Basic Theory

Atomic Absorption Spectroscopy

Bohr model of ATOM

h
+ Energy P+

e-

P+

e-

P+

e-

Ground state
Excitation

Excited state
DECAY

Ground state

If higher energy is absorbed by the atom, the electron can be completely dissociated from the atom

Positively charged ion

Bohr model of ATOM

Energy Level Diagram
atomic absorption ionization/excitation Ion Excited State atomic /ionic emission
ion emission

energy

Ion Ground State Excited States

ionization

3
1 2

Ground State

atom emission

By Plancks equation: E = h and = c/

excitation

where, E = energy (or so-called photon) h = Plancks constant = frequency = wavelength c = speed of light

E = hc/

Theory of AA
Flame

h
Hollow cathode Lamp Monochromator Detector Sample in

Light Source
Hollow Cathode Lamp (HCL)

are a type of discharge lamp that produce narrow emission from atomic species electric discharge ionizes rare gas atoms, which are accelerated into the cathode and sputter metal atoms into the gas phase. Collisions with gas atoms or electrons excite the metal atoms to higher energy levels, which decay to lower levels by emitting light

Light Source HCL vs EDL

HCL Hollow Cathode Lamp Almost all elements $$ Lamp turret Medium lamp intensity EDL Electrodeless Lamp A few elements As, Se, Pb $$$$ Dedicated power supply Stronger lamp intensity

Atomizer
The analyte atoms be in the gas phase. Ions or atoms in a sample must undergo desolvation and vaporization in a high-temperature source

E (measured by
detector) Atomization

M*

MX
Vaporization
(MX)n

E (=h)
from HCL

Desolvation
M(H2O)m,X
-

FAAS: Air-Acetylene / Nitrous oxideAcetylene analyzes solution only GFAAS: electro-thermal furnace accepts solution, slurries and solid samples

GFAAS vs. FAAS

GFAAS more efficient atomizer than flame GFAAS can accept directly very small absolute quantities of sample GFAAS provides a reducing environment for easily oxidized elements samples are placed directly in the graphite furnace and the furnace is electrically heated in several steps to dry the sample, ash organic matter, and vaporize the analyte atoms

GFAAS vs. FAAS

What happen inside atomizer

E (measured by
detector) Atomization

atomic absorption M*

Ion Excited State energy

M MX

Ion Ground State

Excited States

Vaporization
(MX)n

E (=h)
from HCL

ionization excitation

Ground State

Desolvation
M(H2O)m,X
-

Light (energy) from HCL is absorbed

Monochromator

consists of a diffraction grating (dispersing element), slits, and spherical mirrors. The light source emits a broad spectrum of radiation as represented by the multicolored line from the lamp to the grating

Schematic of a Czerny-Turner monochromator

Monochromator

Czerny-Turner (C-T) type most common type Ebert-Fastie type compact type Echelle type mostly for ICP

Schematic of a different monochromatic optics system

Detector
convert photons to an electrical signal consists of a photocathode and a series of dynodes in an evacuated glass enclosure. When a photon of sufficient energy strikes the photocathode, it ejects a photoelectron due to the photoelectric effect
The amplification depends on the number of dynodes and the accelerating voltage. This amplified electrical signal is collected at an anode at ground potential, which can be measured.
Schematic of a PMT

Single beam Vs Double beam

Double beam optics

Single beam optics

Summary
Flame

h
Hollow cathode Lamp Monochromator Detector Sample in

HCL emits unique energy which can only be absorbed by a particular element

single element analysis

By Beers Law

E (measured by Atomic Absorption AA

detector)

E = (E E) = abc c = E /ab cI
atomic absorption

a = coefficient of absorption b = length of burner head c = element concentration I = intensity,

M*

Atomization

M MX

Ion Excited State energy Ion Ground State

Vaporization
(MX)n

E (=h)
from HCL

h
ionization
excitation

Excited States Ground State

Desolvation
M(H2O)m,X
-

Processes take place for a nebulized sample droplet in AA burner head

Theory of ICP-AES
Atomic Emission ICP
plasma Monochromator / Polychromator Sample in Detector

