Detection atomic spectroscopy

Chemical Analysis. The presence of siUcones in a sample can be ascertained quaUtatively by burning a small amount of the sample on the tip of a spatula. SiUcones bum with a characteristic sparkly flame and emit a white sooty smoke on combustion. A white ashen residue is often deposited as well. If this residue dissolves and becomes volatile when heated with hydrofluoric acid, it is most likely a siUceous residue (437). Quantitative measurement of total sihcon in a sample is often accompHshed indirectly, by converting the species to siUca or siUcate, followed by deterrnination of the heteropoly blue sihcomolybdate, which absorbs at 800 nm, using atomic spectroscopy or uv spectroscopy (438—443). Pyrolysis gc followed by mass spectroscopic detection of the pyrolysate is a particularly sensitive tool for identifying siUcones (442,443). This technique rehes on the pyrolytic conversion of siUcones to cycHcs, predominantly to [541-05-9] which is readily detected and quantified (eq. 37). 

Tungsten is usually identified by atomic spectroscopy. Using optical emission spectroscopy, tungsten in ores can be detected at concentrations of 0.05—0.1%, whereas x-ray spectroscopy detects 0.5—1.0%. ScheeHte in rock formations can be identified by its luminescence under ultraviolet excitation. In a wet-chemical identification method, the ore is fired with sodium carbonate and then treated with hydrochloric acid addition of 2inc, aluminum, or tin produces a beautiful blue color if tungsten is present. 

The performance of microwave-assisted decomposition of most difficult samples of organic and inorganic natures in combination with the microwave-assisted solution preconcentration is illustrated by sample preparation of carbon-containing matrices followed by atomic spectroscopy determination of noble metals. Microwave-assisted extraction of most dangerous contaminants, in particular, pesticides and polycyclic aromatic hydrocarbons, from soils have been developed and successfully used in combination with polarization fluoroimmunoassay (FPIA) and fluorescence detection. 

Table 8.4 Atomic spectroscopy detection limits (micrograms/litre) (from Perkin Elmer, Guide to Techniques and Applications of Atomic Spectroscopy, 1988)...

Solid-state NMR spectroscopy has not found as wide an application in soils as it has in other fields. The great advantage of NMR is that it is specific for specific elements that is, it is tuned to a specific element and other elements are not detected. NMR spectroscopy shows the environment or multiple environments in which a particular element exists. For example, in a proton NMR spectrum, primary, secondary, and tertiary protons can be differentiated, as can protons attached to oxygen, nitrogen, and other atoms. 

The selection of a technique to determine the concentration of a given element is often based on the availability of the instrumentation and the personal preferences of the analytical chemist. As a general rule, AAS is preferred when quantifications of only a few elements are required since it is easy to operate and is relatively inexpensive. A comparison of the detection limits that can be obtained by atomic spectroscopy with various atom reservoirs is contained in Table 8.1. These data show the advantages of individual techniques and also the improvements in detection limits that can be obtained with different atom reservoirs. 

An alternative approach is to analyze the samples using procedures or instrumentation that will give the maximum amount of data for each sample. For example, recent advances in atomic spectroscopy, i.e., inductively coupled argon plasma emission spectroscopy (ICP-AES), allow 20 to 30 elements to be detected simultaneously. 

The development of solvent-impregnated resins and extraction-chromatographic procedures has enabled the automation of radiochemical separations for analytical radionuclide determinations. These separations provide preconcentration from simple matrices like groundwater and separation from complex matrixes such as dissolved sediments, dissolved spent fuel, or nuclear-waste materials. Most of the published work has been carried out using fluidic systems to couple column-based separations to on-line detection, but robotic methods also appear to be very promising. Many approaches to fluidic automation have been used, from individual FI and SI systems to commercial FI sample-introduction systems for atomic spectroscopies. 

A comprehensive review of directly coupled gas chromatography-atomic spectroscopy applications has been published [128]. This review list over 100 references classified according to the detection technique and is highly recommended. Another excellent review outlines the advances in interfacing and plasma detection [130]. A review of the gas chromatographic detection of selected trace elements (mercury, lead, tin, selenium, and arsenic) has been published. This article reviews the many different detection methods available including atomic emission techniques [131]. 

Atomic spectroscopy as a means of detection in gas chromatography is becoming popular because it offers the possible selective detection of a variety of metals, organometallic compounds, and selected elements. The basic approaches to GC-atomic spectroscopy detection include plasma emission, atomic absorption, and fluorescence. 

Image Devices. Although he never assembled an actual TV-spectrometer, Margoshes was the first to recognize the potential of TV-type detectors in analytical atomic spectroscopy. In a series of reports (50,51,52) he speculated on the advantages of using an SEC tube [vide infra] to detect radiation dispersed by an echelle spectrograph. These reports and the recent availability of various solid-state array detectors have prompted numerous... 

