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Atomic Emission Spectroscopy: A Tutorial Review *

Anthony F. Lagalante a a Chemical Science and Technology Laboratory, Physical and Chemical Properties Division, National Institute of Standards and Technology, Boulder, CO, U.S.A. Online publication date: 27 September 2004

To cite this Article Lagalante, Anthony F.(2004) 'Atomic Emission Spectroscopy: A Tutorial Review*', Applied

Spectroscopy Reviews, 34: 3, 191 207 To link to this Article: DOI: 10.1081/ASR-100100845 URL: http://dx.doi.org/10.1081/ASR-100100845

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APPLIED SPECTROSCOPY REVIEWS, 34(3), 191207 (1999)

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Atomic Emission Spectroscopy: A Tutorial Review*

ANTHONY F. LAGALANTE Chemical Science and Technology Laboratory Physical and Chemical Properties Division National Institute of Standards and Technology Boulder, CO 80303

I. INTRODUCTION ........................................................................... 192 II. GENERAL DESCRIPTION ........................................................... 192 III. SOURCES ....................................................................................... A. Flame Sources ......................................................................... B. Inductively Coupled Plasma Sources...................................... C. Microwave Plasma Sources .................................................... D. DC Plasma Sources ................................................................. E. DC Arc Sources....................................................................... F. AC Arc Sources....................................................................... G. High Voltage Spark Sources ................................................... H. Laser Microprobe Sources ...................................................... I. Reduced Pressure Discharge Sources ..................................... 193 193 194 196 197 198 199 200 201 201

*Contribution of the U.S. Government. Not subject to copyright in the United States. Certain commercial instruments, materials, or equipment are identified in this entry in order to specify adequately the experimental procedure or discussion. Such identification does not imply recommendation or endorsement by the National Institute of Standards and Technology, nor does it imply that the materials or equipment identified are necessarily the best available for this purpose. 191
Published by Marcel Dekker, Inc. www.dekker.com

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IV. INSTRUMENTATION................................................................... A. Planar Gratings ........................................................................ B. Concave Gratings .................................................................... C. Echelle Gratings ...................................................................... D. Detectors ..................................................................................

201 202 204 205 206

V. PERFORMANCE............................................................................ 206 BIBLIOGRAPHY............................................................................ 207

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I. INTRODUCTION Atomic emission spectroscopy is an important instrumental technique for both quantitative and qualitative analysis of metallic and non-metallic elements in inorganic and organic materials. In this tutorial, the principal components of atomic emission instrumentation will be discussed. In order to understand the instrumental variables associated with the particular instruments, a brief discussion of the theory behind atomic emission is presented as well as some rudimentary aspects of the spectral information obtainable. II. GENERAL DESCRIPTION In the mid 1800s, Kirchoff and Bunsen were the first to explain the emission of radiation by excited state atoms or ions. In the emission process, an atomic or ionic species is excited to a higher electronic state through the absorption of energy. The energy necessary for the electronic transition can be supplied in the form of either thermal energy or incident radiation of the correct frequency. In atomic emission spectroscopy (AES), excitation is accomplished through the absorption of thermal energy. The excited state lifetime is on the order of 10 to 8 seconds and upon relaxation of the atom or ion to its ground state configuration, radiation is emitted. The frequency of this emitted radiation is proportional to the difference in energy between the particular excited state and the ground state. The intensity of the emitted radiation is proportional to the number of atoms or ions undergoing this transition. This measured intensity can be related to the concentration of a particular element in an unknown sample and is the basis for quantitative atomic emission spectroscopy. The technique of AES involves two steps; first, a sample is atomized in a sufficiently hot source to produce an excited-state species that, upon relaxation back to the ground state, will emit radiation; and secondly, the

