Atomic Fluorescence

Spectroscopy
 Background
 First significant research by Wineforder and
Vickers in 1964 as an analytical technique
 Used for element analysis
– Example: Trace elements in ground water
 Has not found wide spread success because
there does not seem to be a distinct advantage
over established methods, i.e. atomic
absorbance
 What is Atomic
Fluorescence?
 “Atomic fluorescence spectroscopy (AFS)
is the optical emission from gas-phase
atoms that have been excited to higher
energy levels by absorption of radiation.”
 “AFS is useful to study the electronic
structure of atoms and to make quantitative
measurements of sample concentrations.”
 Why use AFS?
 it is a quantitative technique for
determination of a large number of
elements
 used mostly in analysis of metals in
biological samples, agricultural samples,
water, and industrial oils
 Jablonski Diagram

S2

Intersystem
S1 crossing

h h fluorescence T1

phosphorescence
S0
 Instrumentation

 Virginia Tech website maintained by Professor Brian Tissue Department of Chemistry

 General process for AFS
 nebulization - converts the sample solution into a mist made up of
tiny liquid droplets
 atomization - flow of gas carries sample into heated region where
sample molecules are broken into free atoms
– desolvation - the solvent is evaporated to produce
a solid molecular aerosal
– dissociation - molecules dissociate to produce an
atomic gas
– The atoms dissociate to produce ions and electrons
 General Process continued
 Excitation due to light source
 Fluorescence of sample
 This fluorescence can be selected for
certain wavelengths by a monochromator
 Then the detector reads the emission and
amplifies the signal
 Then the readout device relays the data
 Problems with Technique
 Precision and accuracy are highly
dependent on the atomization step
 Light source
 molecules, atoms, and ions are all in heated
medium thus producing three different
atomic emission spectra
 Problems continued
 Line broadening occurs due to the uncertainty principle
– limit to measurement of exact lifetime and frequency, or
exact position and momentum
 Temperature
– increases the efficiency and the total number of atoms in the
vapor
– but also increases line broadening since the atomic particles
move faster.
– increases the total amount of ions in the gas and thus
changes the concentration of the unionized atom
 Interferences
 If the matrix emission overlaps or lies too close to the
emission of the sample, problems occur (decrease in
resolution)
 This type of matrix effect is rare in hollow cathode
sources since the intensity is so low
 Oxides exhibit broad band absorptions and can scatter
radiation thus interfering with signal detection
 If the sample contains organic solvents, scattering occurs
due to the carbonaceous particles left from the organic
matrix
Interferences continued
 Detection Limits

 Are similar to those for Atomic Absorption

and Atomic Emission
 Varies for different elements
 * †
Detection Limits (ng/mL) for Selected Elements

Element AAS, Flame AAS, Electrothermal AES, Flame AES, ICP AFS, Flame
Al 30 0.005 5 2 5
As 100 0.02 0.0005 40 100
Ca 1 0.02 0.1 0.02 0.001
Cd 1 0.0001 800 2 0.01
Cr 3 0.01 4 0.3 4
Cu 2 0.002 10 0.1 1
Fe 5 0.005 30 0.3 8
Hg 500 0.1 0.0004 1 20
Mg 0.1 0.00002 5 0.05 1
Mn 2 0.0002 5 0.06 2
Mo 30 0.005 100 0.2 60
Na 2 0.0002 0.1 0.2 —
Ni 5 0.02 20 0.4 3
Pb 10 0.002 100 2 10
Sn 20 0.1 300 30 50
V 20 0.1 10 0.2 70
Zn 2 0.00005 0.0005 2 0.02
* -3 -3
Nanogram/milliliter = 10 g/mL = 10 ppm.
†
AAS = atomic absorption spectroscopy; AES = atomic emission spectroscopy; AFS = atomic
fluorescence spectroscopy; ICP = inductively coupled plasma.
 Final conclusion
 This technique offers some advantages for
some elements while other atomic
spectroscopy techniques may be better for
other elements
 Future work on light sources and atomizers
will increase the analytical uses of this
technique