Atomic absorption spectrometry (AAS)

Done by: Samyah Alanazi

History
Atomic absorption was discovered in 1814 by Joseph von Fraunhofer (German optician) who observed dark lines Fraunhofer lines in the spectrum of the sun. These lines were subsequently found to be due to the elements in outer core of the sun absorbing continuous light emitted from inner zones. Fraunhofer lines were originally given labels from A to Z but these labels are now obsolete in chemistry.

Fraunhofer lines

The atomic absorption spectrometer was invented in 1950 by Sir Alan Walsh.

Principle
When a solution containing a metallic salt is sprayed into flame a small fraction of atoms become thermally excited and emit light. However, most atoms remain in the ground state. These ground state atoms can absorb at the same wavelengths that thermally excited atoms of the same metal emit.

The processes of atomic emission and absorption

Emission
E1

Absorption
E1

Photon E0 E = E1 E0 E = E1 E0

Photon E0

 So, in atomic absorption it is necessary to supply photons of precisely the right energy to excite the atoms, so that their absorbance by the sample can be determined. The way this is done is described in the next slide.

Instrumentation for atomic absorption spectrometry

AAS similar to flame emission spectrometer except that there is a source od radiation of exactly the right wavelength to excite the element being measured. The key components of an atomic absorption spectrometer are shown in the next figure.

Components of an atomic absorption spectrometer

Modulator

Source
The source is almost always a Hollow cathode lamp (HCL) . A hollow cathode lamp contains elements that are made with the same metal as being tested. I.e. if zinc is being analysed a zinc cathode will be used in the lamp. The lamp is filled with Helium or Argon at low pressure and several hundred applied between the electrodes. Energetic electrons from the cathode ionise the gas by collisions.

 E.g. Ar + eAr + + 2e The positively charged ions are accelerated towards the cathode (-ve charged) and sputter metal atoms from the surface. The gaseous metal ions are then excited by collisions with electrons and gas ions: e- , Ar + M (g) M* (g)

 The excited metal atoms then emit the characteristic emission lines : M * (g) M (g) + energy Different cathode lamp will be used to analyse another element . It is possible to use multi- element lamps (e.g. Ca/Mg) .

Electrical modulator
In AA there will not only be absorption of light from HCL but there will be also atomic emission. i.e. if the concentration of sodium atoms is being measured in an AAS, a small proportion of a sodium atoms will be excited in the flame and will emit light . This will give rise to the background emission which will effect the recorded absorption value.

 To overcome this, is to use modulation of the source . The light from HCL is modulated ( the intensity is rhythmically changed ) by either : 1- putting a chopper in the light path. 2- modulating the power delivered to the HCL lamp to alter its output.

Mechanical modulation in AAS

 In effect the signal from the lamp in the detector is now an alternating current (AC) signal. In contrast the background emission is a direct current (DC) signal as it does not change with time. So, the modulation is synchronised to the signal amplifier. This means that the signal amplifier is (tuned) so that it will only amplify signals of the same frequency by the modulator.

Flame
The sample is usually introduced into the flame using a nebuliser. The purpose is to get the sample in the form of aerosol of fine droplets. As in FES the venturi effect is used.

Schematic of an AAS nebuliser

 Efficiency of the nebuliser depends upon: 1- surface tension of liquid (organic liquids give finer aerosols). 2- flow rates of gases (these can be accurately controlled). 3- viscosity. 4- Density. 5- Vapour pressure.

 It is possible to enhance absorbance by including a suitable organic solvent in the calibration/sample solution, e.g. 80% ethanol or methanol. These reduce the surface tension of the aspirated solution, reducing aerosol size and enhancing atomization. Once nebulised, the sample is passed into the burner/atomiser. This is usually long and thin to increase absorption in accordance with Beerlamberts law. It is narrow to reduce scattered light entering monochromator (scattered light will tend to disperse away from the line of the flame rather in line).

The important characteristics of the flame are: 1- Its temperature. 2- whether it is oxidizing/ reducing. Commonly used fuels include: 1- Alkanes. 2- Hydrogen. 3- Acetylene. Commonly used oxidants: 1- Air. 2- Oxygen. 3- Nitrous oxide (NO).

Monochromator
Monochromator functions to ensure only the light of a selected wavelength passes through the flame. Slits on either sides of the monochromator will reduce the amount of a scattered light from the flame and reduce the scattered light energy from the dispersion device.

Detector
The detector in an AAS is usually a photomultiplier. A photomultiplier contains a photo emissive cathode coated with an easily ionised material (e.g. Caesium- antimony alloy). A photon of a suitable energy hitting this material causes the release of an electron- the surface converts a light beam into electrical signal. The electron is accelerated towards a positively charged anode with sufficient energy such that when it hits the anode 2 to 10 electrons are released. These are then attracted to subsequent anodes and the process repeat for more and more electrons each time. Typical photomultiplier have 10 anodes, giving very high amplification.

Recorder
The recorder is usually a digital readout of the absorption. Modern instruments have full computer control and data interfacing.

Procedure

Terms used in AAS

1- Sensitivity: Is a concentration of the element under investigation in ppm that reduces the light intensity by 1%, i.e. : Io = 100 It =99 Flame

 Thus: A = log Io/It = log 100/99 = 0.0044 Therefore, sensitivity is the concentration of the element in ppm giving an absorbance of 0.0044. 2- limit of detection: in AAS is the minimum amount of the element that can be detected with 95% certainty.

 3- It is usually taken as twice the sample standard deviation of the results at one or near the absorbance of the blank. 4- Expressed as concentration of an element in ppm that can be distinguished from zero concentration with 95% certainty.

Some applications of AAS

Biological Samples: 1- Determination of calcium in serum. 2- Determination of cadmium. 3- Determination of lead. 4- Zinc in plant leaves. Environmental Samples: 1- Analysis of airborne particulate matter. 2- Mercury in air/water. 3- Trace elements contamination in soil Industrial Samples: 1- Determination of molybdenum in steel. 2- Tin in canned fruit juice.

Advantages of AAS over FP

1- Sensitivity. 2- Applicability. 3- Smaller flame effect. 4- Less interference from other cations.

Similarities of AAS and FP

AAS suffer the same level of interferences as FP from: 1- Anion due to complexation. 2- Alcohols due to surface tension effects. 3- Sugars due to viscosity effects. 4- Ionisation (overcome by use of releasing agent).

Disadvantages of AAS
1- Many metals absorb in the very far UV region and thus can not be determined. 2- HCL to be changed for different elements in the sample. 3- flame problems .Such as high rate of the flame, loses of samples in the nebuliser, sample amount and absorption of emission lines near 200 nm.

 To overcome these issues Electro-thermal ionisation is used via graphite furnace technique (GF-AAS). The sample is electrically heated in a pyrolytic graphite tube which replace flame.

Advantages of GF-AAS
1- the atom kept in the light beam for long time 2- 100- 1000 fold improvement in detection limits.

Disadvantages of GF-AAS
1- lack of precision. 2- Background absorption. 3- Analyte can be lost during ashing if volatile salts are present. 4- Analysis time is slow. 5- Expensive.