190 ATOMIC EMISSION SPECTROMETRY / Principles and Instrumentation Hatch WR and Ott WL (1968) Determination of submicrogram quantities of mercury

by atomic absorption spectrometry. Analytical Chemistry 40: 20852087. Holak W (1969) Gas sampling technique for arsenic determination by atomic absorption spectrometry. Analytical Chemistry 41: 17121713. MacLaughlin RL and Brindle ID (2002) A new sample introduction system for atomic spectrometry combining vapor generation and nebulization capacities. Journal of Analytical Atomic Spectrometry 17: 15401548. Matousek T, Dedina J, and Selecka A (2002) Multiple microame quartz tube atomizer further development towards the ideal hydride atomizer for atomic absorption spectrometry. Spectrochimica Acta 57B: 451462. Nakahara T (1983) Applications of hydride generation techniques in atomic absorption, atomic uorescence and plasma atomic emission spectrometry. Progress in Analytical Atomic Spectrometry 6: 163223. Sturgeon R and Mester Z (2002) Analytical applications of volatile metal derivatives. Applied Spectroscopy 56: 2002A213A. Sturgeon RE, Willie SN, Sproule GI, Robinson PT, and Berman SS (1989) Sequestration of volatile element hydrides by platinum group elements for graphite furnace atomic absorption. Spectrochimica Acta 44B: 667682. Welz B and Schubert-Jacobs M (1991) Evaluation of a ow injection system and optimization of parameters for hydride generation atomic absorption spectroscopy. Atomic Spectroscopy 12: 91104. Welz B and Sperling M (1999) Atomic Absorption Spectrometry, 3rd edn. Weinheim: Wiley-VCH Publishers. Welz B, Melcher M, Sinemus HW, and Maier D (1984) Picotrace determination of mercury using the amalgamation technique. Atomic Spectroscopy 5: 3742.

ATOMIC EMISSION SPECTROMETRY

Contents

Principles and Instrumentation Interferences and Background Correction Flame Photometry Inductively Coupled Plasma Microwave-Induced Plasma spectrometry is of prominent importance in the production control of both raw materials and nished products. Finally, emission spectrometry allows the elements present in the sun and stars to be identied, helping us to understand better the nature of the universe. These are only a few examples of scientific and technical disciplines in which the technique of emission spectrometry has made a signicant contribution.

Principles and Instrumentation

R M Twyman, University of York, York, UK
& 2005, Elsevier Ltd. All Rights Reserved.

Introduction
Atomic (or optical) emission spectrometry (AES, OES) is an important technique for the multielement analysis of a wide range of materials. Many elements have been discovered using emission spectrometry and it is the most commonly used procedure for the measurement of trace elements in rocks, water, soil, manufactured goods, and biological specimens. The technique is used to monitor the levels of different chemicals and trace elements in the environment and to determine the compositions of solids, liquids, and gases. In geoanalysis, emission spectrometry has been instrumental in the exploration of economic mineral deposits. In metallurgy and in the semiconductor industry, emission

Theory and Signal Generation

Atomic Spectra

AES involves the measurement of electromagnetic radiation emitted from atoms. Both qualitative and quantitative data can be obtained from this type of analysis. In the former case, the identity of different elements reects the spectral wavelengths that are produced, while in the latter case, the intensity of the emitted radiation is related to the concentration of each element. Atomic spectra are derived from the transition of electrons from one discrete electron orbital in an atom to another. These spectra can be understood in terms of the Bohr atomic model.

ATOMIC EMISSION SPECTROMETRY / Principles and Instrumentation 191

In the Bohr model, the atom is depicted as a nucleus surrounded by discrete electron orbits, each associated with energy of the order hn. Every atom has a certain number of electron orbitals, and each electron orbital has a particular energy level. When all the electrons are present in the orbitals, the atoms are in the most stable form (the ground state). When energy (either thermal, resulting from collision, or radiational, resulting from the absorption of electromagnetic radiation) is applied to an atom and is sufcient to lift an electron from a shell with energy Ei to one with Ej, the atom is said to be in the excited state. The state of excitation is unstable and decays rapidly. The residence time of the unstable excited state is very short, in the order of 10 8 s. When electrons return to the stable ground state, energy is emitted and that energy is equal to the difference in the energies between the ground and excited states. The energy is released in the form of electromagnetic radiation and denes the wavelength of the transition. The relationship between the energy and wavelength is described by the Planck equation:
Ej Ei hn hc=l

energy levels and vertical lines depict permissible transitions between them. The arrows show the direction of energy input or output (ascending arrows show the absorption of energy while descending arrows show energy radiation). When an electron in a quantum level j is captured by an ionized atom, energy is liberated according to the following equation:
hn hnj mn2 =2 Ej mn2 =2

