Source inductively-coupled plasma-optical emission

Furthermore, it is desired that atomization and excitation occur in an inert chemical environment to minimize possible interferences. Different flame, spark, and arc somces have been used as the excitation sources since the beginning of the twentieth century however, none of these approximates the fiiU fist of conditions fisted above. It was not until mid-1960s when the analytically useful plasma sources were developed, subsfantially improving fhe capabilities of OES. The first commercially available inductively coupled plasma optical emission spectrometry (ICP-OES) was introduced in 1974 and since then the revival of OES can be noted. 

Since the intensity of the source does not affect sensitivity, but does influence the noise, the high-intensity source increases the DLs of this system by a factor of 2-5 over conventional AAS. The linear dynamic range of the system is 5-6 orders of magnitude, much broader than conventional AAS and similar to inductively coupled plasma-optical emission (ICP-OES) (discussed in Chapter 7). 

As in inductively coupled plasma optical emission (ICP-OES) spectra, in addition to atomic lines, intense ionic lines are also observed, the use of an ICP as an ion source for MS seemed logical, but overcoming the difference in pressure between the ICP (generated at atmospheric pressure) and the mass spectrometer (10 —10 mbar) proved difficult and had to be accomplished via the use of a two-cone interface. Despite the advantages that double-focusing sector field mass spectrometers (higher mass resolution) and TOP analyzers (high data acquisition speed) can offer, approximately 90% of the ICP-MS units used worldwide are equipped with a quadrupole filter for mass analysis. 

The amount of deposited yttrium vs applied current densities was determined using inductively coupled plasma-optical emission spectroscopy (ICP-OES). Concentration profiles were measured by secondary ion mass spectrometry (SIMS) on the coated samples before and after heat treatment, using a 10 keV primary ion source. The yttrium depth profiles were established with signals. The chemical state of the as-deposited and the thermally treated film was also investigated by X-ray photoelectron spectroscopy (XPS) using an Mg Ka X-ray source, without sputtering the surface. 

The measurements were performed using a Thermo Elemental IRIS Inductively Coupled Plasma Atomic Emission Spectrometer (ICP-AES). A 2 kW crystal-controlled radio frequency (RF) generator operating at 27.12 MHz powers the plasma source. An Echelle optical system with a 381-mm focal length diffracts the light from the plasma source before it is focused onto the Charge Injected Device (CID) camera detector [4]. 

Spectroscopic methods for the deterrnination of impurities in niobium include the older arc and spark emission procedures (53) along with newer inductively coupled plasma source optical emission methods (54). Some work has been done using inductively coupled mass spectroscopy to determine impurities in niobium (55,56). X-ray fluorescence analysis, a widely used method for niobium analysis, is used for routine work by niobium concentrates producers (57,58). Paying careful attention to matrix effects, precision and accuracy of x-ray fluorescence analyses are at least equal to those of the gravimetric and ion-exchange methods. 

The Inductively Coupled Plasma (ICP) has become the most popular source for multielement analysis via optical spectroscopy since the introduction of the first commercial instruments in 1974. About 6000 ICP-Optical Emission Spectrometry (ICP-OES) instruments are in operation throughout the world. 

An easy calibration strategy is possible in ICP-MS (in analogy to optical emission spectroscopy with an inductively coupled plasma source, ICP-OES) because aqueous standard solutions with well known analyte concentrations can be measured in a short time with good precision. Normally, internal standardization is applied in this calibration procedure, where an internal standard element of the same concentration is added to the standard solutions, the samples and the blank solution. The analytical procedure can then be optimized using the internal standard element. The internal standard element is commonly applied in ICP-MS and LA-ICP-MS to account for plasma instabilities, changes in sample transport, short and long term drifts of separation fields of the mass analyzer and other aspects which would lead to errors during mass spectrometric measurements. 

Different analytical techniques such as ICP-OES (optical emission spectrometry with inductively coupled plasma source), XRF (X-ray fluorescence analysis), AAS (atomic absorption spectrometry) with graphite furnace and flame GF-AAS and FAAS, NAA (neutron activation analysis) and others, are employed for the trace analysis of environmental samples. The main features of selected atomic spectrometric techniques (ICP-MS, ICP-OES and AAS) are summarized in Table 9.20.1 The detection ranges and LODs of selected analytical techniques for trace analysis on environmental samples are summarized in Figure 9.15.1... 

For these techniques, a dissolved sample is usually employed in the analysis to form a liquid spray which is delivered to an atomiser e.g. a flame or electrically generated plasma). Concerning optical spectrometry, techniques based on photon absorption, photon emission and fluorescence will be described (Section 1.2), while for mass spectrometry (MS) particular attention will be paid to the use of an inductively coupled plasma (TCP) as the atomisation/ionisation source (Section 1.3). The use of on-line coupled systems to the above liquid analysis techniques such as flow injection manifolds and chromatographic systems will be dealt with in Section 1.4 because they have become commonplace in most laboratories, opening up new opportunities for sample handling and pretreatment and also to obtain element-specific molecular information. 

Since the mid-1960s, a variety of analytical chemistry techniques have been used to characterize obsidian sources and artifacts for provenance research (4, 32-36). The most common of these methods include optical emission spectroscopy (OES), atomic absorption spectroscopy (AAS), particle-induced X-ray emission spectroscopy (PIXE), inductively coupled plasma-mass spectrometry (ICP-MS), laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS), X-ray fluorescence spectroscopy (XRF), and neutron activation analysis (NAA). When selecting a method of analysis for obsidian, one must consider accuracy, precision, cost, promptness of results, existence of comparative data, and availability. Most of the above-mentioned techniques are capable of determining a number of elements, but some of the methods are more labor-intensive, more destructive, and less precise than others. The two methods with the longest and most successful histoty of success for obsidian provenance research are XRF and NAA. 

A major difficulty encountered with atomic absorption techniques is the presence of incompletely absorbed background emission from the source and scattered light from the optical system. As the background becomes more intense relative to the absorption of the analyte, the precision of the measurement decreases dramatically. For this reason, several background correction techniques have been implemented. A commonly used method is the method of proximity, which was discussed in relation to inductively coupled plasma spectroscopy. 

With the exception of better optical resolution needed, the basic instrument used for atomic emission is very similar to that used for atomic absorption with the difference that no primary light source is used for atomic emission. One of the most critical components for this technique is the atomisation source because it must also provide sufficient energy to excite the atoms as well as atomise them. The earliest energy sources for excitation were simple flames, but these often lacked sufficient thermal energy to be truly effective sources. The development in 1963 and the introduction in 1970 of the first commercial inductively coupled plasma (ICP) as a source for atomic emission dramatically changed the use and the utility of emission spectroscopy (Thompson Walsh 1983). 

Emission spectrometry using chemical flames (flame atomic emission spectrometry, FAES) as excitation sources is the earlier counterpart to flame atomic absorption spectrometry. In this context emission techniques involving arc/spark and direct or inductively coupled plasma for excitation are omitted and treated separately. Other terms used for this technique include optical emission, flame emission, flame photometry, atomic emission, and this technique could encompass molecular emission, graphite furnace atomic emission and molecular emission cavity analysis (MEGA). 

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