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radiation that is produced is measured at discrete wavelengths by a highresolution spectrometer. The source used in AES is typically much higher in temperature (5000K to 10000K) than the source used in atomic absorption spectroscopy (see the complementary review on atomic absorption spectroscopy in this journal issue). Consequently, both atomic and ionic excited states of an element are produced, in contrast to the largely ground-state atomic species produced by AAS. Although the resultant emission spectrum is complicated due to the multitude of excited-state species produced, it contains a wealth of atomic and ionic lines that can be used for quantitation. The instrumentation required for AES (Figure 1) is similar to that required by AAS. The main difference between the two instruments is that the thermal energy of the source produces the excited-state species in AES, eliminating the need for an atomic line source to generate the excited-state species. In addition, the resolution in AAS is determined by the atomic line source; thus a monochromator of lower resolution can be used in AAS in comparison to that required for AES. III. SOURCES A wide variety of sources exist for production of excited-state atoms or ions in AES. These sources include flames, plasmas, arcs, sparks, and lasers. Ideally, a source should be hot enough to atomize and excite as many elements as possible, operate in a chemically inert environment, be able to analyze solid, liquid, or gaseous samples, possess a low background, produce reproducible, accurate, and precise results, and be easy to operate and maintain. A. Flame Sources Historically, the flame was the first source to be used with AES. Flames are capable of producing temperatures ranging from 1500K to 3000K, which, for atomization purposes, is a relatively low operating range. Although the lowtemperature flame is not an ideal source for AES, it is possible to use a flame-AAS instrument operated in the AES mode by simply not

FIG. 1. The essential components of an atomic emission spectrophotometer.

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using the hollow cathode line source. Typical flame oxidant gases include air, oxygen, and nitrous oxide, while fuel gases include hydrogen and acetylene. Consequently, the number of excited-state species generated in the flame is low, producing low sensitivities. These temperature limitations make the flame suitable for analysis of easily excitable elements, such as the alkali metals. Flame gases can be either premixed before the burner head or be mixed in the burner head. Premixing the fuel and oxidant gases produces a laminar flame. Burners, which operate by premixing the fuel and oxidant gases, include the Meker, Alkemade, single slot, and multi-slot burners. As in flameAAS, the sample to be combusted must first be dissolved in a solvent for subsequent nebulization into these burners. The efficiency of the nebulizer will affect the amount of sample available for combustion, and ultimately the sensitivity of flame-AES. To circumvent the nebulizer efficiency factor, the total-consumption burner can be used to deliver the entire sample to the flame. The fuel and oxidant gases of the total-consumption burner are not premixed and, consequentially, a turbulent flame is produced. The turbulent flame, in addition to the excess of solvent accompanying 100% of the sample delivery, produces a very inhomogeneous flame with a high noise level. In addition to nebulization efficiency, many of the same considerations of flame AAS must be taken into account when operating a flame-AES. The background emission from a flame is high by AES standards. This background emission can be attributed to both the band spectra produced by various molecular fragments and radicals, such as OH O2, CH, CO, CN, CH, and NH, and the continuum spectra produced by blackbody radiators and chemiluminescent reactions. Like flame-AAS, the highly reactive species generated in a flame can result in chemical interferences that lower the sensitivity. B. Inductively Coupled Plasma Sources Of all the sources to be discussed, the one that comes closest to achieving all of the ideal source characteristics is the inductively coupled plasma (ICP), and therefore it is the source most commonly used in AES today. The ICP emission source was co-invented by Fassel (USA) and Greenfield (England) during the 1960s. Due to the popularity of AAS at that time, its potential in AES was not fully realized until the 1970s. The ICP (Figure 2) uses a high-frequency generator that supplies 1 to 5 kW of power to an induction coil that is wrapped about a 15 to 30 mm diameter quartz tube. A spark from a Tesla coil provides seed electrons into the argon support gas (1 L min1 flow rate) to initiate the plasma. Under the influence of the magnetic field produced by the induction coil, the seed electrons will collide with the

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FIG. 2. The inductively coupled plasma source.

argon gas to produce the hot, partially ionized argon gas plasma. The ICP can achieve temperatures as high as 9000K to 10000 K, and consequentially a second coolant gas stream of argon (10 L min1 flow) must be directed around the quartz tube to prevent it from melting. As in flame-AES, the sample to be analyzed by ICP-AES must first be dissolved in a solvent and nebulized into the argon support gas. Typical nebulizers used include the pneumatic and cross-flow nebulizers. The radio-frequency generator typically operates over a range of 3 to 100 MHz, and is usually set to 27 MHz of higher to take advantage of the