The wavelength for the emitted radiation due to a transition Ej Ei is

l hc=E

where Ej Ei is the energy difference between the two levels (and Ej4Ei); h is Plancks constant, 6.624 10 34 J s 1; n is the frequency of the radiation; c is the velocity of light in a vacuum, 2.9979 108 m s 1; and l is the wavelength of the radiation in meters. If enough energy is absorbed by the atom, electrons may escape completely, leaving the atom in the ionized state. The energy required for ionization is called the ionization potential. Ions also possess ground and excited states, through which they can absorb and emit energy by the same processes described for an atom. Figure 1 illustrates the electron shell conguration in terms of energy levels. Horizontal lines represent

where E is the energy difference and l is the wavelength of the emitted radiation. Spectra of neutral excited atoms are denoted as I, and correspond to those deexciting to the ground state (resonance lines) or close to the ground state (nearresonance lines). They are observed in low-energy sources such as ames. Spectra of singly ionized atoms are denoted as II, and they are observed in highenergy sources such as electrical sparks, inductively coupled plasmas (ICPs), and glow discharges. Every element has a characteristic emission spectrum, which is the basis of spectrochemical analysis.
Molecular Spectra

Molecular spectra consist of numerous densely grouped lines. These are called band spectra because they appear as luminous bands. The ne structure can only be observed with high-resolution instruments. Molecular spectra of excited molecules are related to the energy states of a molecule rotating around the principal axes of inertia. Band spectra in the nearinfrared are produced by energy transitions related to oscillatory vibrations of individual molecules.
Continuum

Excitation

Emission Ion excited state e

4

Energy

Ion ground state Excited states a b c d Ground State f g

This is radiation distributed continuously over the wavelength range and can be attributed to recombination processes and other background factors. The intensity of the background increases with temperature.

3 2 1

Instrument Design Overview

A spectrometer consists of three main parts: (1) an emission source, which produces the spectrum; (2) an optical system, which scatters the spectrum; and (3) a device to measure the emitted lines. The two major types of instrument for the analysis of emission spectra are sequential and simultaneous spectrometers, although there are many variants of each in terms of mechanical and optical characteristics. The spectral

Figure 1 Electron shell congurations in terms of energy levels. Arrows depict permissible transitions by absorption and excitation (ascending) or radiation and photon emission (descending), a and b represent excitation, c is ionization, d is ionization plus excitation, e is ion emission, and f, g, and h are atom emissions. (Reproduced with permission from Boss CB and Freeden KJ (1989) Concepts, Instrumentation and Techniques. Inductively Coupled Plasma Atomic Emission Spectrometry, Perkin Elmer Corp.)

192 ATOMIC EMISSION SPECTROMETRY / Principles and Instrumentation

wavelength range of interest is B160900 nm, but not all instruments are capable of covering this range, and the resolution may vary with wavelength. Oxygen and water vapor absorb short-wave UV emissions (o190 nm) and this obscures the emission lines of some common and important elements (e.g., hydrogen, carbon, oxygen, nitrogen, chlorine, phosphorus, and sulfur). Therefore, oxygen and water vapor must be eliminated from the instrument, either by evacuation or by ushing with nitrogen or argon. Nitrogen ushing does not interfere with the analysis of samples containing nitrogen compounds since molecular nitrogen (N2) does not obscure the emission lines from atomic nitrogen in the sample.

Flame Sources

In ame emission spectrometry, the sample solution is sprayed or aspirated into a ame as a ne mist or aerosol. The sample is vaporized in the ame, and atomized by a combination of heat and the action of a reducing gas. The atoms are excited into higher electronic states by the heat, and as they revert to the ground state they emit photons, which are measured by the detector. The layout of a ame photometer is shown in Figure 2.
Discharge Sources (Arcs and Sparks)

Instrument Design Emission Sources

In spectrochemical analysis, atomization and excitation can be achieved using various different emission sources. The spectra derived from low-energy sources such as ames are simpler than those from electrical discharges, although the temperature of ames and furnaces (20004000 K) is inadequate to excite many of the elements. Nevertheless, ame emission spectrometry is widely used for the determination of the alkali elements (lithium, sodium, and potassium), whose excitation states are low enough to be populated at ame temperatures. Higher-energy sources produce higher temperatures and therefore more emission lines. In electrical discharges, arcs and sparks are created by applying currents and potentials across conducting electrodes, and a large quantity of the sample surface is evaporated in this process. Better quantitative analysis is achieved using plasma sources: ICP, direct current plasma (DCP), and microwave induced plasma (MIP), which generally achieve temperatures of 70008000 K. Glow discharge sources, which use high-energy argon atoms and ions to excite atoms ejected from the analyte surface, are often used for the analysis of metals. The degree of excitation by a thermal source can be described by the Boltzmann distribution equation. If N1 is the number of atoms in the excited state and N0 is the number in the ground state, then the excited fraction is given by
N1 =N0 g1 =g0 expE=kT

