Basic Principles of

Atomic Absorption and

Atomic Emission
Spectroscopy

1
 Flame Atomic Emission Spectrometer

P Signal Processor
Source Wavelength Selector Detector Readout

Sample

2
 Flame Atomic Emission Spectrometer

3
 Emission Techniques
Type Method of Atomization Radiation Source
Arc sample heated in an sample
electric arc (4000-5000oC)
Spark sample excited in a sample
high voltage spark

Flame sample solution sample

aspirated into a flame
(1700 – 3200 oC)
Argon sample heated in an sample
plasma argon plasma (4000-6000oC)

4
 Emission Spectroscopy
Flame and Plasma Emission Spectroscopy are based upon those
particles that are electronically excited in the medium.
The Functions of Flame and Plasma
1. To convert the constituents of liquid sample into the vapor
state.
2. To decompose the constituents into atoms or simple molecules:
M+ + e- (from flame) -> M + hn
3. To electronically excite a fraction of the resulting atomic or
molecular species
M -> M*

5
 Emission Spectroscopy

Measure the intensity of emitted radiation

Exc ited State

Emits Special
Electromagnetic Radiation

6 Ground State
7
 Argon Inductively Coupled Plasma as an
atomization source for emission spectroscopy

8
9
 Why plasma source or other high
energetic sources?
• Flame techniques are limited to alkali (Li, Na, K, Cs,
Rb) and some alkaline earth metals (Ca and Mg)
• More energetic sources are used for
– more elements specially transition elements
– simultaneous multielement analysis since spectra
od dozen of elements can be recorded
simultaneously
– Interelement interference is eliminated
– Liquids and solids

10
 Advantages and disadvantages of
emission spectrometry
Advantages
• rapid
• Multielement (limited for alkali and some alkaline earth
metals

• ICP-AES has become the technique of choice for metals

analysis.

Disadvantages
• initial cost of ICP instrumentation
• continuing cost of operation (Ar required)

11
 Flame Atomic Absorption Spectrometer

Po P Signal Processor
Source Wavelength Selector Detector Readout

Chopper

Sample

12
 Flame Atomic Absorption Spectrometer

T
13
 Atomization Techniques
Type Method of Atomization Radiation Source
Atomic sample solution aspirated HCL
(flame) into a flame

atomic sample solution evaporated HCL

(nonflame) & ignited (2000 -3000 oC)
(Electrothermal)

Hydride Vapor hydride generated HCL

generation

Cold vapor Cold vapor generated (Hg) HCL

14
Advantages and disadvantages of atomic
absorption
Advantages
• sensitive (GFAA)
• selective

Disadvantages
• intended for metallic/metalloid atomic species, not
nonmetals or intact molecular species
• lamps - one element at a time
• not easy for solids
• calibration curves nonlinear above A = 0.5
• more costly and less widely applicable than UV vis
• matrix effects - easy for some metals to be masked
15
16
 Flame Fluorescence Spectrometer

Po P Signal Processor
Wavelength Selector Detector Readout

90o

Source

Sample

17
 Fluorescence Techniques
Type Method of Atomization Radiation Source
atomic sample soln. aspirated sample
(flame) into a flame
atomic sample soln. evaporated sample
(nonflame) & ignited
x-ray none required sample
fluoresence

18
 Processes that take place
in flame or plasma

19
T1
 Flames
Regions in Flame Temperature Profile

20
21
22
23
24
25
26
 Flameless atomization
Electrothermal atomization
Graphite furnace atomization

27
28
29
30
Why do we use a temperature program in
flameless AA?

31
 Why do we use an inert gas with
Flameless atomization?

32
 Light source used for AA

• What light source do we use with AA?

• Would it be a continuous light source or a
line light source?

• A line light source is used for AA

33
T2

34
35
How does the line source
provide a single wavelenght?

