petroleum products, biological materials, foodstuffs

geological samples and industrial quality control. The simultaneous multielemental
determinations make it possible to form correlations and to reach conclusions that are
impossible with single element determinations. The excellent sensitivity and wide
working range for many elements together with the low level of interferences make
ICP-AES a nearly ideal method. Let us learn about some typical analytical
determinations in different areas using AES.

11.5.1

Applications of AAS
and AES

Biological Samples

As you have learnt above, a wide range of the samples of biological origin are
subjected to analytical procedures for the determination of the elements present in
them. Let us take up the determination of sodium in serum as a representative example
of the application of AES in biological samples.
Determination of sodium in serum
Determination of sodium in water or serum is carried out by following the
characteristic emission at 589 nm. A calibration plot is prepared between emission
intensity and concentration of the standard solutions. The concentration of the sample
solution is then determined from the calibration plot. In some of the determinations a
known amount of an internal standard like lithium is added to the standard solutions as
well as the sample solution. The calibration curve is drawn between the emission
intensity ratios of the characteristic emissions of sodium to lithium versus the
concentration of the standard solutions of sodium.

11.5.2

Geological Samples

The analysis of geological samples constitutes a major area of the application of

atomic emission spectrometry. A large proportion of the elements of the periodic table
present in the geological samples can be conveniently determined by ICP-AES
spectrometry. These are now routinely being measured well within the limits of the
methods. In past, a number of analytical methods have been described for the
determination of a particular element in a given sample type. These methods could not
be used in a generalised way for samples with analytically different matrices. It
became difficult to determine the other elements present in the matrix. More so, the
elements that are readily detected in mineralised rock samples may not be detectable
in non-mineralised samples such as water. However, when ICP-AES is used for
analysis of normal silicate rocks, the range of elements that can be measured is large.
Only a few of the elements present at concentration above the 10 g g-1 level are not
readily determined by routine ICP analysis.
You might know that in the context of rock analysis, there are ten elements that are
conventionally quoted as oxide equivalents. These are Si, Al, Fe, Mg, Ca, Na, K, Ti,
Mn, P; these can be determined without difficulty. In addition, many of the trace
elements such as Li, Sr, Ba, Sc, Y, La, Zr, V, Nb, Cr, Co, Ni, Cu and Zn, that are
determined in a routine trace analysis programme can also be conveniently measured
by ICP analysis. The detection limits for some typical elements by ICP are compiled
in Table 11.2.
Further, the trace elements including Mo, Ag, Cd and Hg in mineralised geological
samples can readily be determined when they occur at levels above background
concentration. Lead can also be measured in mineralised samples but not as well at
normal levels in silicates (below 20-40 g/g). The detection limits for Sn, W, U and
Th are not good, but concentrations above 50 g/g can be measured. It is also possible
to determine the rare earth elements down to sub g/g level in a rock sample using a
concentration technique.

67

Atomic Spectroscopic
Methods-II

Table 11.2: Detection limits (g/ml) of different elements by ICP-AES

11.5.3

Element

Detection limit

Element

Detection limit

Ag

0.004

Mo

0.0001

Al

0.00008

Na

0.00002

As

0.002

Ni

0.0001

Au

0.04

0.015

0.0001

Pb

0.001

Ba

0.00001

Pd

0.0008

Be

0.000003

Pt

0.08

Ca

0.0000001

Rh

0.003

Cd

0.0002

Sc

0.003

Ce

0.0004

Se

0.03

Co

0.003

Si

0.01

Cr

0.0008

Sn

0.003

Cu

0.0006

Sr

0.00003

Fe

0.00009

Th

0.003

Ga

0.0002

Ti

0.00003

Hf

0.01

Tl

0.2

Hg

0.01

0.03

In

0.03

0.00006

La

0.001

0.0007

Mg

0.000003

Zn

0.00001

Mn

0.00002

Zr

0.00006

Environmental Samples

Environment is an important area wherein the elemental analysis is of significant

importance. Let us take up the analysis of trace elements in airborne particulate matter
by AES as a representative example of this group.
Trace elements in airborne particulate matter
AES has been used extensively for the determination of trace elements in atmospheric
particulates, especially large scale survey studies where simultaneous multielement
analysis is required. Airborne particulate matter is routinely collected by drawing a
measured volume of air through filter material such as fiberglass, asbestos, cellulose
paper, porous plastic, or graphite in the form of discs or electrodes. However, for the
determination of trace elements, the chemical composition of filter is important. For
example glass filters show high concentrations of Ba, Sr, Rb, Zn, Ni, Fe, Ca, As and
other elements. The composition of filter materials is particularly significant in
sampling relatively clean atmospheres because of the low particulate levels collected
in reasonable sampling time.
The particulates are collected, dried, and weighed; then spectroscopic buffer is added
along with internal standards. The sample so prepared is then suitably determined. The
detection limits between 0.1 and 5 ng can be obtained for up to 14 elements.

