Atomic Absorption

Spectroscopy
 Introduction
Classification
• Spectroscopy is a broad field with many subdisciplines, which can be
classified by the type of material being analyzed. This presentation will
focus on the first category, atomic spectroscopy.

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 Introduction
Timeline of Early Developments

1884 1930’s 1941 1952 1961 1962 1964

Hittorf researches Lundgardh Babat Walsh Reed First Greenfield
low pressure, develops experiments with explores potential first major commercial used the
electrode-less Flame Emission RF-ICP application ICP AAS ICP as an
ring discharges technique of atomic for growing analytical tool
absorption crystals at high
temperature

1965 1973 1975 1978 1980 1983

Wendt and Fassel First Gray Fassel & Gray Houk First
used commercial coupled a experimented demonstrated the commercial
the ICP as a ICP-OES capillary direct with inductively possibilities ICP-MS
Spectroscopic current arc coupled argon offered by the
source plasma to a plasmas coupled ICP-MS technique
quadrupole mass to
spectrometer mass
spectrometer

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 Atomic spectroscopy methods
• Atomic spectroscopy methods are based on
light absorption and emission of atoms in the
gas phase. The goal is elemental analysis -
identity and concentration
Atomic absorption spectroscopy is based on the same
principle as the flame test used in qualitative analysis.
 Atomic Absorption Spectroscopy
Principles of Operation
• Atomic absorption spectroscopy (AAS)
techniques rely on the fact that
an atomized element will absorb light
of a characteristic wavelength,
elevating it from the ground state to an
excited state.
• The amount of light energy absorbed
is proportional to the number of
analyte atoms in the light path.
• The technique is calibrated by
introducing known concentrations of
analyte atoms into the light path and
plotting the absorption versus
concentration curve.

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 The high temperature of the flame excites a
valence electron to a higher-energy orbital.

 The atom then emits energy in the form of light as

the electron falls back into the lower energy
orbital (ground state).

The intensity of the absorbed light is proportional

to the concentration of the element in the flame.
  quantitative analysis

Atomic Spectra
 Each element has a characteristic spectrum.
Example: Na gives a characteristic line at 589 nm.

 Atomic spectra feature sharp bands.

There is little overlap between the spectral lines of different

elements.
Atomic absorption spectroscopy and atomic emission
spectroscopy are used to determine the concentration of an
element in solution.
Applying Lambert-Beer’s law in atomic absorption
spectroscopy is difficult due to
variations in the atomization from the sample matrix
non-uniformity of concentration and path length of analyte
atoms.

Concentration measurements are usually determined from

a
calibration curve generated with standards of known
concentration.
 Atomic Absorption Spectroscopy
General Set Up

Mono-
Lamp Atomizer chromator Detector

• Lamp emits light for element of interest

• Atomizer converts liquid sample into free atoms
which absorb energy from the lamp
• Monochromator selects wavelength used for measurement
• Detector measures light absorbed by free atoms

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Atomic Absorption Spectroscopy
Lamp
The source of light primarily used with the
atomic absorption technique is the hollow Getter spot Anode
cathode lamp (HCL).

Typically each lamp is dedicated to the

analysis of a single element, though
in some cases a few elements can be
combined into a single lamp.
Because of this limitation, atomic
absorption is typically used for analysis of Pyrex Electrical
either a single element or a small number envelope Cathode contacts
of elements.

Typical hollow cathode lamp construction

See notes for details

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 Atomic Absorption Spectroscopy
Atomizer

Atomization is the process that converts

a liquid sample into free atoms. Light beam
The diagram shows the different steps Atomization Free atoms
that occur during atomization, starting with Vaporization
the element being prepared as a solution. Liquid melt
Compound
Element M undergoes different stages: decomposition
Solid
•Solution: MAliquid (compound) Desolvation
•Nebulization: MAliquid (compound)
Aerosol
•Desolvation: MAsolid (A = solution anion) Mixing
•Vaporization: MAgas
•Atomization: M0
Nebulization
•Excitation: M*
•Ionization: M+ Droplet
Solution precipitation

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 Atomic Absorption Spectroscopy
Atomizer

Atoms can absorb discrete amounts

of energy: + energy
• Heat -
• Light at discrete wavelengths
+
An electron may change energy
levels
• An atom can pick up (absorption) - energy
or release (emission) energy.
• Atom becomes “excited”
•Excitation is explained by the +E -E
transition of an electron from M 0
M +
M0
an inner orbit (higher energy) Ground Excited Ground
state state state
to an outer orbit.

