Atomic Absorption and

Atomic Fluorescence
Spectrometry Section A
By Matt Boyd, James Joseph,
Jon Blizzard, Jackie Freebery,
Hunter Bodle

Atomization Techniques
AAS and AFS
Two techniques
Flame Atomization
Electrothermal Atomization

Flame Atomization
Analyte is nebulized by flow of
gaseous oxidants
Desolvations
Dissociation
Volitalized

Types Flames
Figure 9-1
Fuel

oxidant

Temperature
(Celsius)

Maximum
Burning (cm s-1)

Natural Gas

Air

1700-1900

39-43

Natural Gas

Oxygen

2700-2800

370-390

Hydrogen

Air

2000-2100

300-440

Hydrogen

Oxygen

2550-2700

900-1400

Acetylene

Air

2100-2400

158-266

Acetylene

Oxygen

3050-3150

1100-2480

Acetylene

Nitrous oxide

2600-2800

285

Flame Structure
Primary Combustion zone
Blue region, rarely used for
spectroscopy

Interzonal region
Most widely used part

Secondary combustion zone

Products of inner core disperse

Flame Atomizers
Uses
Atomic Absorption
Fluorescence
Emission Spectroscopy

Laminar-flow Burners are Commonly

Used
Aerosol, oxidant, and fuel are burned in flame

Performance Characteristics
Most reproducible

Electrothermal Atomizers
Provides enhanced sensitivity
Operates evaporating sample at low
temps
Ashing at higher temp
Measures absorption and
fluorescence
Used in the ICP

Electrothermal Atomization
Occurs in open ended cylindrical
graphite tube
Held between two contacts in water
cooled housing
Two inert gas streams are provided

Output Signal
Transducer output rises to a
maximum
Rapid decay back to zero
Quantitative determinations
Peak height
Peak area

Performance Characteristics
Advantages
Sensitivity
Relative precision

Disadvantages
Furnace methods
Analytical range

Analysis of Solids with

Electrothermal Atomizers
1st- weigh grounded sample into a
graphite boat and insert boat into
furnace.
2nd- prepare slurry of powdered
sample by ultrasonic agitation in an
aqueous solution. The slurry is then
pipetted into furnace atomization.

Specialized Atomization
Techniques
Glow-Discharge Atomization
Hydride Atomization
Cold-Vapor Atomization

Chapter Nine:
Atomic Absorption and Atomic
Fluorescence Spectrometry
Section 9A: Sample
Atomization Technique
By Rachel Conroy
Katie Payne

Flame Atomization
Sample is nebulized by a flow of
gaseous oxidant and fuel that carries it
to a flame
Process
Desolvation
Volatilization
Dissociation
Ionization
Excitation to form spectra

At each phase of atomization spectra can be obtained.

Types of Flames
Oxidants
Air: 1700oC to 2400oC
Oxygen
Nitrous oxide

Burning velocity states when flame is

stable
Too low: causes flashback
Too high: flame will blow of

Table 9-1 Properties of

Flames
Maximum burning
velocity.
cm s -1

Fuel

Oxidant

Temperature
o
C

Natural Gas

Air

1700 1900

39 43

Natural Gas

Oxygen

2700 2800

370 390

Hydrogen

Air

2000 2100

300 440

Hydrogen

Oxygen

2550 2700

900 1400

Acetylene

Air

2100 2400

159 266

Acetylene

Oxygen

3050 3150

1100 2480

Acetylene

Nitrous oxide

2600 2800

285

Flame Structure
Primary
Combustion Zone
Interzonal Area
Secondary
Reaction Zone
Flame Profile

Flame Atomizers Variables

Fuel and Oxidant Regulators
Double-diaphragm pressure regulators
Rotameter

Performance
Most reproducible
Low sensitivity

Schematic of a laminar-flow burner, the typical atomizer used in AAS.

Electrothermal Atomization

Long residence time

Measurements and vaporization
Evaporated at a low temperature
Ashed at a higher temperature

Electrothermal Atomizers

Graphite tube
2 inert gas streams provided
Transverse configuration
Pyrolytic carbon seal

Shown is the
cross-sectional
view of a
graphite
furnace
atomizer. The
Lvov platform
and its position
in the graphite
furnace.