68

11.5.4

Industrial Samples

The application of atomic emission spectroscopy in analysing the industrial samples

can be illustrated by considering the determination of metals in lubricating oil as
discussed below.

Applications of AAS
and AES

Determination of metals in lubricating oil

The determination of metals in lubricating oils used in aircraft, truck, locomotive and
other engines provide an excellent indication of the mechanical wear and tear of the
engine. Infact, as the concentration of certain metals increases, the wearing out parts
or components of the engine can be identified resulting in a decision about their
replacement or repair. This routine programme of wear-metal analysis saves lot of
money all around the world. The most important wear metals that are monitored are
Fe, Al, Mg, Cu and Ag along with other trace metals. Iron appears as an indicator of
more than 80 percent of all component failures detected by wear-metal analysis.
Aluminium usually relates to wear of oil pumps, cases, housings, pistons and cylinder
heads, and copper to wear of bronze parts such as bushings and retainers. Silicon is
useful as an indicator of lubricant contamination from dust. These determinations are
generally made by spark AES method and the spectra of 10 or more elements in the
range of 0.1 to 500 ppm are determined.

SAQ 3
Enlist any five elements present in rock samples that are expressed in terms of their
oxide equivalents.
..
..
...
...

SAQ 4
What do you understand by wear metal analysis? What is its significance?
..
..
...
...
...

11.6

SUMMARY

Atomic absorption spectrophotometry (AAS) and atomic emission spectrometry

(AES) are being widely used for the elemental analysis of geological, biological,
environmental, industrial and other types of samples.
The salient features of AAS and AES along with a comparative account of the two
techniques, followed by the sample preparation for the analytical determination by
these technique have been recapitulated in this unit to give an overall picture of the
two techniques. The importance and principles of some important typical applications
of AAS and AES in diverse areas such as biological sample, environmental samples,
and industrial samples have also been discussed.

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Atomic Spectroscopic
Methods-II

11.7

TERMINAL QUESTIONS

1.

Explain why simultaneous multielemental determination by ICP-AES is easier

compared to that by AAS.

2.

Explain the difference between atomic emission and atomic absorption

spectrometry.

3.

Define the following terms;

a)

Plasma,

b)

Spectral interference

4.

Explain the observation during AAS determination of uranium where a linear

relationship is observed in the concentration range of 500 to 2000 ppm. At lower
concentrations, the relationship is nonlinear which, however, becomes linear if
2000 ppm of alkali metal salt is added.

5.

Explain the following observations:

6.

a)

Atomic emission is more sensitive to flame instability than atomic

absorption.

b)

Monochromators of higher resolution are found in ICP-AE spectrometers

but not in flame AA spectrometers.

c)

Inductively coupled plasmas are suitable for atomic emission

spectrometry but it is rarely used for AAS.

Copper was determined in an aqueous sample by AAS following standard

addition method. First 10.0 mL each of the sample was pipetted into each of
50.0 mL volumetric flasks. A standard containing 12.5 ppm of Cu were added to
the flasks and the solutions were made up to the volume. Following were the
absorbances.
Standard, mL

Absorbance

0.201

10.0

0.292

20.0

0.378

30.0

0.467

40.0

0.554

Plot absorbance as a function of volume of the standard and calculate the

concentration of Cu in the sample.

11.8

ANSWERS

Self Assessment Questions

1.

In the process of preparing the sample for AAS or AES,

70

all possible contamination coming from the air, from the skin of the
sample collector, additives and reagents used in the analysis, as well as
parts of instrumentation including glass or plastic wares should be
avoided.

2.

biological materials of human and plant origin must be handled with

extreme care due to their inhomogeneity especially for trace element
analysis.

body fluids such as blood, viscera, urine, etc should be stabilised and
homogenised so as to avoid occurrence of any changes in their
composition, prior to actual analysis.

the total number of transfers should be kept to a minimum.