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skin effect of the plasma. Below an operating level of 27 MHz, eddy currents reside in the center of the plasma and the nebulized solution preferentially flows to the cooler outer edges of the plasma. This effectively dilutes the analyte species in the observation zone of the plasma, decreasing the analytical sensitivity. Furthermore, the cooler regions of the plasma are higher in ground state species that are available for self-absorption. At and above 27 MHz, these eddy currents move outward toward the skin or edges of the plasma, creating a torroid that has a cooler center (7000 to 8000 K). It is through this central cooler region that the nebulized solution preferentially flows. Therefore, the skin effect effectively concentrates the sample in the narrow central portion of the plasma, resulting in increased sensitivity. This also results in a narrower emission profile that minimizes self-absorption and further increases the sensitivity. The hottest portion of the plasma is the plasma core, which is located inside the induction coil. Complete vaporization and atomization is achieved in the 2 to 3 millisecond residence time of the sample in the plasma. The hottest zone extends only a few millimeters above the top of the induction coil. To achieve a compromise between the signal and background emission, the observation zone of the ICP is placed at a height of 1 to 3 cm above the induction coil. In the observation zone, the only background emission is due to argon line emission and the OH band emission. The chemically inert environment of the plasma results in a long lifetime for the excited state species that are produced. Within the observation zone, there is a temperature gradient and consequently emission intensities for a particular element vary along the observation zone. Therefore, the observation height for the element of interest can be optimized. Above the observation zone of the plasma is the cooler, flame-like zone that is suitable as an observation zone for the easily excited elements, such as the alkali metals. The high temperatures generated by the plasma are capable of producing ionized excited-state species. Emission due to ionized species is typically more intense than ground state atomic emission. Typically, parts-per-billion (where l part-per-billion is 107 percent) detection limits with a linear range of five orders of magnitude are obtainable using ICPAES. Although the ICP approaches an ideal source for AES, the primary disadvantages of an ICP-AES are that it is expensive to purchase, the plasma consumes large quantities of relatively expensive argon gas, and that the instrument cannot directly analyze solid samples. C. Microwave Plasma Sources Another plasma source that has been used, as a source in AES, is the microwave induced plasma (MIP). Similar to the ICP, the MIP is initiated by seed electrons from a Tesla coil discharge. The seed electrons collide with

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the support gas in a microwave cavity that is commonly operated at 2450 MHz. Nitrogen, argon, or helium have been used as support gases for the plasma. Operating power for the MIP can range from 25 to 250 W. Sample introduction into the MIP is again accomplished through nebulization into the supply gas for the plasma. However, the low power levels used in the MIP are not effective for solvent evaporation. Consequentially, complicated sample introduction techniques that will desolvate and vaporize the sample prior to introduction into the plasma must be performed. For the plasma to exist, the coupling element of the microwave cavity must be tuned to match the system impedance. The system impedance can be easily perturbed during sample introduction into the plasma. For example, large nebulized volumes of sample and solvent readily disrupt the system impedance and as a result the plasma may be extinguished. Greater plasma stability is obtainable using a capacitively-coupled microwave plasma. However, the cost advantage of MIP is not realized due to the higher power requirements (200 to 1000 W) of the capacitively-coupled system. The temperatures generated in the MIP are lower than those of the ICP and range between 4000K to 5000K. Microwave plasmas have low background emission due to the inert gases used, however, the lower temperature of the plasma can make chemical interferences troublesome. Sample introduction techniques remain the greatest hindrance to the use of microwave plasmas in AES. However, the same sample introduction limitations associated with the MIP as a source for AES, allow the MIP-AES to function as an ideal element selective detector in gas chromatography. In gas chromatography, the sample to be analyzed has already undergone desolvation and vaporization and is ideally suited to undergo combustion in the MIP. Selective detection of H. C, N. P. B. and O has been accomplished by the interfacing of a MIP-AES to the exit of the chromatographic column. D. DC Plasma Sources The three-electrode dc plasma (Fig. 3) uses two carbon anode electrodes and a tungsten cathode in an inverted Y configuration. The support gas for the plasma is argon (8 L min1 flow rate). The plasma is initiated by moving the electrodes together, and once ignited requires very low power levels (<1 kW) to sustain the plasma. The temperature of the plasma is independent of operating current because increasing the current level only results in increasing the cross-sectional area of the plasma, with no resultant increase in plasma temperature. Therefore, the high temperatures generated by the dc plasma (9000K to 10000K) are obtained by squeezing the plasma with a high-velocity inert gas sheath. This gas sheath cools the outer region of the plasma, maintaining the higher current levels in the interior of the plasma.