Other info
Output Signals
Measures peak height

Performance
Slow because of cooling cycles
Analytical range is narrow
High sensitivity

Analysis of Solids
Finely ground samples, slurry

Specialized Atomization
Techniques
Glow-discharge
atomization
Hydride atomization
Cold-Vapor
atomization

Atomic Absorption Instrumentation

9-B

Brian May
Mandi Kaufman
Tyler MacPherson
Carolyn Inga
Ginny Harrison

Atomic Absorption
Instrumentation
The AAS Consists of
A radiation source
Sample Holder
Wavelength Selector
Detector
Signal Processor
Read Out

Radiation Sources
Potentially highly specific because of
narrow absorption lines.
These narrow lines also cause
problems because a linear relationship
between absorption and concentration
requires narrow source bandwidth
relative to the width of an absorption
line, but even good monochromators
have bandwidths significantly larger
than the absorption lines.

Problems Created
Non-linear calibration curves are
inevitable when the AA is equipped
with an ordinary spectrophotometer
and continuum radiation source.
Small calibration curves are obtained
because only a small amount of the
radiation from the monochromator slit
is absorbed by the sample, this gives
poor sensitivity

Solutions
The use of bandwidths narrower than
the absorption lines. This is done by
exciting the atoms with a lamp, filtering
the light, and choosing appropriate
operating conditions(source
temperature and pressure).
This disadvantage to this method is that
it require an additional source lamps for
each element, or group of elements.

 Hollow Cathode Lamps (9B1)Sample

 -Most common source for atomic

absorption measurements
-Consists of a tungsten anode and a
cylindrical cathode sealed in a glass
tube which is filled with either argon
or neon gas a pressure of 1-5torr
-Cathode is constructed from the
metal whose spectrum is desired (or,
if not constructed from the metal, it
then serves to support a layer of that
metal)

 -When a potential of about 300V is applied

across the electrodes, ionization occurs of
the inert gas (argon or neon). The current is
generated (of about 5-15 mA) as ions and
electrons migrate to the electrodes.
-if potential is large enough the gaseous
cations gather enough kinetic energy to
dislodge the metal atoms from the cathode
surface and produce an atomic cloud in the
process known as sputtering.
-The excited metal atoms (a portion of
those sputtered) emit their characteristic
radiation as they return to ground state

 -Efficiency of the cathode depends on

its geometry and the operating
potential:
High potentials (and thus high currents)
greater intensities
-A down-fall to high currents is that they
produce an increased number of
unexcited atoms in the cloud which
have the potential of absorbing the
radiation emitted from the excited
atoms (Self-absorption)

-This leads to lower intensities

Electrodeless Discharge
Lamps

What are they made of?

Sealed quartz tube
Filled with an inert gas (Ar)
Small amount of metal or its salt

What does it use?

Uses radio frequency
Or microwave radiation to energize it

What happens?
The gas is ionized by the frequency
Once enough energy is obtained it
excites the atoms of metal
The metal spectrum is the desired
spectrum.

What it provides
Provides radiant intensities in greater
supply than a Hollow-Cathode Lamp
(HCL)
Not as reliable as the (HCL)
But better for elements such as
Se, As, Cd, Sb

Source modulation
Emitted radiation is removed via the
monochromator
It is necessary to adjust the output
the source so intensity will fluctuate
at a constant frequency

 Detector receives 2 signal

An alternating from the source
Continuous from the flame.
These signals are then converted into
electrical responses
A high pass RC filter (section 2B-5) can be
used to remove unadjusted signals

 Adjusting the emission can be done by

inserting a circular metal disc (chopper) into
the system between the source and the flame
Rotation of this disk at a constant rate will
create a beam that is chopped to the
desired frequency
Tuning forks with vanes attatched to
alternately allow the beam to pass and to not
pass is another technique
An alternative is the power supply being
designed for intermittent or ac operation so
the source can be switched oin and of at the
desired frequency

AA Spectrophotometer
See Figure 9-13 for block diagrams

Instrument must be capable of

providing a sufficiently narrow
bandwidth to isolate the line chosen for
the measurement
Glass filter alkali metals
Only a few widely spaced resonance lines in
the visible region