Applications of AAS
and AES

Some of the important applications of AAS in the area of environmental

analysis are as follows

Analysis of airborne particulate matter

Determination of mercury in air/water

Determination of trace element contamination in Soil

3.

The following elements are conventionally quoted as their oxide equivalents:

Si, Al, Fe, Mg, Ca, Na, K, Ti, Mn, and P

4.

The wear metal analysis refers to the determination of metals in used lubricating
oils from the aircraft, truck, locomotive and other engines. This provides an
assessment of the mechanical wear and tear of the engine.

Terminal Questions
1.

In case of ICP-AES all the elements get excited at the same time in the plasma
torch. The radiation emitted by them can be measured sequentially or
simultaneously. Hence it is easier to determine several elements
simultaneously. However, in case of AAS a line source hollow cathode lamp is
used as the radiation source. As only one analyte element is able to absorb the
radiation emitted by the cathode lamp we can measure only one element at a
time. For multielemental determination by AAS we need to use a cathode lamp
for each element thus making it a difficult task.

2.

Basic difference between atomic emission (AES) and atomic absorption (AAS)
spectrometry is the source of radiation and the measured parameter. In AES, the
source of radiation is sample itself where the energy for excitation of analyte
atoms is supplied by plasma, a flame, an oven or an electric arc or spark. The
signal is the measured intensity of the source at the wavelength of interest. On
the other hand in case of AAS, the source of radiation is a line source such as
hollow cathode lamp. The signal is in terms of absorbance calculated from the
radiant power of the source and the resulting power after the radiation has
passed through the atomised sample.

3.

a)

Plasma is a conducting gas that contains a large concentration of

and/or electrons.

b)

Spectral interference is due to overlap of lines of an element in the

sample matrix with that of an analyte.

ions

4.

Deviations from linearity at low concentrations are often due to significant

ionization of the analyte. When an easily ionized element salt such as that of
alkali metal is added in excess amount then the ionization of analyte is
suppressed because of the electrons produced by ionization of the metal.

5.

a)

In AES, the analyte signal is produced by the small number of excited

atoms or ions whereas in AAS the signal is obtained from absorption by
much larger number of unexcited species. Any small change in flame

71

Atomic Spectroscopic
Methods-II

conditions influence the number of excited species. Whereas such changes

have insignificant effect on the number of unexcited species.

6.

72

b)

Monochromator plays an important role in the resolution and selectivity of

ICP emission. Thus a high resolution monochromator can isolate the
analyte spectral line from other lines and background emission and reduce
spectral interferences. In AAS, however, resolution comes primarily from
specific line emitted by a hollow cathode lamp. The monochromator
isolates only the emission line of the analyte element from lines of
impurities and fill the gas where a much lower resolution is needed.

c)

Temperature of inductively coupled plasma is quite high which favours

the formation of atoms and ions. Also sample residence times are long so
that desolvation and vaporisation are complete. Further atoms and ions are
formed in a nearly chemically inert atmosphere. Nearly constant electron
concentration leads to fewer ionization interferences. Since excited state is
not formed or it is less stable because of high temperature, it is not useful
for AAS.

Concentration of Cu as obtained from the plot is 28.0 ppm.

SOME USEFUL BOOKS

1.

Vogels Textbook of Quantitative Chemical Analysis by J. Menham, R.C.

Denney, J.D. Barnes and M.J.K. Thomas, 6th Edn, Low Price Edition, Pearson
Education Ltd, New Delhi (2000), Ch. 15.

2.

Quantitative Analysis by R. A. Day and A. L. Underwood, 6th Edn, Prentice

Hall of India, New Delhi (2001), Ch. 14

3.

Instrumental Analysis, Editors, H. H. Bauer, G. D. Christian and J. E. OReilly,

2nd Edn, Allyn and Bacon, Inc., Boston (1991), Ch. 10.

4.

Principles of Instrumental Analysis by D. A. Skoog, F. J. Holler and T. A.

Nieman, 5th Edn, Thomson Brooks/Cole, Bangalore (2004).

5.

Fundamentals of Analytical Chemistry by D. A. Skoog, D. M. West, F. J. Holler

and S. L. Crouch, 8th Edn, Thomson Brooks/Cole, Bangalore (2004).

6.

Analytical Chemistry by G. D. Christian, 6th Edn, John Wiley & Sons Inc,
Singapore (2003), Ch. 15.

7.