T3

36
37
38
 AA spectrophotometer

39
40
41
42
43
Relationship Between Atomic Absorption and
Flame Emission Spectroscopy

• Flame Emission -> it measures the radiation emitted by the

excited atoms that is related to concentration.
• Atomic Absorption -> it measures the radiation absorbed by the
unexcited atoms that are determined.
•Atomic absorption depends only upon the number of unexcited
atoms, the absorption intensity is not directly affected by the
temperature of the flame.
•The flame emission intensity in contrast, being dependent upon
the number of excited atoms, is greatly influenced by
temperature variations.
44
Measured signal and analytical concentration
1. Atomic Emission
Signal = Intensity of emission = KNf = K’Na =K’’C
Nf = number of free atoms in flame
Na = number of absorbing atoms in flame
C = concentration of analyte in the sample
K, K` and K’’ depend upon:
• Rate of aspiration (nebulizer)
• Efficiency of aspiration (evaporation efficiency)
– Flow rate of solution
– Solution concentration
– Flow rate of unburnt gas into flame
• Efficiency of atomization (effect of chemical environment).
This depends upon
– Droplet size
– Sample flow rate
– Refractory oxide formation
– Ratio of fuel/oxygen in flame
• Temperature effect (choice of flame temperature)
45
2. Atomic absorption
Signal = I absorbed = Absorbance = A = k l C

• For the measurement to be reliable k must

be constant; k should not change when a
change in matrix or flame type takes place.
• K depends upon same factors as those
for the atomic emission spectroscopy

46
 Background and
Background Correction

47
• Definition
• Sources of Background
• Background correction:
– Blank correction method
– Two-line correction method
– Continuous source correction
method
– Zeeman effect correction method

48
What is a background?

• It is the signal observed when the element sought is

absent

• The light at a specific wavelength (Analyte wavelength) is

attenuated by the effect of flame components or matrix
components in the sample

• Thus measured absorbance and analyte concentrations are

too high
• If problem from flame, blank aspiration will correct for it

• It is more serious at short wavelengths (< 430 nm) and with

graphite furnace
49
Sources of Background in atomic
absorption
1. Absorption by flame itself (Serious at 
below 220 nm; e.g., As, Se, Zn )
• Water blank can compensate for this flame
absorption
• In flame absorption, background
interference is insignificant at  > 230 nm

50
2. Absorption by concomitant molecular species originating
from the matrix like NaX or solvents containing X
(halogen) like CCl4.
• Halides absorb at  < 300 nm

3. Scattering of radiation from the particulate material in the

flame

• Particulate material: Unevaporated droplets;

unevaporated refractory salt particles
• Scattering is more serious at short 
• 2 and 3 are most common with electrothermal atomizer

51
 Specific Applications Require
background correction
1. Graphite furnace

2. Flame determination of low concentrations of an element

in the presence of high concentrations of dissolved salts

3. Flame analysis where sample matrix may show molecular

absorption at  of the resonance line

4. Flame determination of an element at  where flame

absorption is high

52
 Background correction methods

1. Using a blank
• Measure the absorbance of the metal
resonance line by both flame & blank
(flame system)
• Measure the absorbance of the metal
resonance line by sample and flame system
(flame + blank)
• A is the difference
53
The main two methods used for background correction:

1. Continuous source correction method

2. Zeeman effect correction method
• These two methods are based on the fact that
• Atomic bands are very narrow
• Background bands are molecular in nature thus
they are broad bands

54
 2. The continuous-source correction
method
• This method is an available option with most
instruments
• Deuterium lamp is used in conjunction with the HCL
lamp
• The two lamps are observed by detector
alternatively in time
• Background usually absorb radiation from D2 lamp
and HCL
• Absorption of the analyte from D2 lamp is negligible
• The lamps may be pulsed at different frequencies,
thus the signal processing electronics can
distinguish and process separate absorption signals
• Thus
Acorrected = A HCL - AD2
55
 The continuous-source correction method

Chopper

56
57
 Background correction by continuous source
correction method

HCL

HCL
HCL

58
59
 Disadvantages of the continuous source
correction method
• Correction may degrade detection limit. The
current of HCL is reduced to match the D2
lamp
• The correction may be in error if the
background s (sample and standards) are
not the same
• Alignment of the two sources to pass
through the same area of atomizer is tedious
• Beam splitter reduces the intensity of
radiation which may affect the limit of
detection
• Additional light source and electronics are
needed
60
 Zeeman effect correction method

