ICP-OES

Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES)... 

In Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES), a gaseous, solid (as fine particles), or liquid (as an aerosol) sample is directed into the center of a gaseous plasma. The sample is vaporized, atomized, and partially ionized in the plasma. Atoms and ions are excited and emit light at characteristic wavelengths in the ultraviolet or visible region of the spectrum. The emission line intensities are proportional to the concentration of each element in the sample. A grating spectrometer is used for either simultaneous or sequential multielement analysis. The concentration of each element is determined from measured intensities via calibration with standards. 

ICPMS can be considered a high-sensitivity extension of mass spectrometry, as well as an increased-sensitivity detector replacing optical ICP (ICP-OES) analysis. In fret, both viewpoints are accurate, and the wide application of ICPMS analysis... 

The inductively coupled plasma and the torch used in ICPMS are similar to that used in ICP-OES. In ICPMS, the torch is aimed horizontally at the mass spectrometer, rather than vertically, as in ICP-OES. In ICPMS the ions must be transported physically into the mass spectrometer for analysis, while in ICP-OES light is trans-... 

Sample introduction into the ionizing plasma is normally carried out in the same manner as for ICP-OES. An aqueous soludon is nebulized and swept into the plasma. 

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. 

Approximately 70 different elements are routinely determined using ICP-OES. Detection limits are typically in the sub-part-per-billion (sub-ppb) to 0.1 part-per-million (ppm) range. ICP-OES is most commonly used for bulk analysis of liquid samples or solids dissolved in liquids. Special sample introduction techniques, such as spark discharge or laser ablation, allow the analysis of surfaces or thin films. Each element emits a characteristic spectrum in the ultraviolet and visible region. The light intensity at one of the characteristic wavelengths is proportional to the concentration of that element in the sample. 

The strengths of ICP-OES are its speed, wide linear dynamic range, low detection limits, and relatively small interference effects. Automated instruments with... 

ICP-OES is a destructive technique that provides only elemental composition. However, ICP-OES is relatively insensitive to sample matrix interference effects. Interference effects in ICP-OES are generally less severe than in GFAA, FAA, or ICPMS. Matrix effects are less severe when using the combination of laser ablation and ICP-OES than when a laser microprobe is used for both ablation and excitation. 

An ICP-OES instrument consists of a sample introduction system, a plasma torch, a plasma power supply and impedance matcher, and an optical measurement system (Figure 1). The sample must be introduced into the plasma in a form that can be effectively vaporized and atomized (small droplets of solution, small particles of solid or vapor). The plasma torch confines the plasma to a diameter of about 18 mm. Atoms and ions produced in the plasma are excited and emit light. The intensity of light emitted at wavelengths characteristic of the particular elements of interest is measured and related to the concentration of each element via calibration curves. 

Calibration curves must be made using a series of standards to relate emission intensities to the concentration of each element of interest. Because ICP-OES is relatively insensitive to matrix effects, pure solutions containing the element of interest often are used for calibration. For thin films the amount of sample ablated by spark discharges or laser sources is often a strong function of the sample s composition. Therefore, either standards with a composition similar to the sample s must be used or an internal standard (a known concentration of one element) is needed. 

Table 1 Typical detection limits (ppb) for iCP-OES (using a pneumatic nabuiizer for sample introduction) of the most sensitive amission line betwean 175 nm and 850 nm for each element.

Figura 3 Grating spectrometers commonly used for ICP-OES (a) monochromator, in which wavelength is scanned by rotating the grating while using a singie photomultiplier tube (PMT) detector (b) polychromator, in which each photomultiplier observes emission from a different wavelength (40 or more exit slits and PMTs can be arranged along the focal plane) and (c) spectrally segmented diode-array spectrometer.

Althoi h nonspectral interference effects are generally less severe in ICP-OES than in GFAA, FAA, or ICPMS, they can occur. In most cases the effects produce less than a 20% error when the sample is introduced as a liquid aerosol. High concentrations (500 ppm or greater) of elements that are highly ionized in the... 

ICP-OES is one of the most successful multielement analysis techniques for materials characterization. While precision and interference effects are generally best when solutions are analyzed, a number of techniques allow the direct analysis of solids. The strengths of ICP-OES include speed, relatively small interference effects, low detection limits, and applicability to a wide variety of materials. Improvements are expected in sample-introduction techniques, spectrometers that detect simultaneously the entire ultraviolet—visible spectrum with high resolution, and in the development of intelligent instruments to further improve analysis reliability. ICPMS vigorously competes with ICP-OES, particularly when low detection limits are required. 

Parts I and II. John Wiley and Sons, New York, 1987. An excellent description of the fundamental concepts, instrumentation, use, and applications of ICP-OES. 

R. K. Winge, V A. Fassel, V. J. Peterson, and M. A. Floyd. Inductively Coupled Plasma Atomic Emission Spectroscopy An Atlas of Spectral Information. Elsevier, Amsrerdam, 1985. ICP-OES specrral scans near emission lines usefol for analysis. 

R. I. Botro. In Developments in Atomic Plasma Spectrochemical Analysis. (R. M. Barnes, ed.) Heyden, Philadelphia, 1981. Describes merhod for correction of overlapping spectral lines when using a polychromaror for ICP-OES. 

J. W. Olesik. Analyt. Chem. 63, 12A, 1991. Evaluation of remaining limitations and potential sources of error in ICP-OES and ICPMS. 

In Table 4.3, the Cetac product LSX-200 is the specialized system for coupling with the ICP customer s system. It includes the laser, optical viewing system for exact positioning of the laser focus on a sample surface, and the sample cell mounted on the computer controlled XYZ translation stage. The system is also provided with the appropriate gas tuhing for transport of the ablated material into an ICP-OES/MS. 

The sensitivity, accuracy, and precision of solid-sample analysis have been greatly improved by coupling LA with ICP-OES-MS. The ablated species are transported by means of a carrier gas (usually argon) into the plasma torch. Further atomization, excitation, and ionization of the ablated species in the stationary hot plasma result in a dramatic increase in the sensitivity of the detection of radiation (LA-ICP-OES) or of the detection of ions (LA-ICP-MS). 

Separation methods The methodology for their separation often consists of fractionation methods (see Section 3.3.4) and chromatographic methods of the soluble species. Common detection methods are AAS, ICP-OES, and fluoride electrode methods. 

Separation and detection methods There exists an array of methods for the separation of the Sb species, ranging from liquid-liquid extraction to the formation of complexes with immobilized reagents, followed by HPLC or reversed phase chromatography, and eletroanalytical methods. Detection is based on spectrophotometric measurement, AAS, ICP-OES and ICP-MS. 

Ohls K (1989) Sample introduction into ICP-OES for metallic samples. Mikrochim Acta 111 337-346. 

Applications RPLC-ICP-AES was used for specia-tion and quantification of polar, low-MW silanols [686]. Cr(III, VI) can be determined by IC-ICP-OES at the ppt level. However, many HPLC applications for organometallic compounds demand the use of gradient elution, and a high flow-rate combined with gradient elution results in unstable plasma conditions. 

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