Instrumental Methods of Analysis by H. H. Willard, L. L. Merritt, J. A. Dean

and F. A. Settle, 7th Edn., CBS Publishers & Disributors, New Delhi (1986)
Ch. 10.

8.

Principles and Practice of Analytical Chemistry by F.W. Fifield and D. Kealey,

5th Edn, Blackwell Science Ltd, New Delhi (2004), Ch. 8.

9.

Modern Methods for Trace Element Determination by C. Vandecasteele and C.

B. Block, John Wiley & Sons, New York (1997), Ch. 5.

10.

Handbook of Instrumental Techniques for Analytical Chemistry, Editor, F.

Settle, Low Price Edition, Pearson Education Inc, New Delhi (2004), Ch. 20.

11.

Instrumental methods of Chemical analysis by G. W. Ewing, 5th Edn, Mc-Graw

Hill, Singapore (1985).

12.

Atomic Absorption Spectrometry, Ed. S. J. Haswell, Elsevier, Amsterdam

(1992).

13.

Trace Element Analysis in Biological Specimens, Eds, R. F. M. Herber and M.

Stoeppler, Elsevier, Amsterdam (1994)

Applications of AAS
and AES

73

Atomic Spectroscopic
Methods-II

INDEX
Absorbance 7, 8, 9, 14, 59, 63, 65
Acid digestion method 40, 64
Advantages and disadvantages of GFAAS 16
Agricultural science 51
Analytical methodology in ICP-AES 47
Qualitative analysis using ICP-AES 48
Characteristic line groupings 48
Line coincidences 48
Persistent or RU 48
Spectral line tables 48

Quantitative analysis 48

Appearance of ICP plasma 37

Applications of AAS 62
Biological samples 62
Determination of calcium in serum 62
Determination of cadmium 63
Determination of lead 63
Zinc in plant leaves 64

Environmental samples 64
Analysis of airborne particulate matter 64
Mercury in air/water 64
Trace element contamination in soil 65

Industrial samples 65
Determination of molybdenum in steel 65
Tin in canned fruit juice 66

Applications of AES 66
Biological samples 67
Determination of sodium in serum 67

Geological samples 67
Environmental samples 68
Trace elements in airborne particulate matter 68

Industrial samples 69
Determination of metals in lubricating oil 69

Applications of ICP-AES 51
Agricultural science 51
Environmental science 51
Forensic sciences 51
Geological sciences 51
Health sciences 51
Industry 51
Metallurgy 51

Applications of atomic absorption spectrophotometry 26

Merits and limitations of atomic absorption spectrophotometry 27

Argon gas supply 36

Argon plasma spectroscopy 34
Atomic absorption spectrophotometers 17
Double beam atomic absorption spectrophotometer 18
Single beam atomic absorption spectrophotometer 17

Atomic emission spectrometry based on plasma sources 33

Atomisers 11
Auxiliary gas 35
Background absorption 20
Biological samples 57, 61, 62, 67
Burners 12
Calibration plot method 8
Carbon rod 14
CCD based spectrometers 47
Characteristic line groupings 48

74

Chemical interferences 20
Chemical interferences 50
Choice of argon as plasma gas 38
CID based instruments 47
Comparison between AAS and AES 59
Concentration dependence of absorption 7
Continuum sources 10
Dc electrical source 34
Detectors 13, 39
Direct current plasma 37
Double beam atomic absorption spectrophotometer 18
Dry attack method 41
Echelle spectrometers 46
Electrodeless discharge lamps 11
Electrothermal atomisers 11, 14
Electrothermal vaporisation 42
Environmental samples 64, 66, 68
Environmental science 51
Filament 14
Flame atomiser 11
Forensic sciences 51
Frit nebuliser 42
Fuel-oxidant ratio 12
Furnace atomic absorption spectrophotometry 14
Geological samples 67
Geological sciences 51
Graphite furnace 15, 58, 60
Graphite furnace atomic absorption spectrophotometry 14

Applications of AAS
and AES

Advantages and disadvantages of GFAAS 16

Carbon rod 14
Electrothermal atomisers 14
Graphite furnace 15

Filament 14
Furnace atomic absorption spectrophotometry 14
Graphite tube 14
Handling background absorption in GFAAS 16
LVov furnace 14