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 Atomic Absorption Spectroscopy
Flame AAS Atomizer

• In flame AAS (FAAS) the sample is prepared Flame AAS

as a liquid and nebulized into the flame.
Advantages
• The fundamental characteristic of this
technique is the atomization that happens in • Short analysis time possible
the flame. • Good precision
• Easy to use
• Cheap
Limitations
• Sensitivity
• Dynamic range
• Requires flammable gases
• Unattended operation is not possible
because of flammable gases
• Must not contain excessive amounts of dissolved
solids
Schematic diagram of flame or graphite furnace atomic absorption
spectrometer system
Source:
ToC Atomic spectroscopy applications in the contract environmental
laboratory
 Atomic Absorption Spectroscopy
Graphite Furnace AAS Atomizer
• Dissolution of sample into a liquid form is Graphite furnace
required in most cases.
Advantages
• Sample is injected into a graphite tube and
• High sensitivity due to
electrothermally heated in different stages
− entire sample is atomized at one time
to atomize the analyte.
− free atoms remain in the optical path longer
• In graphite furnace atomic absorption • Reduced sample volume
(GFAAS) the atomization happens in three • Ultra trace analysis possible
stages: • Can run unattended, even overnight
• Drying Limitations
• Ashing • Very slow
• Atomization • Fewer elements can be analyzed
• Graphite furnace operation is a complemen- • Poorer precision
tary technique to conventional flame AA and • More chemical interferences (compared to flame AA)
adds some advantages to the analysis. • Method development requires skill
• Standard additions calibration required more frequently
(compared to flame AA)
• Expensive consumables (graphite tubes)

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 Atomic Absorption Spectroscopy
Graphite Furnace AAS Atomizer
The graphite tube sits in this
apparatus which supplies an inert
gas and a powerful to heat the tube,
which then desolvates and atomizes
the sample.

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 Atomic Absorption Spectroscopy
Other Atomizers

• Hydride generation technique Cold vapor technique

• Suitable for elements forming volatile Used specifically for mercury (has a large
hydrides (As, Sn, Bi, Sb, Te, Ge and Se) when enough vapor pressure at ambient tempera-
reacted with a reducing agent, such as ture) which can be reduced to atomic state
sodium borohydride. by a strong reducing agent, such as sodium
borohydride, tin (II) chloride).

Advantages Advantages
• Separation of specific elements as hydrides which can • Eliminates many matrix interferences
eliminate matrix interference • Good sensitivity due to 100% sampling efficiency
• Good sensitivity due to 100% sampling efficiency • Good precision
• Good precision • Faster than graphite furnace AA
• Faster than graphite furnace AA
Limitations
Limitations
• Limited to mercury only
• Limited to specific elements • Mercury must be stabilized in solution
• Some chemical interferences
• Requires specific sample preparation (analyte
must be converted to a specific oxidation state)

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 Atomic Absorption Spectroscopy
System

Key Applications
• Determination of trace metals/
impurities in oil, plants, water
• Analysis of elements in fluids,
water, soil, food, serum,
semiconductor material
• And many more

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 Example
Flame AAS: Determination of Low Levels of Gold in Mineral Ore

Wavelength Characteristic Detection limit

used concentration (mg/L)
(nm) (mg/L)
242.8 0.079 0.0054
267.6 0.14 0.0098

Flame AAS results for

Au in mineral ore

Source:
ToC Extending the Analytical Range for Gold Using Agilent UltrAA Lamp
s
 Example
GF AAS: Measuring Cd, Cu, Pb, Co, Ni in Marine Invertebrates

