Matthew Brereton V1.

00 04/05/2011
Field Service Engineer
Atomic Absorbance Spectroscopy

An AA is made up of five vital parts which are respectively:

• Light source
• Nebulizer (the kitchen end)
• Burner head (the kitchen end)
• Monochromator
• Photomultiplier

Light source

The most common lamp you will find being used with AA is a hollow cathode lamp.
A hollow cathode lamp basically has a specific element sealed inside along with an
inert gas such as neon or argon. When the elements are electrically excited within the
tube they go into their excited state which causes them to emit a light which is
specific to the particular element. This is your light source being generated. Now if
the atoms in the hollow cathode lamp match the element which has be atomized in the
burner (this is covered in the burner head section) then it will result in absorbance.
Some hollow cathode lamps are multi element lamps (WHY ?)

Another type of lamp is an elctrodeless discharge lamp. But I do not know much
about this and suspect there are not many of them out there. Apparently they use a
radiofrequency coil to excite atoms to a higher energy state.

The kitchen end

The so called kitchen end is where your sample liquid is introduced to the flame
which will atomize you’re your element. This part of the AA is made up of some
main parts. You have a nebulizer which is where the sampler is initially introduced.
Then the spray chamber which is used to unify the sample mist and deliver it to the
burner head. The burner head which is where your flame is lit and your elements are
atomized and the ignition which is usually a glow plug which will rotate over the
burner head during ignition.
Obviously this part of the instrument will get very hot 2300 degrees C hot so
protections is needed not just for the user but the other parts of the machine.
Now because the light source needs to go through the kitchen end of the instrument
and on to the monochromator this means the kitchen needs to have holes to allow the
light through. These holes usually have lenses in which as you can imagine can
become clouded affecting the efficiency of the machine.

Matthew Brereton V1.00 04/05/2011

Field Service Engineer
Matthew Brereton V1.00 04/05/2011
Field Service Engineer
Nebulizer

A nebulizer is basically an aerosol. A liquid is turned into a fine spray with the use of
pressure and gasses.

In the nebulizer you will usually have a mix of air and acetylene flowing in and then
up through the burner head. The pressure of these gasses coming through the
nebulizer draws your sample up and sprays it through the spray chamber and onto the
burner head as a fine mist. The more uniform and finer this mist is the better results
you will achieve with your analysis.

Ways the mist is made finer are nebulizer optimization, a glass bead can centered just
in front of the nebulizer – this works by the spray being impacted on the glass bead
causing a greater mist and a spray cone which is centered in the spray chamber.
Because nebulization isn’t very good at distinguishing between large and small
droplets (the mist) a spray cone is used to catch all of the larger droplets. All of these
steps are aimed at getting the most uniformed spray coming through the burner head.
The more even the spray the more accurate your repeatability and results will be but
most importantly the sensitivity of the instrument will be increased. SENSITIVITY is
the key word when working with atomic absorbance spectroscopy.

Now as you can imagine when you’re feeding pure sample which is possibly
corrosive through this part of the AA you will get a lot of residual build up over time
which will affect the performance of the instrument. It is very important that on a
service you dismantle the nebulizer and spray chamber, changing seals and parts
where needed and cleaning the rest as well as can be done.
Things to look out for are blockages in the polypropylene feeder tube, the gas inlets,
the drain tube, the nebulizer and build up on the glass bead which bears the brunt of
the sample (think how cloudy a lamp housing window gets in a hplc detector this is
because it is the first thing to come into contact with the light the same applies with
the nebulizer and glass bead coming into contact with the sample).

Burner Head (atomizer)

There are two types of burner heads, one for use with acetylene and air and the other
for use with acetylene and nitrous oxide. Where as the acetylene air burner can be
used for most elements generating a heat of (2300 degrees) the nitrous oxide burner
has the advantage of generating greater heat (2700 degrees) which is needed to
atomize some elements. How ever if you tried using the nitrous burner with elements
which need less excitement to become atoms then you will burn the elements off
before they have chance to absorb any of the light from the hollow cathode lamp.

