Atomic Absorption

Spectrometry (AAS)
(Chapter 9)
 AAS
• The most widely used method for
quantitative determination of single
element in analytical samples
 Atomic Absorption
Spectroscopy
• Absorption of radiation by free atoms
• Line spectra are observed
• Specific spectral line can be used for
elemental analysis
– Only for quantitative analysis
 Atomic absorption
• A process where vapourized ground state
atoms absorb radiation
• Absorbance is measured

Po Atomic Absorption Spectroscopy (AAS)

P
A • Absorption rate depends on population of
h h ground state atomic vapour
• Absorbance  concentration

P
A = - log T = - log
P0
 Atomic spectroscopy

• The element must be in the form of

free atoms
• The sample is heated ~ 2000ºC to be
dissociated
 Atomic absorption
• With electrical or flame atomization, most
atoms are in the unexcited state
• If we look at the free atoms, we can
potentially develop a sensitive method of
analysis
Atomic Absorption Spectroscopy (AAS)

A quantitative method of analysis

• Based on the absorption of radiation
by atoms in the free atomic state
• Relies on Beer’s law
• Calculations: A = εbc
 Atomic Absorption Spectroscopy
• A quantitative method of analysis
• Applicable to many metals and a few of
the non metals
Sample atomization techniques
• Flame
• ETV
 Flame atomization
A solution of the sample is
• nebulized by a flow of gaseous oxidant
• mixed with a gaseous fuel
• carried into the flame
(atomization occurs)
Processes occurring during
atomization
Nebulization
Desolvation
• The solvent evaporates to produce
a finely divided solid molecular
aerosol
Volatilization
• Solid aerosol is converted to
gaseous molecules
Dissociation/atomization
• Gaseous molecules are converted
to atomic gas
 Atomic vapour
Processes that also occur to the
atomic vapour in the atomizer

Ionization
• Form cations and electrons
Interaction of fuel and oxidant
with various species in the flame
• molecules are produced
Dissociation
• Atoms are produced
 Ca*(g)

excitation
nebulization desolvation atomization
CaCl2(aq) CaCl2(aq)  CaCl2(s)  CaCl2(g)  Cao(g)+ 2Clo(g)
volatilization

ionization
excitation
CaO*(g)  CaO(g)
CaOH*(g) CaOH(g)

Ca+(g)
 excitation

Ca*+(g)
A fraction of atoms, molecules, ions are
exited by the heat of flame
• Atomic, molecular and ionic emission
spectra
Atomization
• The most critical step
• Limits the precision
Properties of flames
 Flame Burning Velocity
Flame are stable only in certain range of gas
flow rates
• Ideally; flame rises above the burner
where  flow velocity = burning velocity
– The flame is stable
Flow velocity < burning velocity
• Flame propagates back into the burner
– Flashback
At higher flow rates
• flame rises
• blows off the burner

Flow rates depends on

• the type of fuel and oxidant
Regions in a flame
Appearance and relative size
of regions vary with
• Type of fuel and oxidant
• Ratio of fuel:oxidant
Primary combustion zone
• Thermal equilibrium is not
achieved
• Not use for measurement
Interzonal zone
• The most widely used part
of the flame
• Free atoms are prevalent
Secondary combustion
zone
• The products of the inner
core are converted into
molecular oxides
– then, dispersed into the
surrounding
Temperature (C) profiles for a natural
gas-air flame
• Provides useful information
about the processes in
different parts of the flame
• Contour plot reveals regions
of flame that have similar
temperature
• Max temp at about 2.5 cm
above primary combustion
zone
– Focus that region on the
entrance slit for measurements
 Flame absorption profile

