Process atomic emission spectrometry

Inductively coupled argon plasma (icp) and direct current argon plasma (dcp) atomic emission spectrometry are solution techniques that have been appHed to copper-beryUium, nickel—beryUium, and aluminum—beryUium aUoys, beryUium compounds, and process solutions. The internal reference method, essential in spark source emission spectrometry, is also useful in minimizing drift in plasma emission spectrometry (17). Electrothermal (graphite... 

In the context of chemometrics, optimization refers to the use of estimated parameters to control and optimize the outcome of experiments. Given a model that relates input variables to the output of a system, it is possible to find the set of inputs that optimizes the output. The system to be optimized may pertain to any type of analytical process, such as increasing resolution in hplc separations, increasing sensitivity in atomic emission spectrometry by controlling fuel and oxidant flow rates (14), or even in industrial processes, to optimize yield of a reaction as a function of input variables, temperature, pressure, and reactant concentration. The outputs ate the dependent variables, usually quantities such as instmment response, yield of a reaction, and resolution, and the input, or independent, variables are typically quantities like instmment settings, reaction conditions, or experimental media. 

Brenner et al. [ 169] applied inductively coupled plasma atomic emission spectrometry to the determination of calcium (and sulfate) in brines. The principal advantage of the technique was that it avoided tedious matrix matching of calibration standards when sulfate was determined indirectly by flame techniques. It also avoided time-consuming sample handling when the samples were processed by the gravimetric method. The detection limit was 70 ig/l and a linear dynamic range of 1 g/1 was obtained for sulfate. 

Instrumentation. Flame Characteristics. Flame Processes. Emission Spectra. Quantitative Measurements and Interferences. Applications of Flame Photometry and Flame Atomic Emission Spectrometry. 

All four dissolution procedures studied were found to be suitable for arsenic determinations in biological marine samples, but only one (potassium hydroxide fusion) yielded accurate results for antimony in marine sediments and only two (sodium hydroxide fusion or a nitricperchloric-hydrofluoric acid digestion in sealed Teflon vessels) were appropriate for determination of selenium in marine sediments. Thus, the development of a single procedure for the simultaneous determination of arsenic, antimony and selenium (and perhaps other hydride-forming elements) in marine materials by hydride generation inductively coupled plasma atomic emission spectrometry requires careful consideration not only of the oxidation-reduction chemistry of these elements and its influence on the hydride generation process but also of the chemistry of dissolution of these elements. 

Atomic emission spectrometry (AES) is also called optical emission spectrometry (OES). It is the oldest atomic spectrometric multielement method which originally involved the use of flame, electric arc or spark excitation. Recently there has been considerable innovation in new sources plasma sources and discharges under reduced pressure. Littlejohn et al. (1991) have reviewed recent advances in the field of atomic emission spectrometry, including fundamental processes and instrumentation. 

Instrumentation. Flame characteristics. Flame processes. Emission spectra. Quantitative measurements and interferences. Applicaiion.s of flame photometry and flame atomic emission spectrometry. 

Atomic emission spectrometry can be used for on-line monitoring of incineration and other processes where elemental analysis is vital. Developments in the area of on-line... 

Regarding historical insight and descriptions of principles and fundamentals of flame atomic emission spectrometry, a chapter on flame photometry appeared in the first edition of Treatise on Analytical Chemistry (Vallee and Thiers 1965) covering the flame and burner, photometer/spec-trometer, fundamental discussion of excitation and processes within the flame, cation and anion interferences and handling of analytical samples. In an analogous, expanded, detailed and excellent treatment of EAES in the second edition of the Treatise on Analytical Chemistry, Syty (1981) discusses types of flames used for excitation, processes within flames, spectral, chemical and physical interferences and remedies. 

This chapter deals with optical atomic, emission spectrometry (AES). Generally, the atomizers listed in Table 8-1 not only convert the component of samples to atoms or elementary ions but, in the process, excite a fraction of these species to higher electronic stales.. 4, the excited species rapidly relax back to lower states, ultraviolet and visible line spectra arise that are useful for qualitative ant quantitative elemental analysis. Plasma sources have become, the most important and most widely used sources for AES. These devices, including the popular inductively coupled plasma source, are discussedfirst in this chapter. Then, emission spectroscopy based on electric arc and electric spark atomization and excitation is described. Historically, arc and spark sources were quite important in emission spectrometry, and they still have important applications for the determination of some metallic elements. Finally several miscellaneous atomic emission source.s, including jlanies, glow discharges, and lasers are presented. 