61
 Zeeman effect correction method

62
• Under the magnetic field, atomic spectral line
(emitted or absorbed) splits into three or
more polarized components
• Two components will be displaced at equal
wavelength intervals higher and lower than
the original line.
• The original line is polarized in plane parallel
to the magnetic field and the other lines are
polarized perpendicular to the magnetic field
• The original line is absorbed by both
background and analyte. However, the other
lines are absorbed by background only
• The signal corresponding to the analyte is
the difference
63
 Advantages of Zeeman method

• Only a single lamp is required

• Problems of alignment of two beams is
eliminated
• It provides more accurate correction for
background than other methods
because the background absorbance is
measured at or very near the
wavelength that the analyte absorbance
is measured
64
 Disadvantages of Zeeman method
• The implementation is rather complex and
expensive
• The original and the split bands may overlap
causing an increase in the background signal
• This causes a curvature in the calibration curve
• The instrument is bulky because of the magnet
• Spectral lines for some elements may undergo
more complex splitting. Thus sensitivity will be
reduced (It gave good results for 44 elements)
• It is more difficult to engineer with flames

65
 Source self reversal
background correction method

• It is based on self-reversal of the HCL spectral lines

at high current
• At high current, many free atoms are generated
causing an increase in the number of unexcited
atoms that absorb the center of the emitted line
causing the self reversal
• Specially good for correcting for high molecular
absorption for that by phosphate on Se and As
• A total is measure

66
 • Hollow cathode lamps normally operate at
currents of 3-15 mA.
• If the applied power is raised to several hundred
mA, they exhibit a phenomenon called self-
reversal.
• This giant pulse of current changes the nature of
the analyte absorption line so it will only measure
the background absorbance.
• Atotal is measured during the low current period.
Abackground is measured during the high current
period
• The low current (6-20 mA) is pulsed at 100-500
mA

Corrected signal = Signal before the pulse

–Signal After the pulse

67
 Advantages of Smith-Hieftje technique

• Only a single source is used

• It offers all the advantages of other methods
at low cost
• It does not lose radiation like in Zeeman but
this mehtod with the Zeeman one are less
sensitive than the D2 one

• Drawbacks
– less sensitivity
– lamp life decreased

68
 Background in atomic emission

• Sources
1. Emission from flame
2. Emission from the sample matrix

69
 Electrothermal Atomizer
(Graphite Furnace)

• Main components
• Atomization steps
• Interferences and matrix modification

70
 Graphite Furnace Atomic Absorption
Spectrometry, GFAAS

 A technique to minimize dilution during atomization

of the analyte prior to its determination with atomic
absorption spectrometry
 A technique with more interferences than the more
reliable flame atomization
 A technique with high sensitivity and very good
detectability but not so good throughput and
precision

71
 Advantages of GFAS

• Increase in the residence time thus

more sensitivity will be obtained
• Possibility of analyzing samples of
various matrices
• Analyzing small size samples even on
the microliter scale
• Avoiding the formation of refractory
oxides that cause serious interference
sourcse
72
 • Minimize the surface adsorption

73
 Why do we use an inert gas with GFAAS?

74
 Atomization Process

75
Steps in graphite furnace atomization

• The steps of a GF atomization

• 5-100µl sample
– drying
– ashing
– atomization
– burnout
– cool

76
 Steps in GF atomization

• The sample introduction

– The sample is injected, usually
between 10-30µl but sometimes the
range could be extended to 100µl.
– The solution is preferably made up of
dilute nitric acid as matrix
– sometimes solid samples are
introduced
77
• The drying step
– to volatilize the sample solvent
– use some degrees above the solvents
boiling point (for water use 110°C) and
about the same time in seconds as the
injected volume in µl
– check that the solvent only volatilizes
and not boil, otherwise bad
reproducibility may occur

78
• Ashing of the sample
– Maybe the most important step
– Remove sample matrix without losing the
analyte
– Highly dependent on both the analyte and
sample matrix
– Conditions for every new sample type
should be optimized
– Inorganic matrix more difficult, because
higher temperatures are needed

79
• The atomization step
– This step is to vaporize and atomize the
analyte
– the vaporization pressure of the analyte
dominate the supply of analyte atoms
inside the tube
– The convection of expanding gas and
diffusion dominate the transport of
analytes out of the tube
– rapid heating is necessary for good
sensitivity