Optimum position in flame is sample dependent

 Flame absorption profile for
Mg, Cr, Ag
Ag – Not easily oxidized
• increasing atomization as sample rises in flame
– Absorbance (A) increases
Cr – forms stable oxides in flame
• Continuous decrease in A
Mg – combination of both effects
• An increase in number of Mg atom initially, thus A
• Oxidation of Mg begins as the 2 combustion zone is
approached – A decreases
• To achieve max sensitivity, flame is adjusted (up & down)
WRT the beam
• Different portion of the flame should be
used for the determination of each
element
FAAS
• Radiation from a small region of the flame
is sampled
• To optimize signal output – adjustment of
the position of the flame WRT the
entrance slit
 Flame atomizers
Commercial laminar
flow (pre-mixed) • Aeorsol is mixed with
burner with fuel and passes
concentric tube
nebulizer through a series of
baffles
– Remove all but the
finest solution droplets
• The rest of the
solution collect at the
bottom of the mixing
chamber
– Drains to waste
container
 Performance characteristics of
flame atomizers
Advantages
• High sample throughput
• Reproducible
– Continuous representative sample
introduction
• Precision
– 1% or better
Limitations
• Only for liquid samples
• Requires high sample volume (mL)
• Lower sampling efficiency
– A large portion of the sample drains to waste
• Lower sensitivity
– Residence time of individual atoms in the
optical path in the flame is brief (~10-4 s)
Electrothermal atomizers
Enhanced sensitivity
• The entire sample is atomized in a short
period
• Average residence time of the atoms in
the optical path is longer (1 s or more)
 Electrothermal atomizers
Atomization occurs in a cylindrical interchangeable
graphite tube
• 5 cm long
• Internal diameter < 1 cm
• Open at both ends
• Has a central inlet for sample introduction
– Using a micropipette
 Graphite furnace
(a) cross-section
(b) Longitudinal
configuration
 temperature varies
continuously
 maximum at the centre
(c) Transverse
configuration
 temperature profile
(b) (c) is constant along
the path
 Graphite tube
• Fits into graphite electrical contact at both ends
Two inert gas streams
• External stream
– Prevent outside air from entering and burn the tube
• Internal stream – flow into the two ends of the
tube and out the central sample port
– Excludes air
– carry away vapours from the sample matrix during the
first two heating stages
Three step sample preparation for graphite
furnace:
(1) Dry - evaporation of solvents (10 - >100 s)
50 – 200 ºC
(2) Ash/char - removal of volatile hydroxides,
sulfates, carbonates (10 -100 s)
200 – 800 ºC
(3) Fire/Atomize - atomization of remaining
analyte (ms - seconds)
2000 – 3000 ºC [A is measured]
(4) Heat to 2500 – 3500 ºC for 3 s to burn off
any residue
(5) Cooling to room temperature for the next
experiment
 Output signal
At a  at which absorbance occurs
• signal output rises to a maximum after a
few s of ignition
• then a rapid decay back to zero
– The atomization products escape into the
surrounding
• The change is fast (< 1 s)
• Based on peak height
 Determination of Pb (GFAAS)
Molecular evaporation and
particulate ignition products
Typical output; A at 
of Pb peak vs. time
Sample
2 L canned orange juice
calibration
Drying: 20 s
Ashing: 60 s

Sample concentration
 Performance characteristics
Advantages
• Liquid and solid samples
• High sensitivity
– Detection limits 10-10 to 10-13 g of analyte
• Requires a small volumes of samples
– Between 0.5 – 10 L
Limitations
• Low precision
– Between 5% - 10%
• Slow method
– Discontinuous
• Heating – cooling cycles
• Several minutes per elements
• Narrow analytical range
– < two orders of magnitude
Electrothermal atomizers
• When flame or plasma provides
inadequate detection limits
 Samples
• Generally samples are introduced as
solution
Solids
• Weighed finely ground sample in a
graphite boat
• The boat is inserted manually into the
furnace
 AAS Intsrumentation

Sample holder
• Atomizer that contains the gaseous
atomized sample
Atomic absorption instrument
Single beam AA

atomizer
Flame AAS
 Radiation sources
Molecular absorption
• Broad band radiation source is used
Atomic absorption
• Highly specific
– AA lines are narrow 0.002 to 0.005 nm
– Electronic transition energies are unique for
each element
• A line source is required
– To reduce interferences from other elements
and background
 Why narrow line widths
• Beer’s law requires a narrow bandwidth
relative to the width of an absorption line
If a continuum source is used
• effective bandwidth > the width of atomic
absorption lines even with a good
monochromator
• Non-linear calibration curve
• Slopes are small
 Line sources
Determination of Na
• 589.6 nm is used
• A Na emission lines at the same  is
selected is isolated
 Absorption of a resonance line
Po
by atoms
Emission spectrum of radiation
source, Po