Separate filter and light source for each

element
Most use photomultiplier tubes

Single-Beam

Several hollow- cathode sources

Chopper or pulsed power supply
Atomizer
Simple grating spectrometer with a
photomultiplier transducer
100% transmittance is set with a blank
The blank is replaced with samples to
determine absorbance and transmittance

Double Beam
Beam from hollow-cathode source is split by a
mirrored chopper
One half passes through the flame and the other
half goes around it
2 beams recombine by a half silvered mirror and
passed into a Czerny-Turner grating monochromator
Photomultiplier = transducer
Output = input to a lock-in amplifier
Ratio between reference and sample is amplified
and fed to the readout
Since reference beam is not passed through the
flame it cannot correct for loss of radiant power due
to absorption or scattering by the flame

Chapter 9 Section C
Megan Seeger, Andrea Lando,
Joe Bailey, and Sarah Duncan

Spectral Interferences
Can be caused by overlapping lines but is
very rare due to the emission lines of the
hollow-cathode sources being so narrow
Can also result from the presence of
combustion products that exhibit
broadband absorption or particle products
that scatter radiation
Both reduce the power of the transmitted
beam and lead to positive analytical
errors

Continued
A more troublesome problem occurs
when the source of absorption or
scattering originates in the sample
matrix
Interferences because of scattering by
products of atomization is most often
encountered when concentrated
solutions containing elements such as
Ti, Zr, and W are aspirated in the flame

Continued
Interferences caused by scattering
may also be a problem when the
sample contains organic species or if
organic solvents are used to dissolve
the sample
Flame atomization spectral
interferences by matrix products are
not widely seen and can be avoided by
variations in the analytical variables

Radiation Bufer
When an excess of the interfering
substance is added to the sample
and standards
If the concentration added is large
compared to the concentration in the
sample matrix then the contribution
from the sample matrix is
insignificant

Two-Line Correction Method

Uses a line from the source as a
reference it should be as close as
possible to the analyte line
This makes any decrease in power of
the reference line from that observed
during the calibration arises from
absorption or scattering and is then
used to correct the absorbance of the
analyte line

The Continuum-Source
Correction Method
Deuterium lamp provides a source of
continuum radiation throughout the
ultraviolet region
The radiation from the continuum
source and the hollow cathode lamp
are passed alternately through the
electrothermal atomizer, the
absorbance from the deuterium
radiation is then subtracted from the
analyte beam

Chemical Interferences
More common than spectral
interferences
Can be minimized by suitable
operating conditions

Most Common Interferences

Occurs when anion form low-volatility
compounds with the analyte only a
fraction of analyte is atomized and
the outcome is low results
Ex. Decrease in calcium absorbance with
increasing concentrations of sulfate or
phosphate

Common Interferences
Cont
Cation Interferences
Outcome: low results
Ex: Aluminum causes low results when
determining magnesium (forms a heat
stable compound)

Solutions to Interferences
When caused by formation of species
of low volatility, interference can be
eliminated by use of higher temps
Releasing Agents: cations that react
preferably with the interferent and
prevent analyte interaction
Protective Agents: prevent
interferences by forming a stable,
volatile species with the analyte

Background Correction
Based on the Zeeman
Efect
p.242-243

Zeeman Efect
When an atomic vapor is exposed to a strong magnetic
field, a splitting of electronic energy levels of the atoms
takes place that leads to the formation of several
absorption lines for each electronic transition. The sum
of the absorbencies of the lines is equal to exactly the
value of the original line from which they were formed.

A,B,C
--------------

--------C
---------

A
--------B

Splitting Pattern
Most common type of splitting:
Central line () and two equally spaced
satellite lines (). This is observed with a
singlet but for more complex transitions these
lines will be split further.
The line absorbs only plane polarized light in a
parallel direction to the magnetic field
The lines absorb only polarized radiation at a 90
degree angle to the magnetic field

How it works
Turn to page 243 in textbooks
Radiation from a cathode tube
Rotating polarizer
Separates the beam into two parts that are
polarized at 90 degrees to each other

These go into a graphite furnace that splits the

energy levels into three peaks (D)
This information then goes to a monochromator,
photomultiplier tube, and into a data analysis system.
This system subtracts the perpendicular cycle from
the parallel half cycle giving a background correction.

