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