Signal graphics for Ni in CRM 786 R Mussel Tissue

Source:
ToC Sequential Determination of Cd, Cu, Pb, Co and Ni in Marine Invert
ebrates by Zeeman GFAAS
 Atomic Emission Spectroscopy
General
• Due to the limitations in AAS, techniques that don’t require dedicated lamps
for each element have come into use. These techniques, called
atomic emission spectroscopy (AES), rely on the fact that once an
atom of a specific element is excited (as in atomic absorption), it emits
light in a characteristic pattern of wavelengths (an emission spectrum)
as it returns to the ground state.
• The flame is not an ideal excitation source for atomic emission.
Therefore hotter sources are used.
• We will discuss the following techniques:
• Microwave plasma atomic emission spectroscopy (MP-AES)
• Inductively coupled plasma optical emission spectroscopy (ICP-OES)

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 Atomic Emission Spectroscopy
Microwave Plasma Atomic Emission Spectroscopy

• Nitrogen plasma is used to desolvate, MP-AES

atomize, and excite the atoms in the liquid
Advantages
sample that has been nebulized into it.
The nitrogen plasma is considerably hotter • Safe (no flammable gas)
(up to 5,000o K) than the air-acetylene • Low operating costs as nitrogen can
flame used in AA. be extracted from compressed air using
a nitrogen generator
• The atomic emission is quite strong for most • No lamps required for analysis
elements, leading to improved detection • Identification and quantitation of virtually
capability and linear dynamic range over all metals and many metalloids.
flame AA for most elements. • Better performance than flame AAS
Limitations
• The intensity of the light emitted is measured
using optical detection at the wavelengths • Higher initial cost than AAS
characteristic of the elements of interest. • More interferences compared with flame AA
(including spectral interferences)
• Not as sensitive as graphite furnace AAS or ICP-MS
• Not as productive as ICP-OES
• No isotope determination

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 Microwave Plasma Atomic Emission Spectroscopy
System
Key Applications Monochromator Wavelength
with CCD detector drive mechanism
• Trace elements in geological
samples
Pre-optics
• Metals in soil extracts
• Major elements in food and
beverages
• Analysis of petroleum
• Analysis of waste water

Waveguide Plasma

Sample introduction system Torch

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 Microwave Plasma Atomic Emission Spectroscopy
How Does It Work?
• Agilent MP-AES runs from nitrogen extracted from air using a nitrogen
generator.
• Axial magnetic and radial electrical fields sustain the nitrogen plasma
• Sample aerosol is introduced into nitrogen plasma

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 Microwave Plasma Atomic Emission Spectroscopy
How Does It Work?
• Axial emission from the nitrogen plasma is directed into the fast-scanning
monochromator optics
• Wavelength-specific emissions are detected using a high-efficiency CCD

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 Microwave Plasma Atomic Emission Spectroscopy
Determination of Nutrients in Soil (Multielement Testing)

Cu Fe Mn Zn
Wavelength (nm) 324.754 324.7 259.94 372 257.61 280.1 213.857 213.9

Technique MP-AES FAAS MP-AES FAAS MP-AES FAAS MP-AES FAAS

Measured conc. μg/g
SSTD-Trail 1 1.44 1.42 7.76 8.44 24.26 26.22 0.64 0.62

SSTD-Trail 1 1.46 1.45 7.96 8.24 24.40 25.96 0.64 0.64

SSTD-Trail 1 1.44 1.42 8.08 8.64 23.70 26.50 0.62 0.58

Av. µg/g 1.45 1.43 7.93 8.44 24.12 26.23 0.63 0.61

Standard dev. 0.01 0.02 0.16 0.20 0.37 0.27 0.01 0.03
MP-AES results for Cu, Fe, Mn, and Zn in DTPA extraction of soil, compared to FAAS

Source:
ToC Determination of available nutrients in soil using the Agilen
t 4200 MP-AES
 Microwave Plasma Atomic Emission Spectroscopy
Measuring Major and Minor Elements in Milk

Element Certified Uncertainty Result Recovery (%)

