Instrumentation atomic absorption spectroscopy

Atomic absorption spectroscopy instrumentation can conveniently be considered under the following subheadings. 

Atomic absorption spectroscopy instruments place a sample in a high temperature flame that yields atomic species and passes selected, element specific, illumination through the flame to detect what wavelengths of light the sample atoms absorb. Either acetylene or nitrous oxide fuels the analytical flame. This process again demands that solid samples be digested (dissolved in an acid or fused with a salt) and dissolved to form a solution that can be aspirated or sprayed into the instrument s flame, while protecting the sample material from contamination or adulteration. 

Atomic absorption, along with atomic emission, was first used by Guystav Kirch-hoff and Robert Bunsen in 1859 and 1860, as a means for the qualitative identification of atoms. Although atomic emission continued to develop as an analytical technique, progress in atomic absorption languished for almost a century. Modern atomic absorption spectroscopy was introduced in 1955 as a result of the independent work of A. Walsh and C. T. J. Alkemade. Commercial instruments were in place by the early 1960s, and the importance of atomic absorption as an analytical technique was soon evident. 

Instrumental Quantitative Analysis. Methods such as x-ray spectroscopy, oaes, and naa do not necessarily require pretreatment of samples to soluble forms. Only reUable and verified standards are needed. Other instmmental methods that can be used to determine a wide range of chromium concentrations are atomic absorption spectroscopy (aas), flame photometry, icap-aes, and direct current plasma—atomic emission spectroscopy (dcp-aes). These methods caimot distinguish the oxidation states of chromium, and speciation at trace levels usually requires a previous wet-chemical separation. However, the instmmental methods are preferred over (3)-diphenylcarbazide for trace chromium concentrations, because of the difficulty of oxidizing very small quantities of Cr(III). 

Atomic absorption spectroscopy of VPD solutions (VPD-AAS) and instrumental neutron activation analysis (INAA) offer similar detection limits for metallic impurities with silicon substrates. The main advantage of TXRF, compared to VPD-AAS, is its multielement capability AAS is a sequential technique that requires a specific lamp to detect each element. Furthermore, the problem of blank values is of little importance with TXRF because no handling of the analytical solution is involved. On the other hand, adequately sensitive detection of sodium is possible only by using VPD-AAS. INAA is basically a bulk analysis technique, while TXRF is sensitive only to the surface. In addition, TXRF is fast, with an typical analysis time of 1000 s turn-around times for INAA are on the order of weeks. Gallium arsenide surfaces can be analyzed neither by AAS nor by INAA. 

Magnesium may conveniently be determined by atomic absorption spectroscopy (Section 21.21) if a smaller amount (ca 4 mg) is used for the separation. Collect the magnesium effluent in a 1 L graduated flask, dilute to the mark with de-ionised water and aspirate the solution into the flame of an atomic absorption spectrometer. Calibrate the instrument using standard magnesium solutions covering the range 2 to 8 ppm. 

With flame emission spectroscopy, there is greater likelihood of spectral interferences when the line emission of the element to be determined and those due to interfering substances are of similar wavelength, than with atomic absorption spectroscopy. Obviously some of such interferences may be eliminated by improved resolution of the instrument, e.g. by use of a prism rather than a filter, but in certain cases it may be necessary to select other, non-interfering, lines for the determination. In some cases it may even be necessary to separate the element to be determined from interfering elements by a separation process such as ion exchange or solvent extraction (see Chapters 6, 7). 

The data presented in Table 21.4, in conjunction with the experimental details given in Sections 21.21-21.26, will enable the determination of most elements to be carried out successfully. For detailed accounts of the determination of individual elements by atomic absorption spectroscopy, the Bibliography (Section 21.27) should be consulted. In addition, most instrument manufacturers supply applications handbooks relative to the apparatus in which full experimental details are given. 

Two different instrumental measurements were used to test the oxidation hypothesis GC and atomic absorption (AA). GC was used to determine the chain length distribution of the EO. From the GC results, an average chain length number was calculated. The gas chromatogram is shown in Fig. 21.1. In addition, headspace GC measurement of the gaseous compounds dissolved in the liquid ethoxylate was made and compared to typical or good product. Atomic absorption spectroscopy was used to determine the levels of several trace metals known to catalyze oxidation of fatty chemicals. 

Limit of detection The method you choose must be able to detect the analyte at a concentration relevant to the problem. If the Co level of interest to the Bulging Drums was between 1 and 10 parts per trillion, would flame atomic absorption spectroscopy be the best method to use As you consider methods and published detection limits (LOD), remember that the LOD definition is the analyte concentration producing a signal that is three times the noise level of the blank, i.e., a S/N of 3. For real-world analysis, you will need to be at a level well above the LOD. Keep in mind that the LOD for the overall analytical method is often very different than the LOD for the instrumental analysis. 

Quantitative analysis in flame atomic absorption spectroscopy utilizes Beer s law. The standard curve is a Beer s law plot, a plot of absorbance vs. concentration. The usual procedure, as with other quantitative instrumental methods, is to prepare a series of standard solutions over a concentration range suitable for the samples being analyzed, i.e., such that the expected sample concentrations are within the range established by the standards. The standards and the samples are then aspirated into the flame and the absorbances read from the instrument The Beer s law plot will reveal the useful linear range and the concentrations of the sample solutions. In addition, information on useful linear ranges is often available for individual elements and instrument conditions from manufacturers and other literature. 

