Atomic Absorption Spectrometry
Poppy Yentsch
Atomic absorption spectroscopy (AAS) and atomic emission spectroscopy (AES) is a spectroanalytical procedure for the quantitative determination of chemical elements by free atoms in the gaseous state. Atomic absorption spectroscopy is based on absorption of light by free metallic ions.
Atomic absorption spectrometry has many uses in different areas of chemistry such as clinical analysis of metals in biological fluids and tissues such as whole blood, plasma, urine, saliva, brain tissue, liver, hair, muscle tissue. Atomic absorption spectrometry can be used in qualitative and quantitative analysis.
In order to analyze a sample for its atomic constituents, it has to be atomized. The atomizers most commonly used nowadays are flames and electrothermal (graphite tube) atomizers. The atoms should then be irradiated by optical radiation, and the radiation source could be an element-specific line radiation source or a continuum radiation source. The radiation then passes through a monochromator in order to separate the element-specific radiation from any other radiation emitted by the radiation source, which is finally measured by a detector.
A glow-discharge device (GD) serves as a versatile source, as it can simultaneously introduce and atomize the sample. The glow discharge occurs in a low-pressure argon gas atmosphere between 1 and 10 torr. In this atmosphere lies a pair of electrodes applying a DC voltage of 250 to 1000 V to break down the argon gas into positively charged ions and electrons. These ions, under the influence of the electric field, are accelerated into the cathode surface containing the sample, bombarding the sample and causing neutral sample atom ejection through the process known as sputtering. The atomic vapor produced by this discharge is composed of ions, ground state atoms, and fraction of excited atoms. When the excited atoms relax back into their ground state, a low-intensity glow is emitted, giving the technique its name.
Hydride generation techniques are specialized in solutions of specific elements. The technique provides a means of introducing samples containing arsenic, antimony, selenium, bismuth, and lead into an atomizer in the gas phase. With these elements, hydride atomization enhances detection limits by a factor of 10 to 100 compared to alternative methods. Hydride generation occurs by adding an acidified aqueous solution of the sample to a 1% aqueous solution of sodium borohydride, all of which is contained in a glass vessel. The volatile hydride generated by the reaction that occurs is swept into the atomization chamber by an inert gas, where it undergoes decomposition. This process forms an atomized form of the analyte, which can then be measured by absorption or emission spectrometry.
The cold-vapor technique is an atomization method limited only for the determination of mercury, due to it being the only metallic element to have a large vapor pressure at ambient temperature.[citation needed] Because of this, it has an important use in determining organic mercury compounds in samples and their distribution in the environment. The method initiates by converting mercury into Hg2+ by oxidation from nitric and sulfuric acids, followed by a reduction of Hg2+ with tin(II) chloride. The mercury, is then swept into a long-pass absorption tube by bubbling a stream of inert gas through the reaction mixture. The concentration is determined by measuring the absorbance of this gas at 253.7 nm. Detection limits for this technique are in the parts-per-billion range making it an excellent mercury detection atomization method.
We have to distinguish between line source AAS (LS AAS) and continuum source AAS (CS AAS). In classical LS AAS, as it has been proposed by Alan Walsh,[10] the high spectral resolution required for AAS measurements is provided by the radiation source itself that emits the spectrum of the analyte in the form of lines that are narrower than the absorption lines. Continuum sources, such as deuterium lamps, are only used for background correction purposes. The advantage of this technique is that only a medium-resolution monochromator is necessary for measuring AAS; however, it has the disadvantage that usually a separate lamp is required for each element that has to be determined. In CS AAS, in contrast, a single lamp, emitting a continuum spectrum over the entire spectral range of interest is used for all elements. Obviously, a high-resolution monochromator is required for this technique, as will be discussed later.
In LS AAS the high resolution that is required for the measurement of atomic absorption is provided by the narrow line emission of the radiation source, and the monochromator simply has to resolve the analytical line from other radiation emitted by the lamp.[citation needed] This can usually be accomplished with a band pass between 0.2 and 2 nm, i.e., a medium-resolution monochromator. Another feature to make LS AAS element-specific is modulation of the primary radiation and the use of a selective amplifier that is tuned to the same modulation frequency, as already postulated by Alan Walsh. This way any (unmodulated) radiation emitted for example by the atomizer can be excluded, which is imperative for LS AAS. Simple monochromators of the Littrow or (better) the Czerny-Turner design are typically used for LS AAS. Photomultiplier tubes are the most frequently used detectors in LS AAS, although solid state detectors might be preferred because of their better signal-to-noise ratio.
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 few examples known that an absorption line from one element will overlap with another.[citation needed] 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. There are several techniques available to correct for background absorption, and they are significantly different for LS AAS and HR-CS AAS.
In LS AAS background absorption can only be corrected using instrumental techniques, and all of them are based on two sequential measurements:[12] firstly, total absorption (atomic plus background), secondly, background absorption only. The difference of the two measurements gives the net atomic absorption. Because of this, and because of the use of additional devices in the spectrometer, the signal-to-noise ratio of background-corrected signals is always significantly inferior compared to uncorrected signals. It should also be pointed out that in LS AAS there is no way to correct for (the rare case of) a direct overlap of two atomic lines. In essence there are three techniques used for background correction in LS AAS:
This is the oldest and still most commonly used technique, particularly for flame AAS. In this case, a separate source (a deuterium lamp) with broad emission is used to measure the background absorption over the entire width of the exit slit of the spectrometer. The use of a separate lamp makes this technique the least accurate one, as it cannot correct for any structured background. It also cannot be used at wavelengths above about 320 nm, as the emission intensity of the deuterium lamp becomes very weak. The use of deuterium HCL is preferable compared to an arc lamp due to the better fit of the image of the former lamp with that of the analyte HCL.
This technique (named after their inventors) is based on the line-broadening and self-reversal of emission lines from HCL when high current is applied. Total absorption is measured with normal lamp current, i.e., with a narrow emission line, and background absorption after application of a high-current pulse with the profile of the self-reversed line, which has little emission at the original wavelength, but strong emission on both sides of the analytical line. The advantage of this technique is that only one radiation source is used; among the disadvantages are that the high-current pulses reduce lamp lifetime, and that the technique can only be used for relatively volatile elements, as only those exhibit sufficient self-reversal to avoid dramatic loss of sensitivity. Another problem is that background is not measured at the same wavelength as total absorption, making the technique unsuitable for correcting structured background.
In HR-CS AAS background correction is carried out mathematically in the software using information from detector pixels that are not used for measuring atomic absorption; hence, in contrast to LS AAS, no additional components are required for background correction.
It has already been mentioned that in HR-CS AAS lamp flicker noise is eliminated using correction pixels. In fact, any increase or decrease in radiation intensity that is observed to the same extent at all pixels chosen for correction is eliminated by the correction algorithm.[citation needed] This obviously also includes a reduction of the measured intensity due to radiation scattering or molecular absorption, which is corrected in the same way. As measurement of total and background absorption, and correction for the latter, are strictly simultaneous (in contrast to LS AAS), even the fastest changes of background absorption, as they may be observed in ET AAS, do not cause any problem. In addition, as the same algorithm is used for background correction and elimination of lamp noise, the background corrected signals show a much better signal-to-noise ratio compared to the uncorrected signals, which is also in contrast to LS AAS.
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