Another route to depopulation of the upper level is spontaneous emission, which is described by an analogous spontaneous emission coefficient This mechanism is the basis of atomic emission spectrometry in the ultraviolet-visible spectrum particularly. In the MMW region with its much lower frequency transitions it is not a significant contributor, as will be demonstrated below. Modifying Equation 1.2 to bring in the populations N of the upper and lower states one can write for the absorption and emission processes... 

An EPA-approved procedure for the analysis of plutonium in water is listed in Table 6-2. In addition, the following ASTM standard methods relate to the measurement of plutonium in water D 3648, D 3084, D 3972, and D 1943 (ASTM 1981, 1982a, 1982b, 1987). Recent work has focused on more rapid analytical methods in order to determine monitor plutonium levels in waste process streams at nuclear facilities. For example, Edelson et al. (1986) have investigated the applications of inductively-coupled plasma-atomic emission spectrometry (ICP-EAS) to routinely analyze water samples. 

Fundamentals. The composition of liquids with respect to both identity and concentration of dissolved species can be determined with inductively coupled plasma atomic emission spectrometry (ICP-AES) [972]. The employed spectrometer can be coupled directly with an electrochemical cell wherein processes like corrosion or anodic dissolution occur. Continuous aspiration of very small liquid volumes transferred into the spectrometer allows determination of rates of dissolution as a function of various experimental parameters like electrode potential [973]. 

Flame atomic absorption was until recently the most widely used techniques for trace metal analysis, reflecting its ease of use and relative freedom from interferences. Although now superceded in many laboratories by inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry, flame atomic absorption spectrometry still is a very valid option for many applications. The sample, usually in solution, is sprayed into the flame following the generation of an aerosol by means of a nebulizer. The theory of atomic absorption spectrometry (AAS) and details of the basic instrumentation required are described in a previous article. This article briefly reviews the nature of the flames employed in AAS, the specific requirements of the instrumentation for use with flame AAS, and the atomization processes that take place within the flame. An overview is given of possible interferences and various modifications that may provide some practical advantage over conventional flame cells. Finally, a number of application notes for common matrices are given. 

AFS is a method of elemental analysis that involves the use of a light source to excite gaseous atoms radiatively to a higher energy level, followed by a deactivation process that involves emission of a photon. This emission process provides the measured fluorescence signal. AFS can be distinguished from the related atomic spectrometric techniques of atomic absorption spectrometry (AAS) and atomic emission spectrometry (AES) because it involves both radiative excitation and deexcitation. 

See also Activation Analysis Neutron Activation. Atomic Absorption Spectrometry Principles and Instrumentation. Atomic Emission Spectrometry Principles and Instrumentation. Chromatography Overview Principles. Gas Chromatography Pyrolysis Mass Spectrometry. Headspace Analysis Static Purge and Trap. Infrared Spectroscopy Near-Infrared Industrial Applications. Liquid Chromatography Normal Phase Reversed Phase Size-Exclusion. Microscopy Techniques Scanning Electron Microscopy. Polymers Natural Rubber Synthetic. Process Analysis Chromatography. Sample Dissolution for Elemental Analysis Dry... 

Many methods used for qualitative analysis are destructive either the sample is consumed during the analysis or must be chemically altered in order to be analyzed. The most sensitive and comprehensive elemental analysis methods for inorganic analysis are ICP atomic emission spectrometry (ICP-AES or ICP optical emission spectrometry [ICP-OES]), discussed in Chapter 7, and ICP-MS, discussed in Chapters 9 and 10. These techniques can identify almost all the elanents in the periodic table, even when only trace amounts are present, but often require that the sample be in the form of a solution. If the sample is a rock or a piece of glass or a piece of biological tissue, the sample usually must be dissolved in some way to provide a solution for analysis. We will see how this is done later in this chapter. The analyst can determine accurately what elements are present, but information about the molecules in the sample is often lost in the sample preparation process. The advantage of ICP-OES and ICP-MS is that they are very sensitive concentrations at or below 1 ppb of most elements can be detected using these methods. 

Spontaneous emission of photons. This process refers to a spontaneous transition of the electron from the excited state 2 to the lower energy state 1 with emission of a photon of frequency vi2 = E2 - Ef jh. This process constitutes the photophysical basis of atomic emission spectrometry, which will be termed here optical emission spectrometry in order to use the acronym OES instead of AES because the latter acronym can be confused with that for Auger electron spectroscopy. 

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