Sample absorption spectrum

P
A  log
Po
Absorption bandwidth > emission line

Emission spectrum after passage

P through sample and monochromator,
P
• A separate lamp is needed for each
element
 Radiation Sources
Need a narrow line source. . . . Why?
• Atomic spectral features are very narrow
– (linewidths typically < 10-2 Å or 10-3 nm)
• Continuum source necessitates monochromator
with ∆ λeff < 10-3 Å
– not easily done!
Therefore, need a source which can
provide emission at discrete wavelengths
with line widths less than those found in
atomizer (flame or graphite furnace cell)
 Radiation sources
Types
• Hollow cathode lamp (HCL)
– The most common
• Electrodeless discharge lamp (EDL)
 Hollow cathode lamp
Consists of
• Tungsten anode
• Cylindrical cathode
– Is constructed of the same metal
or
– To support a layer of the same metal
• Sealed in a glass tube
– Filled with Ne or Ar at a low pressure, 1 – 5
torr
 Hollow Cathode Lamp

• Produces the line source specific for the

element used to construct the cathode
• The cathode must be capable of
conducting a current
 Hollow cathode lamp

Hollow cylinder cathode is made of/coated

with the same element as the analyte
 Hollow cathode lamp

Ionization of Ar
High potential difference, creating
current
Anode pulls e- off fill gas atom, creating
argon cations
Sputtering
• if the voltage is high, fill gas cations (Ar+) acquire
KE to dislodge some of the metal atom from the
cathode surface
• produces ground state metal atomic vapor (Mo (g))
Excitation
• High energy collisions excite a portion of
sputtered metal atoms
• Mo(g)  M*(g)
Emission
• Excited atom returns to ground state
• emits characteristic narrow beam (~0.5 nm) high intensity
radiation (several emission lines) at which the analyte
absorbs
Eventually, the metal atoms diffuse back to
• the cathode surface
or
• the glass walls of the tube
and are redeposited
Cylindrical cathode
• Concentrate the radiation in the limited
region of the metal tube
• Enhance the probability that redeposition
occurs at the cathode
Efficiency of HCL depends on
• Its geometry
• Operating voltage (high voltage, high
current)
– produces greater intensity radiation
– also increases Doppler broadening
– Increased number of unexcited atoms in the
cloud
• Capable of absorbing the emitted radiation
– Self-absorption
» leads to lower intensity
• Lamps available for about 64 different
analytes (~RM1000, last ~ 5 - 10 years)
• Multi-element lamps are available (more
expensive)
 Hollow cathode lamp
• will only produce the emission lines for the
cathode element
• Not all metals will make suitable cathodes
– too volatile
– may not good conductors
• a good cathode cannot be produced
 Electrodeless Discharge Lamp

RF coil

Quartz window

Bulb
Ceramic
holder
 EDL
Sealed quartz tube containing
• low pressure inert gas (Ar) and
• a small quantity of the metal (or its salt)
whose spectrum of interest
• Contains no electrode
– Energized by intense field of RF or microwave
radiation.
• Ionization of Ar gas produce ions
• Accelerated by high-frequency field to
excite the atoms
 EDL
• Available commercially for about 15
elements
• Higher radiant intensity compared to HCL
• Not as reliable as HCL
Se, As, Cd, Sb EDL’s
• Show better detection limits than HCL
 Line broadening
• Please refer to earlier discussions
 Flame Emission Effects
Emission of radiation by excited atoms in the
flame
• Interferences
To be eliminated
• Much of this is removed by the
monochromator
• Emitted radiation of the same  as the
monochromator setting present
 Superimposition of absorption and
emission of the same element
• A fraction of atoms of certain elements
are excited
– Emit photons
• Of the same energy as the ground state
atoms are able to absorb
• Must correct the measurement
• The emitted intensity has to be
subtracted
To eliminate the effects of flame emission
• Source modulation
• Use a chopper
 Source Modulation
Modulate the output of the radiation source so that
• the intensity fluctuates at a constant
frequency
The detector receives 2 types of signals
• An alternating signal from the radiation source
• Continuous signal from the flame
These signals are converted to the corresponding
types of electrical signal
 Signal modulation
HCL voltage is pulsed
• Permits differentiation between
– the emission signal (constant)
and
– the absorption signal (pulsed)
 Single beam AA