Background Corrections with

Source Self Reversal
Also known as the Smith-Hieftje method
Based on the self reversal or self absorption of
radiation from a cathode lamp
the absorbance is collected at periods where the
lamp is running at a low current
The background is collected when the lamp is at
high voltage
High currents = high number of nonexcited
electrons that will absorb the radiation of the
excited species

Dissociation Equilibria
Dissociation reactions involving
metal oxides and hydroxides play an
important role in determining the
emission and absorption spectra for
an element.
MO M + O
The M is the analyte atom and the OH is
the hydroxyl radical.

Dissociation Equilibria
Dissociation equilibria which involve
anions other than oxygen may also
influence flame emission and
absorption.
Line intensity for Na is decreased by
presence of HCl
NaCl Na +Cl
Adding HCL decreases Na concentration
thereby lowering line intensity.

Dissociation Equilibria
V, Al, and Ti interact with such
species as O and OH. These are
represents as Ox. These are always
present in flames.
VOx V + Ox
AlOx Al +Ox
TiOX Ti + Ox

Ionization Equilibria
Ionization of atoms is small in
combustion mixtures that involve air
as the oxidant, it is often neglected.
Ionization is important in higher temp.
flames where oxygen or nitrous oxide
is the oxidant. There are free electrons
produced by the equilibrium.
M M+ + e -

Ionization Equilibria
The equilibrium constant K for the
reaction:
K= [M+][e- ]/ [M]
Degree of Ionization of metals at flame
temps. Table 9-2 pg. 246

Ch. 9 Atomic Absorption

Spectrometry
Section D
Atomic Absorption Analytical
Techniques

Sample Preparation
1. Flame Spectroscopic Methods
Sample materials:

Soils
Animal tissues
Plants
Petroleum products
Minerals
Common problem: most are insoluble in aqueous
solutions so preliminary treatment to the sample
is required

Preliminary Treatments
Decomposition of material
Rigorous treatment of the sample at high temperatures
Con: risk losing the analyte by volatilization or as particulates in smoke

Treatment with specific reagents

Con: can cause chemical and spectral interferences or can cause the analyte to appear as in
impurity in the solution

Common Decomp. Methods

1. Treatment with hot mineral acids
2. Oxidation with liquid reagents (sulfuric, nitric, or perchloric
acids: wet ashing)

3. Combustion in an oxygen bomb (or other closed container)

4. Ashing at high temperatures
5. High temperature fusion with reagents ( boric oxide, sodium
carbonate, sodium peroxide, and potassium pyrosulfate)

Sample Preparation
2. Electrothermal Atomization
Sample Types
1. Liquid Samples: blood, petroleum products, and organic solvents.
* liquid solvents can be pipetted directly into the furnace for ashing and
atomization.
2. Solid Samples: plant leaves, animal tissues, and inorganic substances.
* solids can be weighed directly into a cup-type atomizer or into specific
containers for introduction into a tube type furnace.

Sample Introduction by
Flow Injection
Introduce samples into a flame atomic absorption
spectrometer
Peristaltic pump and valve arrangements help insure
efficiency while conserving the sample
Carrier system: Deionized water or diluted electrolyte
are used to provide continuous flushing of the flame
atomizer
This reduces build up from samples containing high levels of salts
or suspended solids

Organic Solvents
Low Molecular-weight organic solvents:
1. Alcohols
2. Esters
3. Ketones
Why Organic Solvents?
1. Increased nebulizer efficiency- increases the amount of sample
that reaches the flame
2. Rapid evaporation of the solvent
Solvent Ratios:
Leaner fuel-oxidant ratios must be used to ofset the presence of any
added organic material

This produces lower flame temperatures, which can increase the

potential for chemical interferences

Organic Solvents (cont.)

Immiscible Solvents
ex: Methyl isobutyl ketone

These solvents extract chelates of metallic ions

The resulting extract in then nebulized directly into a flame

Enhance absorption lines

Only small amounts are required to extract from relatively large
volumes of aqueous solutions
Enhance the sensitivity of the sample, which reduces interferences

Common Chelating Agents1. Ammonium pyrrolidinedithiocarbamate

2. Diphenylthicarbazone
3. 8-hydroxyquinoline
4. Acetylacetone

Calibration Curves
Should Follow Beers Law:
A= abc
A: absorption (L/ g cm)
a: absorptivity
b: path length through medium
c: concentration

Calibration Curves (cont.)