Measure the emitted light during the excited atoms decay back to ground state

multiple element analysis

By Beers Law Ei = hi = bc c = Ei / b cIi

= coefficient of emission b = length of burner head c = element concentration Ii = intensity, Ei i= 1,2,3,4, . n

M+ * M+
Ionization

h 2

atomic /ionic emission Ion Excited State Ion Ground State Excited States 3 1 2 energy
atom emission
ion emission

M*

M
Atomization

h 1

MX
Vaporization
(MX)n

Ground State
-

Desolvation
M(H2O)m,X

Processes take place for a nebulized sample droplet in ICP discharge

Detection Limits

AA vs. ICP-AES : Detection Limits

ICP-AES Level of measurement Detection Limit Typical Linear Dynamic Range Precision short term long term (>4 hrs) Very good for most elements Very good for some elements Excellent for some elements Flame AAS GFAAS

105 10 6*
0.3 - 2%** < 5%

103
0.1 - 1%

103
1 - 5%

Remarks: For comparing the typical ICP-AES, FAAS and GFAAS in the market * Can reach to108 with range extension ** precision improves with the use of internal standards

AA vs. ICP-AES :
ICP-AES Interferences Spectral Chemical (matrix) Ionization Dissolved solids (max tolerable conc) Semi-quantitative analysis common almost none minimal 2 - 30% yes & easy

Matrix & Interferences

Flame AAS almost none many some 0.5 - 3% no GFAAS few many minimal > 20% no

Remarks: For comparing the typical ICP-AES, FAAS and GFAAS in the market * Can reach to108 with range extension ** precision improves with the use of internal standards

AA vs. ICP-AES : Speed & Cost

ICP-AES No. of elements Sample throughput Sample Usage Routine operation Method development Unattended operation Combustible gases Hollow Cathode Lamp / Electrodeless Dicharge Lamp (EDL) Capital cost Sample running cost > 75 5-30 elements /min/sample high easy skill required yes no no high affortable Flame AAS > 68 GFAAS > 50 15 sec/elements 4 min/elements /sample /sample Very high easy easy no yes yes low low Very low easy skill required yes no yes medium/high high

Remarks: For comparing the typical ICP-AES, FAAS and GFAAS in the market

Interference & Solutions

Technique
Flame AAS

Type of Interference
Ionization Chemical Physical

Method of Compensation
Ionization buffers Releasing agent or nitrous oxide-acetylene flame Dilution, matrix matching, or method of additions Standard Temperature Platform Furnace (STPF) conditions, standard additions

GFAAS

Physical and chemical

Molecular absorption
Spectral

Zeeman or continuum source background correction

Zeeman background correction

ICP-OES

Spectral
Matrix

Background correction or the use of alternate analytical lines

Internal standardization Interelement correction (IEC), use of alternate masses, higher resolution systems or reaction/collision cell technology Internal standardization

ICP-MS

Spectral

Matrix

Application

Choosing a Technique for the Determination of Copper in an Electroplating Bath

Flame AAS SingleElement GFAAS Multi-Element GFAAS Radial/Axial ICP-OES ICP-MS

Criteria Detection limits Accuracy/precision Concentration range Sample volume Elements per sample Sample throughput Purchase price

Source: Choosing The Right Trace Element Technique, R. Thomas, Todays Chemist at Work, Vol 8, No. 10, 42-48

Application

Choosing a Technique for the Determination of Lead and Cadmium in Blood

Flame AAS Single-Element GFAAS Multi-Element GFAAS Radial/Axial ICP-OES ICP-MS

Criteria Detection limits Accuracy/precision Concentration range Sample volume Elements per sample Sample throughput Operator expertise Purchase price

Source: Choosing The Right Trace Element Technique, R. Thomas, Todays Chemist at Work, Vol 8, No. 10, 42-48

Other Applications

Pb poisoning : detection of Zn and Pb in human hair Se and Hg analysis in sea food, such as fish tissue, mussels, oyster & etc.

Advantages of AA over ICP-AES

Wide dynamic range

measure from ppm to sub-ppb levels (FAAS + GFAAS) Gas supply : Acetylene vs. Argon Labour skill : Less in AAS Training time : Less in AAS Method development time : Less in AAS Maintenance : Less in AAS

Low running cost

Spectral Interference Zero