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FIG. 3. The do plasma source. (Reproduction courtesy of Beckman Instruments)

The temperature in the excitation region of the plasma is approximately 6000K and offers detection limits similar to that of the ICP. Like the ICP, the observation region and the main plasma are spatially separated. The dc plasma suffers from similar disadvantages to those of other plasma sources. The dc plasma can only be used to analyze samples that have been previously dissolved in a solvent, and it is relatively expensive to operate due to its consumption of large volumes of argon gas. A major disadvantage of the dc plasma is that the high temperature of the plasma physically deforms the electrodes. Therefore, it is necessary to reshape the electrodes after only approximately two hours of use. E. DC Arc Sources The various plasma sources discussed provide many advantages for the analysis of liquid samples. However, it is the arc and spark sources that are predominantly used for the analysis of solids. Since the 1920s, the dc arc has been used extensively as a qualitative method of trace-elemental analysis for metallurgical samples. A continuous high-current discharge (1 to 30 A) at low voltage (10 to 25 V) is formed between the two metal or graphite electrodes under atmospheric conditions. Graphite is the electrode material that is most commonly used because of its inertness, high-purity, and refractory

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properties. Like the dc plasma, the arc can be initiated by physically moving the electrode gap together, or by a low-current spark discharge. Following initiation, the arc plasma is maintained by ionization of the material between the gap. In a dc arc source manufactured in the United States, the anode is used to hold the sample and the cathode is the counter electrode, whereas in a European instrument the cathode is the electrode that holds the sample while the anode is the counter electrode. The solid sample to be analyzed can be mixed with graphite and placed in the electrode cup in the case of powders, or evaporated to dryness in the cup in the case of dissolved samples. In the analysis of conductive solids, the electrode can be machined directly from the sample to be analyzed. The resulting arc discharge generates temperatures from 3000K to 8000K along the distance of the arc, with the highest temperatures generated at the sample surface. The high temperatures at the electrode surface vaporize the sample, which then subsequently undergoes collisional excitation in the discharged plasma. The background emission accompanying dc arcs is severe. Both band and continuum emission from species in the atmospheric plasma is prevalent. To eliminate the troublesome CN (cyanogen) band emission accompanying atmospheric operation, the dc arc can be operated in an argon or helium atmosphere. An additional source of background radiation is due to the heated electrodes, which emit as blackbody radiators. Self-absorption is also troublesome in dc arc sources due to the ground state species residing in the outer, cooler portions of the arc. Since the dc arc source slowly wanders about the electrode surface, only a small portion of the entire sample is vaporized at a single instant. This slow random sampling of different areas of the sample may produce errors in the results, often because the analyte concentration at the surface of a solid sample is not homogeneous. However, the high-detection limits of the dc arc have popularized the technique as a qualitative method of analysis. Today, the dc arc is used to qualitatively identify approximately 70 elements in solid samples ranging from geological ores to biological solids. F. AC Arc Sources Two types of ac arcs can be used as a source for AES. The highvoltage ac arc operates from 2000 to 4000V, while the low-voltage ac arc operates from 100 to 400V. Both of the ac arcs self-extinguish at every halfcycle due to the change in the voltage polarity. The high-voltage ac arc selfignites itself every half-cycle when the applied voltage exceeds the dielectric breakdown voltage of the gas between the two electrodes. The low-voltage ac arc is re-ignited by a low-current spark every half-cycle. An advantage of