Values (g/kg) (g/kg) (g/kg)

Ca 13.9 0.7 14.21 102

K 17 0.8 16.66 98

Mg 1.26 0.07 1.31 104

Na 4.19 0.23 4.25 101

P 11 0.6 11.27 102

Certified Uncertainty Result Recovery Determination of Ca, K, Mg, Na, P, Fe, Zn and Cu in TMAH, Triton
Values (g/kg) (mg/kg) (mg/kg) (%)
X-100, EDTA and ionization buffer by MP-AES 4200
Zn 44.9 2.3 45.89 102

Fe 53 4 50.51 95

Cu 5 0.23 5.13 103

Source: Measuring major and minor elements in milk using the

ToC Agilent MP-AES 4200
 Inductively Coupled Plasma Optical Emission
Spectroscopy
Principles of Operation
• An argon inductively coupled plasma (hotter ICP- OES
than MP, up to 10,000o K) is used to
desolvate, atomize, and excite the atoms in Advantages
the liquid sample that has been nebulized • Fastest sample throughput
into it. • Simultaneous multi-element analysis
(up to 73 elements)
• The intensity of the light emitted is measured • Wide dynamic range (from sub-ppb to % level)
using optical detection at the wavelengths • Tolerates complex matrices
characteristic of the elements of interest. • Low argon gas consumption
• ICP-OES is capable of measuring both atomic • Safe (no flammable gas)
and ionic emission so more wavelengths can Limitations
be monitored • Higher initial costs than AAS or MP-AES
• These measurements can be compared to a • More spectral interferences compared with
standard to quantify the concentration of the MP-AES
elements in the sample. • Not as sensitive as graphite furnace AAS or
ICP-MS
• No isotope determination

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 Inductively Coupled Plasma Optical Emission
Spectroscopy
General Set Up
Plasma torch can be
viewed axially or
radially. Some “dual
view” instruments
allow viewing of both
orientations,
depending on the
analysis being
performed. (Axial
view gives longer path
length and thus
greater sensitivity.)

Argon plasma Spectrometer Quantification

Simplified schematic diagram of ICP-OES spectrometer system

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 Inductively Coupled Plasma Optical Emission Spectroscopy
System
Key Applications
•Monitoring of water/wastewater/solid wastes
•Determination of trace elements in water
•Mercury monitoring in environmental samples
Electronics
•Quantitative analysis of multiple elements in
water/soil/sediment environment samples Vertical torch

•Analysis of soil – analysis of micronutrient content

(Agriculture)
•Determination of precious metals and gold
Pumping system

Solid State RF
Sample introduction
system

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 Inductively Coupled Plasma Optical Emission
Spectroscopy
Analysis of Milk Powder
Element Certified value (mg/kg) Measured value (mg/kg) Recovery (%) Analysis of NIST milk
powder 8435 SRM using
Major nutrients the 5100 SVDV ICP-OES
K 766.491 13630 13070 96
Ca 315.887 9220 9750 106
P 213.618 7800 7160 92
Na 589.592 3560 3530 99
S 181.792 2650 2650 100
Minor and trace nutrients
Mg 279.078 814 749 92
Zn 202.548 28.0 28.9 103
Sr 421.552 4.35 4.37 101
Fe 259.940 1.8 1.9 107
Cu 327.395 0.46 0.46 100
Mo 204.598 0.29 0.27 92
Mn 257.610 0.17 0.18 103

Source: Analysis of milk powders based on Chinese standard

ToC method using the Agilent 5100 SVDV ICP-OES
 Inductively Coupled Plasma Optical Emission
Spectroscopy
Analysis of Biodiesel Oil
Element  Background Calibration Correlation MDL
(nm) correction used range (mg/kg) coefficient (ppm)

Ca 422.673 Fitted 0-2 0.99995 0.004

K 766.491 FACT 0-2 0.99996 0.008

K 766.491 Fitted 0-2 0.99935 0.048

Mg 279.553 Fitted 0-2 0.99994 0.0004

Na 588.995 FACT 0-2 0.99991 0.002

Na 588.995 Fitted 0-2 0.99996 0.048

Calibration curve for P 213.618 nm line, using FBC P 213.618 Fitted 0-2 0.99996 0.013
background correction, shows excellent linearity
across the calibrated range, with a correlation S 181.972 Fitted 0-2 0.99967 0.31
coefficient of 0.99986.