The physico-chemical properties of the analytes and the way they reach the detector have made atomic spectroscopy the detection technique of choice in most instances. A heated quartz cell or a similar device is connected directly to the gas outlet of the separation cell [26]. The use of an atomic fluorescence detector has provided methods for selenium [25,27] and mercury [28,29] that possess excellent analytical features and use inexpensive instruments. On a less affordable level are ICP emission [30] and atomic emission cavity spectrometers [31]. 

The nebulizer is normally interfaced directly to the LC column. It combines the eluent with a stream of gas to produce an aerosol. Much of the theoretical and practical basis of nebulization comes from atomic spectroscopy. The average droplet diameter and uniformity of the aerosol are the most important factors for ELSD sensitivity and reproducibility. As larger solute particles scatter light more intensely, an aerosol with large droplets and a narrow droplet size distribution leads to the most precise and sensitive detection. A good nebulizer should produce a uniform aerosol of large droplets with narrow droplet size distribution. The droplets cannot be too large, however otherwise, the solvent in a droplet will not be completely vaporized and errors in detection will occur. The nebulizer properties that can be adjusted to obtain the desired droplet properties are, primarily, the gas flow rate and the LC mobile phase flow rate. ... 

The identification of the chemical forms of an element has become an important and challenging research area in environmental and biomedical studies. Two complementary techniques are necessary for trace element speciation. One provides an efficient and reliable separation procedure, and the other provides adequate detection and quantitation [4]. In its various analytical manifestations, chromatography is a powerful tool for the separation of a vast variety of chemical species. Some popular chromatographic detectors, such flame ionization (FID) and thermal conductivity (TCD) detectors are bulk-property detectors, responding to changes produced by eluates in a characteristic mobile-phase physical property [5]. These detectors are effectively universal, but they provide little specific information about the nature of the separated chemical species. Atomic spectroscopy offers the possibility of selectively detecting a wide rang of metals and nonmetals. The use of detectors responsive only to selected elements in a multicomponent mixture drastically reduces the constraints placed on the separation step, as only those components in the mixture which contain the element of interest will be detected... 

The discussion of emission spectroscopy will be concluded by a description of a rather unusual application. Bay and Steiner have measured atomic hydrogen concentrations in the presence of molecular hydrogen by microwave excitation of the atomic hydrogen line spectrum. With low power fed into the gas (ca. 5 watts), there is not enough energy available for the dissociation of molecular hydrogen and subsequent excitation. Thus the measured intensities of the atomic hydrogen lines correspond to the concentrations of atoms already present in the reaction mixture. The method is curiously similar to that adopted to detect atoms and free radicals by mass spectrometry (see Section 3). 

The viewing region of the plasma can achieve a temperature of 5000-6000°C and is reasonably stable. The sample solution is aspirated into the core area between the two arms of the Y where it is atomised, excited and viewed. This technique keeps with the atomic spectroscopy theory in that the measurements are obtained by emission from the valence electrons of the atoms that are excited, and the emitted radiation consists of short well-defined lines. All these lines fall in the UV or VIS region of the spectrum and identification of these lines permits qualitative/quantitative detection of elements. 

The application of atomic spectroscopy methods to the analysis of petroleum products is important to the oil industry. All oil samples must be prepared in solution form and be at a concentration so as to be detected to quantify all metals of interest with accuracy and precision. Solutions containing petroleum products in organic solvents may be measured directly or with the use of internal standards to correct for viscosity effects. It is important that the selected solvent dissolves the oil and products and does not cause erratic flickering of the plasma, or quenches it. It is also important that the same solvent can be used to prepare calibration standards. The following methods are common sample preparation methods for metal analysis of crude and lubricating oils. 

In the application of atomic spectroscopy to FIA the sample plug is carried first to the nebuliser and eventually to the plasma source for excitation and atomisation for detection to give signal responses for the corresponding concentrations of analyte, as shown in Figure 7.3. 

An additional problem is that known elements in the periodic table, e.g. boron (B), tungsten (W) and molybdenum (Mo) tend to stick in the transport fine, nebuliser, spray chamber and torch causing memory effects in atomic spectroscopy. Elements that stick cause problems with quantification, and detection Emits and it is important that methods of reducing these are rigorously applied in analysis of these elements. However, memory effects in ICP-OES are not as pronounced as they are with graphite furnaces for refractory elements but they are present to some extent, and must be reduced or removed. 

In most cases the determination of organometallic complexes by atomic spectroscopy techniques is the only acceptable method because the analysis is selective, accurate and precise. Analysis of these complex salts may only involve a simple dilution in a solvent or destruction methods depending on the matrix it is formulated into. The presence of some sample matrices containing organometallic complexes can be severely restricted by the matrix material to achieve accurate detection and quantification of these salts. 

In the last 20 years atomic spectroscopy has made great strides, particularly with the introduction of new improved optic designs and detection methods. These improvements have led to superior resolution of the wavelengths of the excited atoms and detection techniques measuring lower levels of metals with ease. After a slow and problematic start, inductively coupled plasma optical emission spectrometry (ICP-OES) has become an established technique in most laboratories analysing a wide range of sample matrices reporting accurate and precise results. 

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