80
• The burnout step
– it is used for taking away parts of the
sample not completely volatilized during
atomization
– temperatures in the range 2700-3000°C is
most often used
– if vaporization of the sample is achieved,
completely, the sensitivity will slowly
decrease and the imprecision increase

• Cooling step
– its purpose is to cool down the furnace
before next sample is added

81
 Steps in GF atomization

temperature progamme
3000

2500

2000
Temp (°C)

Atomization
1500

1000
Ashing
500
Drying time (sec)
0
0 20 40 60 80
82
 Interferences with graphite furnace
and its control

• In the early days this technique was

accepted as a highly interference
technique
• Later, new instrumental and analytical
procedures were developed which
avoided the conditions found to be the
source of interference problems

83
 Interferences in GFAAS
• The graphite furnace atomization technique is much
more affected by interferences than the flame which
depends on higher concentrations of non-analytes
–physical
• change in surface properties of the graphite tube
influences the atomization rate
–Spectral
• molecular absorption by molecules or atoms other
than the analyte atoms
• light scattering
–non spectral or chemical
• molecular binding between analyte and matrix
• formation of less volatile compound
84 • reactions with the graphite tube
 Interference removal

Spectral interferences

• Emission interference
• Non-analyte absorption and scattering

85
1. Emission interference
• Radiation emitted by the hot graphite tube or
platform that covers a wide range of
waqvelengths (250-800 nm)
• Following elements will be obscured:
– Zn 213.9 nm; might be ok
– Cr 357.9 nm
– Ca 422.7 nm
– Ba 553.7 nm mostly affected
• This effect is eliminated by removing the
graphite tube wall or platform from the view
of the detector. This is achieved by ine of the
86following arrangements:
• Setting a narrow monochromator slit
• Furnace alignment
• Cleaning graphite tube and windows to
prevent light scattering
• Atomization temperature should not be
higher than required

87
2. Non-analyte absorption and scattering
• It is considered as a background absorption
• It is the most severe spectral interference
problem
• It occurs as a non specific attenuation of light at
the analyte wavelength due to matrix
components in the sample
• It leads to having a broad band covering 10-
100’s nm due to molecular absorption caused by
“undissociated sample matrix” components in
the light path at atomization
Remedy?
• Matrix modification
• Furnace control procedures
• 88Background correction as with flame techniques
 Matrix modification
• Matrix should be more volatile than the anayte so as
to be removed before atomization
1. Formation of easily volatile matrix components, e.g.,
Using NH4NO3 or ammonium acetate to modify NaCl
matrix
NaCl + NH4NO3 NaNO3 + NH4Cl

nonvolatile matrix More volatile compounds

Matrix modifier

• The more volatile components can be driven off at

lower pyrolysis temperature

89
2. Converting the analyte element into a less
volatile (if it is too volatile) component using
a modifier e.g., Ni (NO3)2 for Se
determination.
• Se is a highly volatile component
• With the modifier Se form nickel selenide.
Thus, Se can be heated up to 900 oC without
loss. Consequently the matrix would be
removed without affecting Se.

90
3. Varying the sample volume
• Can be done if concentration allows
• Reduce the sample size by injecting smaller
samples, thus the mass of background producing
matrix components will be reduced.

4. Spectral background correction

• A continuous background correction is not very
efficient specially for complex matrices. Matrix
modification is a must.
• Zeeman background correction is very efficient for
complex matrices

91
 Chemical Interference

• It occurs when other components of the sample

matrix inhibit the formation of free analyte atoms

M o + Xo MX

Free analyte atoms Different matrix component

92
 Interference Removal
1. Ashing with the optimal temperature
–matrix modification (mentioned above)
• Delay of anayte release to furnace allows time for a
constant furnace temperature
• thermal stabilization of analyte (to hold the analyte
on the graphite surface to a higher temperature)
and vaporization of interference during the ashing
step
– Thus, volatility of interfering matrix compound
is increased
• On the other hand volatility of interfering
compound is decreased and selective vaporization
during the atomization step
takes place
93
 2. Use of pyrolytically coated Tubes and Platforms