Modulated
power Amplifier
source
 Chopper
• Circular metal disc
• Placed in the beam between the source
and flame
• A simple and effective method of
eliminating noise from flame emission
 Chopper
Common types
• Rotating disk
• Rotating vane
 Mechanical choppers for
modulating a radiation source

(a)Rotating disc chopper

(b)Rotating vane chopper
Chopper
To discriminate between
• the radiation from the
hollow cathode lamp
and
• the radiation given off
by excited atoms in the
flame
by alternately passing
through the flame and
being blocked off
 Interferences in Atomic Spectroscopy
(AA and AE)
Types
• Spectral
– Absorption or emission of an interfering
species overlaps or lies close to the analyte
absorption or emission
• Impossible to be resolved by monochromator
• Chemical
– Various chemical processes occuring during
atomization
• Alter absorption or emission characteristics of the
analyte
 Spectral interferences
Overlapping of lines
• Not common in AAS
– Emission lines of HCL are very narrow
 Spectral interferences
The presence of combustion products
• Show broadband absorption
Or
• Scatter radiation
Effect
• Reduces P (power of transmitted
radiation)
– Leads to positive analyte errors
 Spectral interferences
Sources of particulates that scatter the
radiation
• Product of fuel and oxidant mixture
• From sample matrix
• Product of atomization (metal oxides)
• Sample contains organic species
• Organic solvents are used to dissolve the
samples
 To minimize spectral
interferences
If the source of interference is matrix products
• Not common with flame atomizer
If the source is known
• Add excess of radiation buffer to samples
and standards
• The interfering substance
– High concentration of radiation buffer compared
to sample matrix
– Contribution from sample matrix will be
insignificant
 Chemical interferences
More common than spectral interferences
• Formation of low volatility compounds
• Dissociation equilibria
• Ionization equilibria
 Effects of Flame Temperature
• Higher flame temperatures increase the
total atom population in the flame
– The sensitivity
• However, the increase in atom population
is offset by the loss of atoms by
ionization
 Effects of Flame Temperature
Flame temperatures determine
• The efficiency of atomization
– The fraction desolvation, vapourization,
atomization, excitation and ionization of the
analyte
• The relative number of excited and
unexcited atoms in the flame
 Effects of Flame Temperature
• The number of unexcited atoms in the
flame exceeds the number of excited
atoms by a factor of 103 to 1010 or more
• Flame absorption methods should show
lower detection limits than flame emission
methods
 As the temperature increases,
more atoms are excited.
T1 Most are in the ground state.
T2
Number of atoms

T3 Minimum
energy
for excitation

T1<T2<T3

energy
 Temperature Effects
• In atomic absorption, an increase in
temperature usually increases efficiency of
the atomization process and hence
increases the total number of atoms in the
vapor.
 Temperature Effects
• Line broadening increases at high
temperature. The Doppler effect is
increased as atoms are moving faster.
• Excitation and ionization increases as the
temperature increases
 Following atomization, collision among
the analytes and particles in the flame
will initiate the competing processes of
analytes
• Excitation
– Produces excited atoms
• Ionization
– produces cations and electrons
• Reaction with other flame components
– Many metal atoms (M) are oxidized to
oxides (MO) or hydroxides (MOH)
 Formation of low volatility compounds

• Analytes reacts with anions or cations to

form low volatility compounds
Effects
• Reduce the fraction of atomized analyte
• Lower signals
 Choosing the right flame condition is often
a trade-off
• Use different flames for different element
 Formation of low volatility compounds
Anion interferences
Example: to determine the concentration of
Ca in a sample
• The presence of SO42- or PO43-
• Ca will react with anions
• The products are difficult to volatilize
 Formation of low volatility compounds