Agilent 5100 ICP-OES wavelengths and calibration parameters.

All results are shown in solutions.

Source: Analysis of biodiesel oil (as per ASTM D6751 & EN

ToC 14214) using the Agilent 5100 SVDV ICP-OES
 Inductively Coupled Plasma Mass
Spectrometry
General
• ICP-MS combines two advantages:
1. Argon ICP as a highly efficient ion source
2. A mass spectrometer for fast scanning, high ion transmission and unit mass
resolution
• The main difference to ICP-OES is to analyze atomic ions. Most elements
have the first ionization potential of 4 to10 eV, which are efficiently ionized
in argon ICP.
• Ions are passed into the high vacuum region for separation and detection.
Photons and neutral species are rejected.
• The mass spectrometer separates ions based on their mass-to-charge ratio
(m/z).

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 Inductively Coupled Plasma Mass
Spectrometry
General
An electron multiplier detector ICP-MS
generates a pulse for each ion Advantages
reaching it.
• Most sensitive technique
Since the charge on a singly • Multi-element analysis
ionized element is 1, the m/z is • Isotopic information (IR, ID analysis)
equal to the mass, so ICP-MS • Wide dynamic range
measures the elements as a • Tolerates complex matrices
simple spectrum of characteristic Limitations
atomic (isotopic) mass from 6Li
• Less matrix tolerance than ICP-OES
to 238U.
• Most expensive technique
(purchase and running costs)
• Subject to isobaric interferences

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 Inductively Coupled Plasma Mass Spectrometry
General Set Up
Simplified schematic
diagram of the major

mass spectrometer
components of a

Collision reaction
quadrupole ICP-MS
system.

Quadrupole
Ion lenses
Interface

Detector
cell

Argon plasma Vacuum system Quantification

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 Inductively Coupled Plasma Mass Spectrometry
System
Octopole reaction cell
system (ORS)
Inductively coupled
plasma

Detector

Nebulizer and Quadrupole mass

spray chamber spectrometer

Peristaltic pump Turbo vacuum

pump

RF generator

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 Inductively Coupled Plasma Mass
Spectrometry
How Helium Collision Cell Mode Removes Spectra Interference

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 Inductively Coupled Plasma Mass Spectrometry
ICP-MS as a Chromatography Detector
• In addition to its common use as a standalone metals analyser, ICP-MS is increasingly
applied as a detector for a range of chromatographic separation methods
– Capillary electrophoresis (CE)
– Field-flow fractionation (FFF)
– Ion chromatography (IC)
– Liquid chromatography (HPLC)
– Gas chromatography (GC)
• In this configuration, the front-end technique separates the different species
(with time), and the ICP-MS operates as a mass selective detector to measure
the element(s) associated with the compound(s) of interest as they elute from
the chromatograph.

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 Inductively Coupled Plasma Mass Spectrometry
Speciation with LC-ICP-MS and GC-ICP-MS
• HPLC-ICP-MS application examples:
• Inorganic vs. organic arsenic
• Organo-tin
• Methyl-mercury

• GC-ICP-MS examples:
• Pesticides
• OP nerve agent residues Seven overlaid chromatograms of apple juice spiked with 500
• PBDEs ng/L As standard.

• Nanoparticles

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 Inductively Coupled Plasma Mass Spectrometry
Drinking Water Analysis
• Most developed countries have enacted regulations and monitoring programs to ensure that the supply
of drinking water is free from potentially harmful chemicals. The fast, multi-element technique of
ICP-MS is widely used for this.