•Ordinary graphite has a porous surface thus it forms

with the analyte a carbide that is nonvolatie
•The tubes are more or less always fabricated from
pyrolytic carbon or covered with a pyrolytic carbon layer.
It’s a more inert form of the graphite. It is more dense
surface and less absorption
•Tubes could sometimes be coated with tungsten or
tantalum for prolonged lifetime or other special
applications
•The platform technique is used to vaporize the analyte
into a more uniform and higher temperature than the
release from the wall. The analyte vaporizes after the
tube
94 wall and gas phase reach a steady state
• L'vov Platform – Thin graphite plate inserted into
tube with flat trough
– L'vov barely contacts sides of tube
– Sample is heated more uniformly by air
– Platform delays the appearance of analyte until
the furnace has reached atomization temp

95
 Functions of the platform
• It resists tndency for sample to saok into surface
before or during drying
• It tolerates high acid concnetration
• It gives bigger signal and less background
– It is heated gradually by radiation from walls
– When atomization step is reached the temperature of
the sample and furnace environment will be similar
– No chance for sudden cooling and recombination
forming molecular species inhibiting atomization
I

96
Disadvantages of Graphite Furnace

• Prone to interferences, poor precision

• Must take Step to control Precision:

1. Autosamplers vs. Manual Injection - more precise
2. Duplicate analyses for all samples (repeat if poor
agreement)
3. Standard addition method - making standards up in
sample

4. Background correction for Molecular Absorption)

1. D2
2. Zeeman Background Correction
3. Matrix Modifiers to control
atomization

97
 INDUCTIVELY COUPLED
PLASMA
• Main components of the instrument
• Performance of ICP
• ICP-mass spectrometry
• interferences

98
 Introduction
• The device which produces the ICP is commonly
referred to as the ICP torch. It consists of two to four
Argon flows depending on the manufacturer:
• Nebulizer gas (inner Argon flow), at about
1 L/min, carries the analyte aerosol
• Sheath gas for producing a laminar flow to
improve low excitation energy elements eg group
•
I & II elements
• Auxiliary gas (if present), lifts the plasma above
the injector tube, used when measuring organics
• Plasma gas, at about 12-16 L/min, sets the
plasma conditions, e.g., excitation temperature

99
 Sample Introduction
• An ICP-AES instrument consists of a sample
delivery system, an IC plasma to generate the signal,
one or more optical spectrometers to measure the
signal, and a computer for controlling the analysis.

• The most common sample delivery system consists

of a peristaltic pump and capillary tube to deliver a
constant flow of analyte liquid into a nebulizer.

100
 Inductively Coupled Plasma Torch

101
 How does plasma generate?

• RF induction coil powered by RF generator

will generate a fluctuating magnetic field
around the coil
• Ionization of Ar is initiated by a spark
• Ar+ and e- will interact with the magnetic field
thus they will be forced to move in annular
paths
• Omic heating is the result of their resistance
to the forced movement in limited area

102
 Inductively Coupled Plasma
Emission Source

103
 Inductively Coupled Plasma
Emission Source and Supply

104
105
106
 • An ICP torch can be used to atomize and
ionize materials for quantitative trace and
ultratrace elemental analysis
• The compounds in the samples are broken
down into their elemental form and some
fraction of each elemental species is
simultaneously ionized
• The monocationic (+1) form is preferred
for the assay, and conditions are set to
enhance production of that form
• The torch is normally operated at a
temperature of ~3000K
107
 Schematic diagram of a typical ICP-OES instrument

108
 Schematic diagram showing the different
regions in the IC Plasma

109
 Processes that take place in the plasma

•Aerosol vapor is transported to the plasma

•Vapor desolvates

•Atomization occurs within the plasma

•Atoms get excited to atomic and ionic states

•Rich spectra produced because of presence of both

atomic and ionic lines

•Because of their different excitation energies,

different emission lines will have maximum intensities
at different vertical positions in the plasma
110
 Typical detection limits in ICP-OES

111
112
 Typical detection limits in ICP-OES

113
 Sampling

Liquids
• Form an aerosol (<5 µ droplet size) of the liquid
sample
• Eliminate larger droplets
• The use of liquids facilitates automatic sampling:
Gases
• May use gasses directly or indirectly, e.g., form
hydrides
Solids
• May use slurries (if 95% of particles <5 µ)
• May use spark ablation or laser ablation to generate
a small metal vapor

114
 Viewing position

• The plasma generated in an ICP can be viewed

by the spectrometer, side-on or end-on.
• These viewing positions are called radial and
axial viewing, respectively.
• Each has advantages and disadvantages, so
each tends to be used for different applications:
radial viewing for normal analysis and complex
materials, axial viewing for low detection limits
in simpler materials.