Cation interferences
Example: Determination of Mg in the
presence of Al
• Formation of heat stable Al-Mg
compounds
 To minimize the effects of low
volatility compounds
(1) Use higher flame temperature
– To volatilize the products
• Can lead to other interferences
 To minimize the effects of low
volatility compounds
(2) Add releasing agents
• Cations that react preferentially with the
interferant
• Prevents the analyte from reacting with the
interferant
 Releasing agents
Example:
Determination of Ca in a sample
Determination of Mg in the presence of Al
• Add excess of Sr+ or La2+
• La or Sr will react with the interferant
– Replacing the analyte
 To minimize the effects of low
volatility compounds
(3) Add protecting agents
• Prevent interference by forming stable but
volatile species with the analyte
Common reagents
• EDTA – eliminate interference of Al, Si, PO43-,
SO42- in the determination of Ca
• 8-hydroxiquinoline – supresses interference of
Al in the determination of Ca and Mg
• APDC
 Dissociation Equilibria
• Dissociation and association reactions in
the hot, gaseous environment
• Lead to elemental states of the metallic
constituents
Examples:
MO  M + O
M(OH)2  M + 2OH-
 MO and MOH
• Not atoms
–does not absorb or emit at the
same wavelength;
–therefore signal decreases
“Rich” flames
• rich in fuel, tend to reduce MO and
MOH to M so can get better signal.
– Flames are cooler, not many atoms are
atomized and excited
“Lean flames”
• low in fuel, high in oxidant,
– higher tendency to oxidize metals.
– Flames are hotter, more M in excited
state
 Ionization in Flames
• All elements ionize to some degree in
flame
– A mixture of atoms, ions and electrons in the
flame
 Ionization Equilibria
At higher flame temperatures, ionization becomes
important
An equilibrium is established in the interzonal region
of the flame
M(g)  M+(g) + e-
The position of the equilibrium depends on
• the temperature of the flame
• the total concentration of M(g)
• the concentration of e- produced from all elements
present in the sample
Degree of ionization of metals at
flame temperatures
 Ionization Equilibria
The degree of ionization of a metal will be
influenced by
• the presence of other ionizable metals in the
flame
• If a flame contains M and B
M(g)  M+(g) + e- (ionization of analyte)
B(g)  B+(g) + e- (ionization of B)
• The degree of ionization of M will decrease by
the effect of electrons formed from B
 Ionization Equilibria
Intensities of AE or AA lines for alkali metals (low
IP) especially K, Rb, Cs are affected by
temperature
• Increased temperature causes
– an increase in population of excited atoms
– a decrease in population of ground state atom due to
ionization
• A decrease in emission and absorption
observed in hotter flames
• In the determination of alkali metals
– Use lower temperature
 To minimize the effects of shifts in
ionization equilibria
Add ionization suppressor
• An easily ionizable species
• Provides a relatively high concentration of
electrons in the flame
• Results in suppression of ionization of the
analyte
Effect of a suppressor in calibration
curves for Sr
An increase in the slopes
• Sr ionization is repressed
by
– increasing [K] and
– increasing [e-]
Enhanced sensitivity by
using N2O as oxidant
• Higher temperature
increases the degree of
decomposition and
volatilization of Sr
compounds
 Monochromator (AAS)
• A high resolution, holographic grating is
used to resolve the lines
– Not designed to be used in the scan mode
 Detector
UV-Vis detector
• PMT (photo multiplier tube)
• A sensitive detector
 Atomic spectroscopic methods