Graphite tube 14
Handling background absorption in GFAAS 16
Health sciences 51
Hollow cathode lamp 11
Hydride generation 42
Hydride generation technique 24
Industrial samples 59, 65, 69
Industry 51
Instrumentation for ICP-AES 39
Detector 39
Monochromator 39
Nebuliser 39
Plasma source 39
Processing and readout device 39
Sample Introduction 40
Dry attack method 41
Electrothermal vaporisation 42
Frit nebuliser 42
Hydride generation 42
Nebulisation 41
Nebuliser 42
Nebulisers for ICP-AES 42

75

Atomic Spectroscopic
Methods-II

Sample preparation 41
Acid digestion method 41

Ultrasonic 42

Instrumentation for atomic absorption spectrophotometry 10

Atomisers 11
Burners 12
Premix nebuliser-burner 12
Total consumption burner 12
Turbulent flow burner 12

Flame atomiser 11
Fuel-oxidant ratio 12

Detectors 13
Monochromators 13
Radiation sources 10
Continuum sources 10
Electrodeless discharge lamps 11
Hollow cathode lamp 11
Line sources 10

Readout devices 14

Interferences in ICP-AES 50
Chemical interferences 50
Physical interferences 50
Spectral interferences 50

Interferences in atomic absorption spectrophotometry 19

Chemical interferences 20
Physical interferences 20
Spectral interferences 19
Background absorption 20

Internal standard method 8

Lvov furnace 14
Lambert-beers law 7
Line coincidences 48
Line sources 10
Mechanism of plasma formation 36
Merits and limitations of atomic absorption spectrophotometry 27
Metallurgy 51
Microwave digestion 22
Microwave digestion system 22
Microwave frequency generator 34
Microwave induced plasma 38
Monochromators 13, 39
Nebulisation 41
Nebuliser 39, 42
Nebulisers for ICP-AES 41
Persistent or RU 48
Physical interferences 20, 50
Plasma and its characteristics 34
Argon plasma spectroscopy 35
Choice of argon as plasma gas 38
DC electrical source 35
Direct current plasma 37
Inductively coupled plasma 35
Appearance of ICP plasma 37
Argon gas supply 36
Auxiliary gas 35
Mechanism of plasma formation 36
Quartz tube 35
Radio frequency power generators 36
Three electrodes DCP 37
Torch 35
Toroidal plasma 36
Work coil 36

Microwave frequency generator 35

76

Microwave induced plasma 38

Plasma sources 34
Radio frequency generator 35

Applications of AAS
and AES

Plasma source 34, 39

Polychromators 45
Premix nebuliser-burner 12
Preparation of the sample 21
Principle of atomic absorption spectrophotometry 6
Concentration dependence of absorption 7
Absorbance 7
Lambert-beers law 7

Quantitative methodology 7
Calibration plot method 8
Internal standard method 8
Standard addition method 9

Principle of atomic emission spectrometry 32

Atomic emission spectrometry based on plasma sources 33

Processing and readout device 39

Qualitative analysis using ICP-AES 48
Quantitative analysis 48
Quantitative methodology 7
Quartz tube 35
Radiation sources 10
Radio frequency generator 35
Radio frequency power generators 36
Readout devices 14
Rowland circle 47
Sample handling in atomic absorption spectrophotometry 21
Microwave digestion 22
Microwave digestion system 22

Preparation of the sample 21

Sample introduction methods 23
Electrothermal vapourisation 24
Hydride generation technique 24
Ultrasonic nebulisation 24

Scrubbing 21
Use of organic solvents 22

Salient Features of AAS 58

Salient Features of AES 59
Sample introduction 40
Sample introduction methods 23
Sample preparation 40, 61
Scrubbing 21
Sequential spectrometers 44
Simultaneous spectrometers 45
Single beam atomic absorption spectrophotometer 17
Skew scan instruments 44
Solid state array detector spectrometers 46
Spectral interferences 19
Spectral interferences 46, 50
Spectral line tables 48
Standard addition method 9
Three electrodes DCP 37
Torch 35
Toroidal plasma 36
Total consumption burner 12
Turbulent flow burner 12
Types of instruments for ICP-AES 44
Sequential spectrometers 44

77

Atomic Spectroscopic
Methods-II

Skew scan instruments 44

Simultaneous spectrometers 45
Polychromators 45
Echelle spectrometers 46

Solid state array detector spectrometers 46

CCD based spectrometers 47
CID based instruments 47
Rowland circle 47

Ultrasonic 42
Ultrasonic nebulisation 24
Use of organic solvents 22
Work coil 36

78