115
116
 Advantages of Radial View

• Should collect signal from the entire normal

analytical zone
– no torch adjustment for different elements
– fewer matrix effects and interferences, especially in
organics
– less stray light
– better detection limits in difficult matrices, especially
in alkalis and organics
– can run any matrix
– less maintenance of the torch
– torches last longer especially with dissolved salts
– lower consumption of argon

117
 Advantages of Axial View:
• More intensity
118
• Better detection limits in simple matrices
RF-Generator
• ICP's generally require an RF power of 1-2 kW maximum output
to maintain the plasma.
• High efficiency required - especially for organics (not less than
1.5 Kw)

Frequency
• Fixed versus Free Running
– Fixed: Crystal controlled, eg at 40 MHz
– Free running: floats eg at 40 MHz ± 2 MHz
• 40 MHz versus 27 MHz
– Because of the skin-effect in RF plasmas, higher
frequency gives a thinner plasma with a wider
dynamic range (less self-absorption), with lower
backgrounds and fewer interferences.

119
120
• > 90% element coverage
• 0.1 to 10 ppb sensitivity for most
elements
• RSD ~ 2% to 4%

121
Typical laser ablation/ICP-MS mass spectrum of a rock sample

122
 Comparison of Detection Limits
Black = ICP/MS Cross-Hatch = ICP/AES Gray = Furnance AA

123
 Comparison of ICP/AES & ICP/MS for the analysis of
Cerium solutions

ICP/AES (100 ppm Ce)

Background ions
originated from
the Ar, O, H and
N elements

ICP/MS (10 ppm Ce)

• Simple to interpret, especially
for rare elements
• Less interference from
atmospheric contaminants or
molecular bands

Nitric acid is commonly used as acidification agent rather than hydrochloric acid, sulfuric acid and
124
phosphoric acid in sample preparation. Why?
 Limitations for ICP/MS Quantitation

• Formation of monocationic ions, doubly-charged ions

and stable metal oxides ions in the torch depends on
the identity of the element and several experimental
conditions, such as the plasma r.f. power and the
nebulizer gas flow rate.
• Spectroscopic interference:
1. Isobaric Interference
- isotopes of different elements (or isobaric
interference) e.g. 87Rb+ and 87Sr+; 40Ar+ and
40Ca+; 58Ni+ and 58Fe+

125
 – Polyatomic Ion Interference
• interactions between species in the plasma
and species in the matrix or atmosphere, e.g.
molecular ions from the acids of digestion
• e.g. ClO+ and 51V+

Which element(s) does not have isobaric

interference caused by the presence of other
elements?

126
 • Matrix effect:
(a)Limited tolerance for salt concentration
(< 1% is acceptable but < 0.1% is preferred!)
– The deposition of salts leads to a
decrease in the aperture diameter, so the
sensitivity worsens and the signal
gradually decreases as a function of time
(b)Organic solvents tend to quench the plasma
torch

127
 Approaches to reduce the occurrence of
polyatomic interferences
• Adjust the plasma conditions to minimize the formation of
polyatomic species
e.g. use 5-10% N2 in Ar, the axial temperature of the plasma
increases by ~ 1000 K and the electron density increases by
30%. A marked reduction of MO+ ions
• Minimizing the amount of water vapor introduced into the
plasma in order to limit the signal intensity of oxygen-
containing species
e.g. reduce the spray chamber temperature(?)
• Use He instead of Ar as plasma gas to avoid interference from
polyatomic ions containing argon
• Use electrothermal volatilization for sample introduction
• 128
Use high resolution ICP/MS
Approaches to correct for or overcome
matrix effect
• Dilution
• Matrix matching
• Use of internal standards
– Addition of a known and preferably an equal
concentration of an internal standard to all samples (&
standards). The analytical signal is taken as the ratio of
the signals for the analyte elements in the sample (&
standards) and the signal for the internal standard
• Standard addition
– A known amount of the element(s) of interest is added to
the sample and hence suffers the same matrix effect as
the analyte
129