Allan Walsh, in 1955, was the pioneer for the introduction of atomic absorption spectroscopy (AAS), which eventually proved to be one of the best-known-instrumental-techniques in the analytical armamentarium, that has since been exploited both intensively and extensively in carrying out the quantitative determination of trace metals in liquids of completely diversified nature, for instance blood serum-for Ca2+, Mg2+, Na+ and K+ edible oils-Ni2+ beer samples-Cu+ gasoline (petrol)-Pb2+ urine-Se4+ tap-water-Mg2+ Ca2+ lubricating oil-Vanadium (V). 

Figure 1.2 shows the basic instrumentation necessary for each technique. At this stage, we shall define the component where the atoms are produced and viewed as the atom cell. Much of what follows will explain what we mean by this term. In atomic emission spectroscopy, the atoms are excited in the atom cell also, but for atomic absorption and atomic fluorescence spectroscopy, an external light source is used to excite the ground-state atoms. In atomic absorption spectroscopy, the source is viewed directly and the attenuation of radiation measured. In atomic fluorescence spectroscopy, the source is not viewed directly, but the re-emittance of radiation is measured. 

A variety of mathematical models can be used to establish appropriate relationships between instrumental responses and chemical measurands. Quantitative analysis in single-element atomic absorption spectroscopy is typically based on a single measured signal that is converted to concentration of the analyte of interest via the calibration line ... 

Chemical Properties. Elemental analysis, impurity content, and stoichiometry are determined by chemical or instrumental analysis. The use of instrumental analytical methods (qv) is increasing because these are usually faster, can be automated, and can be used to determine very small concentrations of elements (see Trace and RESIDUE ANALYSIS). Atomic absorption spectroscopy and x-ray fluorescence methods are the most useful instrumental techniques in determining chemical compositions of inorganic pigments. Chemical analysis of principal components is carried out to determine pigment stoichiometry. Analysis of trace elements is important. The presence of undesirable elements, such as heavy metals, even in small amounts, can make the pigment unusable for environmental reasons. 

Many of the instrumental methods that have been developed are quite sophisticated. Some methods are suited to identifying elements. For example, atomic absorption spectroscopy allows the element to be identified and also allows the quantity of the element that is present to be found (Figure 2.8). 

Instrumental techniques Instrumental methods of analysis that are particularly useful when the amount of sample is very small. Examples are atomic absorption spectroscopy and infrared spectroscopy. 

ICP offers good detection limits and a wide linear range for most elements. With a direct reading instrument multi-element analysis is extremely fast. Chemical and ionization interferences frequently found in atomic absorption spectroscopy are suppressed in ICP analysis. Since all samples are converted to simple aqueous or organic matrices prior to analysis, the need for standards matched to the matrix of the original sample is eliminated. 

Atomic Absorption Spectroscopy. One of the more sensitive instruments used to detect metal-containing toxicants is the AA spectrophotometer. Samples are vaporized either by aspiration into an acetylene flame or by carbon rod atomization in a graphite cup or tube (flameless AA). The atomic vapor formed contains free atoms of an element in their ground state, and when illuminated by a light source that radiates light of a... 

While atomic absorption spectroscopy and inductively coupled plasma techniques will continue to be the workhorse instrument in the metals analytical laboratory, an evergrowing need exists for the complementary... 

In 1952, Walsh in Australia realized the inherent advantages of atomic absorption spectroscopy over methods based on flame emission for quantitative analysis, and he has given a personal account of the development of the technique.197 Walsh s death in 1998 resulted in a memorial issue of the journal Spectrochimica Acta (B). As well as a brief biography of Walsh and a list of his publications, this contained 22 papers on all aspects of the history of atomic absorption spectroscopy. Together they constitute a valuable record of the birth of this important technique, the difficulties of bringing satisfactory instruments to market, and the history of the application of the method to quantify metals in a wide variety of materials and environments.198... 

C. Flameless Atomic Absorption Spectroscopy. A Jarrell-Ash Model 810 Dual Monochromator Atomic Absorption Spectrophotometer was used for this work. The instrument was equipped with the Bames Instrument s tantalum ribbon flameless atomizer and a two-... 

Multielement analysis will become more important in industrial hygiene analysis as the number of elements per sample and the numbers of samples increases. Additional requirements that will push development of atomic absorption techniques and may encourage the use of new techniques are lower detction and sample speciation. Sample speciation will probably require the use of a chromatographic technique coupled to the spectroscopic instrumentation as an elemental detector. This type of instrumental marriage will not be seen in routine analysis. The use of Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES) (17), Zeeman-effect atomic absorption spectroscopy (ZAA) (18), and X-ray fluorescence (XRF) (19) will increase in industrial hygiene laboratories because they each offer advantages or detection that AAS does not. 

Thirty-two sherds representing five different examples of Kayenta Anasazi Pueblo II pottery (Tusayan Corrugated [TC], Medicine Black-on-Red [MB], Tusayan Black-on-Red [TB], Dogoszhi Black-on-White [DB], and Sosi Black-on-White [SB]) have been analyzed for the elements As, Ba, Co, Cr, Cm, Fe, Mn, Ni, Pb, Se, V, and Zn by using the techniques of flame atomic absorption spectroscopy (.FAA) and electrothermal atomic absorption spectroscopy (ETAA). Analytical procedures for the chemical analysis of ceramics afford accuracy and sensitivity and require only a modest capital investment for instrumentation. The sherd samples were collected at two sites, one in southern Utah (Navajo Mountain [NM]) and the second in northern Arizona (Klethla Valley [KV]). These sites are approximately 60 km apart. Statistical treatment of the data shows that only three clay types were used in the 32 sherds analyzed, and that only three elements (Fe, Pb, and Ni) are necessary to account for 100% of the dispersion observed within this sample set. 

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