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the voltage polarity change at every half-cycle of the ac arc is that both anodic and cathodic sampling is possible. Using a 60 Hz source, the ac arc re-ignites 120 times per second, allowing the ac arc to rapidly sample different portions of the sample surface. This higher sampling rate gives the ac arc better precision than the slow wandering sampling of the dc arc. However, the self-extinguishing and re-ignition lowers the arc temperature, making the ac arc less sensitive than the dc arc source. The lower temperatures generated, however, do extend the lifetime of the electrode material. One solution to the compromises evident between ac and dc arcs is to use an intermittent ac arc. The intermittent ac arc does not change voltage polarity and samples the anode on both half-cycles of the voltage wave. The intermittent ac arc produces the sensitivity advantages of the dc arc, with the increased precision advantages of the ac arc. G. High Voltage Spark Sources Similar to the ac arc source, the high-voltage ac spark source randomly samples the electrode surface, resulting in higher precision. As in the other electrical discharge sources, electrodes can be machined from conducting samples, or mixed with graphite and pressed into pellets for powdered samples. The firing of the spark is regulated either by a capacitively-controlled discharge (voltage-thresholded spark) or by a rotary gap (time-thresholded spark). The gap breakdown occurs at a rate of hundreds of times per second. The high-current levels of the discharge generate high temperatures from a spark source. The high temperatures allow metals to undergo single and multiple ionization in spark sources to produce an emission spectrum that is quite complex. This high extent of ionization decreases the sensitivity in comparison to a single atomic emission line and reduces the overall sensitivity of the measurement for a particular element. Time-resolved emission spectroscopy is possible with the spark source because the emission due to atomic and ionic species will vary over the duration of the spark. By maximizing the signal-to-background emission intensity, in time one can alleviate some of the background problems that plague electrical-discharge sources. Additionally, both arc and spark sources, or electrothermal atomizers (see the review on AAS), can be used as a sample introduction technique for ICP-AES. Since ICP is not suited for analysis of solids, arc and spark sources can be used for the sole purpose of vaporizing a solid into the support gas stream of an ICP source. The spark source has also been used as a gas chromatography detector to provide element selective detection of C, B. N. O. and S.

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H. Laser Microprobe Sources A high-powered pulsed laser such as the ruby or Nd:YAG laser can be used as a source for the volatilization and excitation of samples for AES. The laser is focused on a spot 5 to 50 m in diameter on the sample. A vapor of atoms, ions, and molecular species is produced when the laser discharges. As the vapor passes through the electrode gap of two graphite electrodes, a spark will ignite. The energy from the spark provides the energy to excite the atoms and ions of the sample. The laser can be focused on select portions of a sample for spatial analysis, and the region of the sample that is vaporized is so infinitesimally small that the technique can be considered non-destructive. I. Reduced Pressure Discharge Sources The hollow cathode lamp (HCL), which is used primarily as a line source in AAS, also can be used as an AES source. The element selectivity of the HCL is achieved by fabricating the cathode, or coating the interior of the cathode, with the element of interest. The removable cathode HCL design is most suited to function as a source in AES. The cathode is machined from conductive solid samples, or can be pressed into a pellet in the case of powdered samples. As in the HCL, the Pyrex cylinder containing the anode and cathode is back-filled with an inert fill gas (Ar, Ne) at reduced pressures. At low currents (10 to 30 mA), the fill gas is ionized and accelerated toward the cathode surface, where upon contact with the cathode, the accelerated gas atoms sputter atoms off the cathode into the vapor phase. These atoms undergo further collisions with other accelerated fill-gas ions, and are elevated to their excited-state configurations. Upon relaxation back to the ground state, the sample atoms emit radiation at their characteristic atomic lines. The HCL is operated at low temperatures, and therefore narrow atomic lines are produced. The electrical discharge source is primarily suited for elements with high vapor pressures in matrices of low vapor pressure. IV. INSTRUMENTATION The key to the selectivity of AES is to have a monochromator of sufficient resolution to separate closely spaced elemental emission lines and the ability of the monochromator to separate these emission lines from the background emission. The entrance optics of the monochromator selects a solid angle element from the emission source and focuses a maximum amount of

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the emitted radiation on the monochromator. In flame AES this is accomplished by adjusting the burner position, while in plasma and electrical discharge sources this is accomplished by adjusting the focusing optics. Following focusing of the radiation by the entrance optics, wavelength selection is accomplished by use of high-resolution diffraction gratings. High-resolution gratings have replaced dispersive prism elements due to their ability to overcome the problems associated with prisms; absorption of radiation by the prism, polarization problems, and the wavelength dependence of resolution. The purpose of the grating is to spatially separate the incident radiation into its component wavelengths for subsequent detection. The monochromator must be of sufficient resolving power to be able to separate the analyte emission lines from the non-analyte background emission. Grating surfaces can be either planar or concave in geometry. The surface of the diffraction grating is comprised of very closely spaced lines. In AES, the gratings used are typically reflection gratings, in which radiation directed onto the grating surface is reflected (diffracted) from the grating surface. The incident radiation is separated into its component wavelengths, , according to the formula: m = d(sin + sin ) (1)