• Standard conditions for all elements

are available
• A computer based system will help to
set up the proper conditions
 AAS methods
For each element, factors to consider
• Which λ and slit width to use
– Determines sensitivity and linear range
– Narrowness of line source increases sensitivity and
linear range
• Flame AAS
– Flame type
– Fuel, oxidant, ratios
• GFAAS
– Optimum temperature to use
 Flame atomizers
• AAS more sensitive than AES
• AAS less suitable for
– Weak absorbers (forbidden transitions)
– Metalloids and non-metals (absorb in UV
region)
– Metals with low IP (alkali metals)
• High temperature for atomization
necessary (flame and electrothermal)
• Very high temperature for atomization not
necessary for AAS
– Generally no plasma/arc/spark AAS
Organic Solvents – alcohols, esters, ketones
• tend to increase nebulization efficiency
• enhancing absorption
• useful as immiscible extraction solvents for
metal chelates
 Sample preparation
Disadvantage of flame spectroscopic methods
• Sample introduced is in the solution form
usually an aqueous solution
• Many materials of interest are not directly
soluble in common solvents
– Soils, animal tissues, plant, petroleum products
and minerals
• Requires extensive preliminary treatment
 Sample preparation
Decomposition and solution steps
• More time-consuming and introduce more
errors than the spectroscopic
measurement itself
 Sample preparation
Decomposition step
• Requires rigorous treatment at high
temperature
• Risk of losing analytes
– By volatilization
Or
– As particulates in smoke
 Sample Introduction - Liquids
• Hydride Generation – volatile As, Sb, Sn,
Se, Bi, Pb hydrides formed by reaction with
1% NaBH4 (aq), into inert gas flow

3 BH4- + 3 H+ + 4 H3AsO3  3 H3BO3 + 4 AsH3 (g) + 3 H2O

Volatile hydrides
 Sample Preparation
Decomposition step
• High temperature
– Risk of losing analyte by volatization or as
particulates in smoke
• The reagents introduce chemical and spectral
interferences
• Analyte may be present in the reagent as
impurity
– In trace analyses, the reagents are a larger source
than the samples
 Sample Preparation
Decomposition and dissolution of samples,
• treatments with hot acids
• oxidation with liquid reagents
– H2SO4, HNO3, HClO4
– wet ashing
• combustion in oxygen bomb
• high temperature fusion with reagents
• microwave assisted acid digestion
 Sample Preparation
GFAAS
• Some samples can be atomized directly
• Pipetted directly into furnace
– Blood, petroleum products, organic solvents
• Solid samples can weighted directly into cups or
tantalum boats
– Plant leaves, animal tissues, inorganic substances
Disadvantages
• calibration is difficult
• Requires compositions of standards that
approximate the sample
 Applications
AAS is still widely used
• Less expensive/complex
instrumentation
• Lower operating cost
• Greater precision
 Applications / Data Quality
• 60+ metals / metalloids quantitatively measured
by atomic absorption
Detection limits for atomic absorption (Table 9-3)
• Flame atomization 1 – 20 ng/mL (0.001 – 0.020
ppm)
• Electrothermal atomization
• 0.002 – 0.01 ng/mL (2-10 ppt)
Accuracy
• 1-2% for flame
• 5-10% for electrothermal
 Calibration curves
Plot of absorbance vs. concentration

Non ideal
Absorbance
 Standard addition method
Matrix
• Everything in the sample aside from the
analyte that we wish to determine

To account for the matrix effects, standard

addition method is used
 Standard addition method
In a sample, the analyte is generally not isolated
from other components in the sample
The MATRIX is everything in the sample except
the analyte
Efficiency of atomization in the flame depends on
the matrix
Sometimes certain components interfere in the
analysis by either enhancing or depressing the
analytical signal → matrix effect
But, the extent to which the signal is affected is
difficult to measure
 Standard addition
• Standard addition must be used whenever the
matrix of a sample changes the analytical
sensitivity of the method.

In other words,
The slope of the working curve for standards made
with distilled water is different from the same
working curve made up in river water (or whatever
your real world matrix happens to be)
Standard addition method
How is this best done in practise?

Vx containing cx

Vs of std solution cs

Vt
• Add a quantity of standard solution such
that the signal is increased by about 1.5 to
3 times that for the original sample.
• The solutions in the above flasks all have
the similar concentration of the matrix.
• Analyse all solutions
 Standard addition method

bc s
cx 
m Vx

Vx is the volume of the unknown solution with a concentration cx

Variable volumes of Vs of standard of the analyte with a known
Concentration of cs are added to the different flask
 Standard Addition Method

• useful when encounter with difficulties

associated with production of standards with
an overall composition resembling that of the
sample
• requires adherence to Beer’s law, must be
confirmed experimentally
• the absence of any background or the use of
an accurate blank measurement
• employ single point or multiple point standard
addition methods