Should cover range of concentration found in the
sample
1 standard solution should be measured after
each time an analysis is performed. Using 2
standards that bracket the analyte concentration
would be more efficient in identifying any
uncontrolled variables that result from
atomization and absorbance measurements

Application of AAS

Sensitive men for the quantitative determination of more than 60

metals or metalloid elements

Table 9-3 shows Detection Limits

Columns 2 & 3 present detection limits for a number of common
elements by flame and electrothermal atomic absorption
Detection Limits
1. Flame Atomization: 0.001 0.020 ppm
2. Electrothermal Atomization: 2 x 10-6 1 x 10-5 ppm
Accuracy
Relative error

Flame Analysis: 1-2 %

Electrothermal Analysis: errors extend flame errors by a factor of 5-10

9D ATOMIC ABSORPTION
ANALYTICAL TECHNIQUES

9D-1 Sample Preparation

Sample has to be introduced into the
excitation in the form of a solution
(disadvantage).
Many materials are not soluble in common
solvents; extensive treatment is required.
Treatment with hot minerals, oxidation with
liquid reagent, ashing at high temperature, etc.

Some minerals can be atomized directly.

Solid samples are weighed into cup-type
atomizers (advantage).

9D-2 Sample Introduction by

Flow Injection
FIA Introduces samples into a flame
atomic absorption spectrometer.
Carrier stream of the FIA system
provides continuous flushing of the
flame atomizer (advantage).

9D-3 Organic Solvents

The efect of organic solvents is attributable
to increased nebulizer efficiency. More rapid
solvent evaporation also contribute to the
efect.
Use of immiscible solvents is the most
important analytical application of organic
solvents to flame spectroscopy.
Resulting extract is nebulized into the flame
(sensitivity increases).
Part of the matrix components remain in the
solvent (advantage).

9D-4 Calibration Curves

Theory is that calibration curves
should follow Beers Law which does
not happen very often
Absorbance should be directly
proportional to concentration
Use two standards that bracket the
concentration of the analyte.

9D-5 Standard Addition

Method
Should use method found in Section
1D-3
Need to compensate for chemical
and spectral interferences of the
sample

9D-6 Application of AAS

A sensitive way of determining 60 metals
and metalloid elements
Detection Limits
Flame Atomization Atomic Absorption
Spectroscopy are in the range of 1-20ng/mL,or .
001-.020ppm
Electrothermal Atomization are in the range of .
002-.01ng/mL or 2x10-6 - 1x10-5ppm

Accuracy
Error in Flame Ionization Atomic Absorption
Spectroscopy 1-2%
Electrothermal Atomization increase by a factor
of 5-10

Atomic Fluorescence
Spectroscopy
Keri Franz
Kyle Howard
Lauren Kaminsky

Fluorescence

Atomic Fluorescence
Spectroscopy
Useful and convenient for quantitative
determination of many elements
Not used as often as atomic emission
and atomic absorption
Useful for determining elements that
form vapors and hydrides- Pb, Hg, Cd, Zn
Fluorescence instruments are generally
harder to maintain and thus more
expensive

Instrumentation Sources
Sample container is usually a flame or
electrothermal atomization cell, glow discharge,
or an inductively coupled plasma
Continuum source is ideal
Hollow cathode lamps were used frequently but
now EDLs (electrodeless discharge lamps) are
more common
EDLs have greater intensity than hollow cathode
lamps
Lasers are good sources despite increased costs
and operational intricacies

Dispersive Instrumentation
Contains:
Modulated Source
Atomizer (flame or nonflame)
Monochromator or Interference Filter
System
Detector
Signal Processor
Readout

Nondispersive
Instrumentation
Contains:
Source
Atomizer
Detector

Advantages:
Low Cost & Simplicity
Multi-element Analysis Adaptability
High Sensitivity
Simultaneous Collection of Energy

For accuracy, make sure source output lacks

elemental contamination and background radiation
should not be emitted

Applications
Determination of Metals
Lubricating Oils
Seawater
Geological Samples
Clinical Samples
Environmental Samples
Agricultural Samples