where m is the order of diffraction, is the angle of incidence normal to the grating, is the angle of diffraction normal to the grating, and d is the groove spacing of the grating. By rotating the grating, and changing the angle of incident radiation, radiation of different wavelengths is focused on the detector. Gratings where the surface is blazed at a finite angle are called Echelle gratings. These are used to concentrate higher orders of reflected radiation. Radiation separated by the grating is focused on a detector. The detector can be a photographic plate, a photomultiplier tube (PMT), a photodiode array (PDA), or a charged-coupled-device (CCD) camera. Usually only qualitative determinations are made using a photographic plate (and these are rarely used today), while both qualitative and quantitative determinations are made using PMTs or array devices. In modern instruments, the use of detector array devices is now widespread. The output from the detector is recorded on either a chart recorder or more commonly directly into a computer interface. In the latter case, the computer may be built into the instrument or mounted externally in the form of a standard PC or workstation. A. Planar Gratings The grating configurations that most commonly use reflection from a plane or planar grating surface are the Czerny-Turner and Ebert mounting

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(Figure 4). In the Czerny-Turner configuration a single concave mirror functions as both the collimating and final imaging mirror, whereas in the Ebert mounting, two independent mirrors are used. Both configurations utilize planar ruled or replicated gratings that are commonly rotated under computer control. Additionally, the spectral lines that are dispersed are true images of the slit (stigmatic); therefore, the intensities of these lines are independent of

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FIG. 4. The (a) Czerny-Turner and (b) Ebert mounting plane grating configurations.

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the slit height. In these configurations the gratings are typically used in firstorder dispersion to avoid the large rotation angles of the grating. The design of the monochromator makes the spectrometer compact due to the positioning of the slits and detector placement on the same side of the instrument. Overall resolution of the instrument depends on several instrumental variables. Both configurations are capable of providing the high-resolution (<0.1 nm bandpass) necessary for AES, however. Multi-element detection is possible in either of the planar grating configurations; however, simultaneous multi-element determination is not. These grating monochromators are typically capable of slew-scanning under computer control. In slew-scanning the monochromator is rapidly scanned through wavelengths that are not of analytical interest and are slowly scanned through spectral regions in which a qualitative or quantitative determination is to be made. Background correction is obtainable by measuring the intensity of emission on either or both sides of the analyte emission peak, and then performing a simple subtraction to give the emission due solely to the analyte species. B. Concave Gratings The Paschen-Runge mounting (Figure 5) is capable of both focusing and dispersing radiation from the source. In the Paschen-Runge mounting, a concave grating lies on the circumference of a Rowland circle. Also about this circumference are the entrance slit and the focal plane of the dispersed radiation. The radius of curvature of the Rowland circle is one-half of the radius of curvature of the grating. Sufficient resolution can be obtained in a focal length of approximately one meter. The adjustable exit slits are positioned about the Rowland circle to pass only radiation of interest for as many as 60 elements. A photomultiplier tube is positioned behind each of the exit slits to measure a particular element in an independent channel. This configuration provides true simultaneous multi-element analysis. Background correction in the Paschen-Runge mounting is somewhat difficult. One scheme is to position some of the photomultiplier tubes to measure the background emission intensity for subsequent non-analyte emission correction. However, the exit slits are not typically changed very often due to the time necessary to realign them. Another method is to use a quartz refractor plate to scan background intensities on either side of an analytical line. Both the high cost and size requirements of a concave grating monochromator have lowered its popularity compared to that of the plane grating monochromator. They have been popular for direct reading style of spectrograph in popular use with the arc-spark emission instruments.

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FIG. 5. The Paschen-Runge mounting.

