Spectroscopy is a broad field with many sub disciplines, which can be

classified by the type of material being analyzed.

ATOMS MOLECULES CRYSTALS NUCLEI

Atomic Molecular • X-ray • Nuclear magnetic
spectroscopy spectroscopy crystallography resonance
• AAS • UV-VIS
• MP-AES • UV-VIS-NIR
• ICP-OES • FTIR
• ICP-MS • Fluorescence
• Atomic spectroscopy includes
Atomic Spectroscopy
a number of analytical techniques
Identification based on
used to determine the elemental
Electromagnetic spectrum Mass spectrum
composition of a sample by
examining its electromagnetic Atomic Absorption
• Flame AAS
spectrum or its mass spectrum.
• Graphite Furnace AAS
• Vapor (Hydride) Generation AAS

Atomic Emission
• MP-AES
• ICP-MS
• ICP-OES
• X-ray Fluorescence (XRF)

Atomic Interference
• X-ray Diffraction (XRD)
 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 of atomic application ICP for AAS ICP as an
ring discharges technique absorption growing crystals analytical tool
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
What’s Measured?

Emission 1. Absorption of energy causes

an electron to move to a higher
E2 energy level (E2) → AA
2. The excited electron will eventually
drop back to the ground state and
E1 emit light
at a particular wavelength
(emission) → MP-AES, ICP-OES
3. If there is enough energy, the
electron will leave the atom
completely and leave behind
Nucleus a positively charged ion (ionization)
Electron → ICP-MS
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.
 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
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

 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
 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”
+E -E
• Excitation is explained by the
M0 M+ M0
transition of an electron from
Ground Excited Ground
an inner orbit (higher energy) state state state
to an outer orbit.
 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: 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
electrothermally heated in different stages • High sensitivity due to
− 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)
 Atomic Absorption Spectroscopy
Elemental Coverage in AAS

H Flame Only He
Li Be Flame & Furnace B C N O F Ne
M
Na Al Si P S Cl Ar
g
M
K Ca Sc Ti V Cr Fe Co Ni Cu Zn Ga Ge As Se Br Kr
n
M
Rb Sr Y Zr Nb Tc Ru Rh Pd Ag Cd In Sn SB Te I Xe
o
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra Ac
P S T
Ce Pr Nd Eu Gd Tb Dy Ho Er Yb Lu
m m m

A C F M
Th Pa U Np Pu Bk Cf Es No Lr
M m m o
 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)
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
 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)
 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 flame all metals and many metalloids.
AA for most elements. • Better performance than flame AAS
• The intensity of the light emitted is measured Limitations
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
 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

 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 the liquid Advantages
sample that has been nebulized into it. • Fastest sample throughput
• The intensity of the light emitted is measured • Simultaneous multi-element analysis
using optical detection at the wavelengths (up to 73 elements)
characteristic of the elements of interest. • Wide dynamic range (from sub-ppb to % level)
• Tolerates complex matrices
• ICP-OES is capable of measuring both atomic
• Low argon gas consumption
and ionic emission so more wavelengths can
• Safe (no flammable gas)
be monitored
• These measurements can be compared to a Limitations
standard to quantify the concentration of the • Higher initial costs than AAS or MP-AES
elements in the sample. • More spectral interferences compared with
MP-AES
• Not as sensitive as graphite furnace AAS or
ICP-MS
• No isotope determination
 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

 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
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).
 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
• Tolerates complex matrices
measures the elements as a
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
Inductively Coupled Plasma Mass Spectrometry
General Set Up
Simplified schematic
diagram of the major
components of a
quadrupole ICP-MS
system.

mass spectrometer
Collision reaction

Quadrupole
Ion lenses
Interface

Detector
cell

Argon plasma Vacuum system Quantification

 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.
 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
 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