Calibration plot
of Cd and Hg

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 Inductively Coupled Plasma Mass Spectrometry
Trace Metallic Impurity Analysis in High Purity HCl
HCl is frequently used to remove metallic impurities on the surface of silicon
wafers. The manufacturing process of semiconductor devices requires routine
monitoring of ultra-trace contaminants in HCl.

Element m/z Mode DL ppt BEC ppt

Li 7 cool 0.016 0.004
Be 9 no gas 0.13 0.11
B 11 no gas 4.5 9.7
Na 23 cool 0.44 1.3
Mg 24 cool 0.11 0.22
Al 27 cool 0.79 1.1
K 39 cool/NH3 0.40 0.50
Ca 40 cool/NH3 1.1 2
As, which suffers ArCl+ interference, can As 75 He 4.0 16
be measured at trace levels.
Source: Direct analysis of trace metallic impurities in high
ToC purity hydrochloric acid by Agilent 7700s ICP-MS
 Summary
Atomic Spectroscopy Techniques
AAS MP-AES ICP-OES ICP-MS

FAAS GFAAS SQ QQQ

Detection Limits 100’s 10’s-100’s ppb – 10’s 100’s <ppt <ppt

ppb ppt ppb ppt-ppb

Sequential
Measurement Sequential Sequential Sequential Simultaneous Sequential (*MS/MS for difficult
mode (MS) interference problems)

Maximum 100-200 50-100 300-500 2000-2500 750-1000 500-750

samples/day (~6 elements) (~2 elements) (~10 elements) (50+ elements) (~50 elements) (~50 elements)

Working 3-4 2-3 4-5 7-8 10-11 9

dynamic range

Operator skill Low Mid Low Mid High Highest

required

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Schematic diagram of an atomic absorption spectrometer
Light Source
Hollow-cathode lamp: The cathode
contains the element that is analysed.

Atomization
Desolvation and vaporization of ions or atoms in a sample:
high-temperature source such as a flame or graphite
furnace

 Flame atomic absorption spectroscopy

 Graphite furnace atomic absorption spectroscopy

1- Flame atomic absorption spectroscopy:
Sample introduction:
 Process in a Flame AA
M* M+ + e _ Ionization

Mo M* Excitation

MA Mo + A o Atomization

Solid Solution Vaporization

Graphite furnace atomic absorption spectroscopy

Sample holder: graphite tube

 Samples are placed directly in

the graphite furnace which is
then electrically heated.
 Beam of light passes through the
tube.
 Graphite Flame
Advantages Solutions, slurries and solid samples Inexpensive (equipment,
can be analyzed. day-to-day running)
Much more efficient atomization High sample throughput
greater sensitivity Easy to use
Smaller quantities of sample High precision
(typically 5 – 50 µL)
Provides a reducing environment
for easily oxidized elements

Disadvanta- Expensive Only solutions can be

ges Low precision analyzed
Low sample throughput Relatively large sample
Requires high level of operator skill quantities required (1 – 2
mL)
Less sensitivity (compared
to graphite furnace)
Applications of Atomic Absorption Spectroscopy

water analysis (e.g.Ca, Mg, Fe, Si, Al, Ba content)

food analysis; analysis of animal feedstuffs ( e.g. Mn, Fe, Cu, Cr, Se, Zn)
analysis of additives in lubricating oils and greases (Ba,Ca, Na, Li, Zn, Mg)
analysis of soils
clinical analysis (blood samples: whole blood, plasma, serum; Ca, Mg, Li,
Na, K, Fe)
Detection Limits
Atomic Absorption Overview
 Schematic Diagrams

Absorption

Emission
 Five Basic Optical Instrument
Components

1) Source - A stable source of radiant energy at the

desired wavelength (or l range).
2) Sample Holder - A transparent container used to hold the
sample (cells, cuvettes, etc.).
3) Wavelength Selector - A device that isolates a restricted
region of the EM spectrum used for measurement
(monochromators, prisms, & filters).
i) Photoelectric Transducer - (Detector) Converts the
radiant energy into a useable signal (usually electricity).
>) Signal Processor & Readout - Displays the transduced
signal on a readout device such as a meter, digital
readout, chart recorder, computer, etc.