C. Echelle Gratings The Echelle grating configuration is accomplished by placing a prism before an Echelle grating using the Czerny-Turner mounting. The Echelle grating configuration is capable of maximizing the intensity of the separated incident radiation at the optimum order. This is accomplished by using a prism to order separate the radiation and the Echelle grating to wavelength separate the radiation. The result is a compact two-dimensional array on which exit slits can be positioned to measure the emitted radiation. The sensitivity of the instrument is increased because the blaze angle for each element is maximized in a shorter focal length. When using an Echelle grating, the slit height must be kept small (1 mm) to minimize the overlap of radiation of different orders, which reduces the sensitivity some. The Echelle spec-

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trometer eliminates spectral interferences due to line overlap by non-analyte atoms through order separation. D. Detectors The first detectors in AES were those using photographic film. Following dispersion of the emitted radiation from the source, the spectral lines were recorded on photographic film. The photograph was typically compared to a standard photograph for a given element to qualitatively ascertain the existence of a particular element. Although semi-quantitative analysis is possible using photographic film, through line-to-background ratios using a densitometer, the procedure is tedious compared to other quantitative techniques. Photographic detection was used, however, in qualitative analysis such as when samples were analyzed using arc and spark sources. Photomultiplier tubes have been commonly used as detectors for AES. The two main sources of noise in AES arise from the source flicker and the dark current from the photomultiplier tube. Generally, the entrance slit is narrowed until the noise from the photomultiplier tube is the dominant source of noise. The signal-to-noise ratio of the element of interest can be enhanced by modulating the source and through signal averaging of the response from the photomultiplier tube. Many modern instruments now feature array-based detector systems. In most cases these minimize or eliminate the use of scanning devices or even the use of conventional-style monochromators. The use of arrays provides a means to record the entire spectrum in a very short time, and it provides the means to produce a complete output of an entire spectral region. In such arrangements it is possible to have an accurate accounting of the background effects, although the impact of stray light and its rejection can be an issue. Several types of array devices are available that are suitable for emission spectrometry, these include linear photodiode arrays, charge-coupled device (CCD) detectors and charge injected device (CID) detectors. All have been used in various commercial instruments. At issue is often how to provide adequate spectral resolution for separation of the atomic lines while providing an adequate spectral range. Sometimes compromises have to be made relative to range and/or spectral resolution. Various designs of instruments have been designed that include either limited scanning (for range selection), custom-designed detectors or the use of special grating designs that provide two dimensional imaging on a two dimensional CCD array. V. PERFORMANCE In the case of the quantitative analysis of solutions, standardization of an unknown sample by AES is accomplished by creating a calibration curve.

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The Beer-Lambert law is used to directly relate emission intensity to the concentration of an element in a standard solution. The measured emission intensity is dependent on atomizer efficiencies, instrumental variables, and the source excitation temperature. In flame-AES, the calibration curve spans 2 to 3 orders of magnitude in sensitivity, whereas in plasma-AES the calibration curve spans 4 to 5 orders of magnitude in sensitivity. Care must be taken to ensure that the unknown solution lies within the linear region of the calibration curve. Atomic emission calibration curves are non-linear at higher concentrations due to self-absorption by atoms in cooler parts of the source. If one is working in a non-linear portion of the calibration curve, the solution may be diluted until it is within the linear region. In the case of solids analysis by AES, standardization may be accomplished by the use of standard reference materials that are available from the National Institute of Standards and Technology. As in AAS, care must be taken to ensure that vaporization and excitation conditions are similar between unknowns and standards and that the impact of interferences is minimized. BIBLIOGRAPHY
Ingle, J. D., Crouch, S. R. Spectrochemical Analysis, Prentice Hall, New Jersey, 1988. Mika, J., Torok, T. Analytical Emission Spectroscopy, Crane, Russak and Company, New York, 1974. Robinson, J. W. Atomic Spectroscopy, Marcel Dekker, New York, 1996. Zander, A. T., Atomic Emission Sources for Solution Spectrochemistry, Anal. Chem. 1986, 58, 1139A. Varnes, A.W., Inductively Coupled Plasma Atomic Emission Spectroscopy, Handbook of Instrumental Techniques for Analytical Chemistry, ed. Frank Settle, pp. 395418, Prentice Hall PTR, NJ, 1997. Dean, J.A., Atomic Spectroscopy, Analytical Chemistry Handbook, McGraw Hill, NY, 1995. Kellner, R.A., Mermet, J.-M., Otto, M., and Widmer, H.M. Eds., Elemental Analysis: Atomic Emission Spectrometry, Analytical Chemistry, pp. 435452, Wiley-VCH Verlag GmbH, Weinheim, 1998. Hareland, W.A., Atomic Emission Spectroscopy, Analytical Instrumentation Handbook, 2nd Edition, Galen Wood Ewing Ed., pp. 221256, Marcel Dekker, NY, 1997.

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