Obviously the burner head needs to be clean just like the spray chamber to insure
uniform spray through the flame. The mouth of the burner needs to be unblocked all
the way along so that you get a solid flame if you have blockages, you will easily be
able to see them due to the fact that the flame will have inconsistencies. The flame is
Matthew Brereton V1.00 04/05/2011
Field Service Engineer
Matthew Brereton V1.00 04/05/2011
Field Service Engineer
generated by the air and acetylene which is in the aerosol. These two gasses can have
their ratio’s adjusted depending on what type of flame you want and the type of flame
you want is usually dictated by the element you are looking for. The two flame types
are usually referred to as a lean and a reach flame, the lean flame being biased to
more air than acetylene or with a nitrous burner more nitrous and vice versa for a rich
flame.

The previous two atomizers are used for liquid samples but what if you need to
atomize a solid state sample ?

Electro thermal atomizers

An electro thermal atomizer works by having a graphite tube and running a current
through it. The natural ohmic resistance the graphite tube has generates heat once it
has a current running through it. The graphite tubes are typically 20-25mm in length
and have a 5-6mm ID. And the measure volumes are usually 10-50 microleters or a
weighed mass of around 1mg. Now rather than just blasting the sample with a lot of
heat strait off a temperature profile is used. The typical stages of this profile are as
such:

• Drying – any solvent or moisture is dryed off

• Pyrolysis – the majority of the sample is removed
• Atomization – the element atomizes
• Cleaning – residual sample is burnt off under a high temp

With this type of atomizer there is not as much cleaning needed and usually as long as
it has not been mistreated.

Monochromator

Once the light source has passed through the kitchen end of the instrument any light
that was not absorbed will pass though to the monochromator. Its first port of call
after the entrance slit is grating. The grating is used to diffract the light into all of the
many wavelengths. The monochromator is very much like any monochromator
whether it is in a UV hplc detector or a spectrophotometer. There is very little to do in
the way of servicing this part of the instrument due to its delicate nature.

Photomultiplier tube

The PMT is used to change the photons that are being sent from the monochromator
into electrons and thus creates a signal. The way this works is the photons hit an
electrically charge metal foil inside the PMT which results in electrons being emitted.
This is then amplified and collected by an anode and transmitted to data collection
software.

Matthew Brereton V1.00 04/05/2011

Field Service Engineer
Matthew Brereton V1.00 04/05/2011
Field Service Engineer

There can be additional parts to an AA. Such as a deuterium lamp. This lamp is used
for back ground correction, which is very important for reducing noise.

Back Ground absorption and correction.

“The relatively small number of atomic absorption lines (compared to atomic emission
lines) and their narrow width (a few pm) make spectral overlap rare; there are only very
few examples known that an absorption line from one element will overlap with another.
Molecular absorption, in contrast, is much broader, so that it is more likely that some
molecular absorption band will overlap with an atomic line. This kind of absorption
might be caused by un-dissociated molecules of concomitant elements of the sample or
by flame gases. We have to distinguish between the spectra of di-atomic molecules,
which exhibit a pronounced fine structure, and those of larger (usually tri-atomic)
molecules that don’t show such fine structure. Another source of background absorption,
particularly in ET AAS, is scattering of the primary radiation at particles that are
generated in the atomization stage, when the matrix could not be removed sufficiently in
the pyrolysis stage.

All these phenomena, molecular absorption and radiation scattering, can result in
artificially high absorption and an improperly high (erroneous) calculation for the
concentration or mass of the analyte in the sample.”

Background absorption can be corrected using two measurements. The first being
total absorption and background absorption. The difference between the two gives
you the net atomic absorption

There are a few ways of dealing with background absorption which will be discussed
here.

Deuterium background correction.

A deuterium lamp is used to measure the background absorption over the entire width
of the entrance slit on the monochromator.

Smith – hieftje background correction

This technique is uses the hollow cathode lamp at normal current to achieve the
measurement of total absorption and it achieves the background absorption
measurement with a high current pulse.

Matthew Brereton V1.00 04/05/2011

Field Service Engineer
Matthew Brereton V1.00 04/05/2011
Field Service Engineer

Set up of an AA

A lot of AA’s now are completely automated so they will automatically optimize
them selves for the specific element you are analyzing. How ever on older
instruments you will need to change align the hollow cathode lamp, adjust its current,
adjust the high voltage current (this controls the signal which is amplified by the
PMT) and set up the gasses.

Here is an example for lead:

Here is an example for copper:

Technical terms and there meanings.

Matthew Brereton V1.00 04/05/2011

Field Service Engineer