The rst discharge sources produced direct current (DC) arcs by electrically heating the sample in an electrode cup and vaporizing the analytes into a low-voltage, high-current discharge. The temperature of the arc plasma varies from 4000 to 5000 K. The limits of detection are good and the entire sample can be consumed. However, due to variations in the volatilization process, the accuracy is usually poor. Reproducibility can be improved by using internal references and optimizing the conditions of vaporization (graphite electrode designs, addition of modiers). The spectral range of the source is limited due to the presence of cyanogen bands with heads at 421.6, 388.3, and 359.0 nm when graphite is used. Argon can be injected into the arc to minimize these effects. In the so-called cathode region, intensity is relatively higher (1050 times) than in the central and anode regions of the arc. Spark sources produce lower average temperature than arcs, but the local temperature can be as high as 40 000 K. Like arc sources, sparks produce atomic lines, but also more pronounced lines for ions, which are known as spark lines. The emission source consists of a sparking stand and a spark generator. A spark forms between the cathode and the sample (which acts as the anode). The adjustable gap

Mirror

Lens Slit Filter Photodetector Aerosol enters flame

where E is the energy difference between the ground and excited states, T is the absolute temperature (K), k is the Boltzmann constant (1.38 10 23 J K 1), and g1 and g0 are quantum statistical weighting factors.

Fuel Air from compressor Sample Drain

Figure 2 Schematic of a ame emission spectrophotometer.

ATOMIC EMISSION SPECTROMETRY / Principles and Instrumentation 193

between the cathode and the sample is sometimes termed the entrode, and is lled with argon. The generator initially produces a brief low-energy discharge that ionizes the argon and creates the plasma. A second, high-energy discharge then causes the sample to vaporize at the sparking point, exciting the atoms and generating the emission spectrum. A large number of sparks is generated, each lasting only a few microseconds. Due to the lower sample consumption, the limits of detections are poorer than in the arc. The high-voltage alternating current (AC) arc is intermediate in analytical performance between the DC arc and the high-voltage spark. These sources are used mainly in the metallurgical industry.
Direct Current Plasmas

water-cooled discharge tube inserted in a reentranttype cavity that does not require tuning. It is generally considered that a laminar ow torch is more suitable than tangential ow for GC detection. In its usual form, the MIP operates with a low helium ow rate (1 l min 1). MIPs are very suitable for the determination of halides and other nonmetals. A microwave plasma torch (MPT) has been developed consisting of concentric copper tubes. The carrier gas and aerosol enter the inner tube while the outer tube serves as the microwave cavity. The plasma is formed at the top of the MPT and extends out like a ame, but with a central channel for the introduction of the aerosol. The MPT is superior to the conventional MIP since it allows the introduction of wet aerosols at lower power.
Inductively Coupled Plasmas

The DCP evolved from DC arcs and can be classied into two types: discharges conned within a chamber (wall-stabilized) and unconned plasmas. Various designs and congurations of the electrode exist for injecting the sample aerosol-carried gas into the plume, one of which is shown in Figure 3. Magnetic elds can be used to enhance the coupling of the sample into the plasma, as is useful for the analysis of very complex materials. It is characterized by ease of operation, robustness, and optimization for a great variety of complex matrices. Analyte signals are observed in the tail ame or close to the region where the sample is injected into the discharge and where the density of excited species is greatest. The discharge has been shown to be suitable for the analysis of slurries and solutions containing very high salt concentrations.
Microwave-Induced Plasmas

MIPs have been used widely in gas chromatography (GC) detection. Low-power MIPs (50150 W) do not accept liquid aerosols efciently. One way of overcoming this disadvantage is to desolvate the sample solution or to employ electrothermal vaporization. A commercial system is available consisting of a

Cathode

ICP sources have brought about a revolution in multielement analysis. ICPs are generated from radiofrequency (RF) magnetic elds induced by a water- or air-cooled copper coil looped around a quartz tube. The RF magnetic eld oscillates at 27.12 or 40.68 MHz, at incident powers ranging from 0.5 to 2.5 kW. Higher powers are usually applied when organic solvents are aspirated. Argon gas ows through a torch, which consists of three concentric tubes usually constructed from fused silica. The plasma is initiated by seeding the argon stream with electrons provided from a Tesla coil. The electrons, detached from the argon atoms, collide with further argon atoms and populate the coil region with positive and negative charges. Because of the magnetic eld, the particles ow in a closed annular path. Due to the conductance of the gases in the coil region, the charged particles are heated by inductive coupling to a temperature equaling the ionization temperature of the support gases B 70008000 K in the case of argon. A chain reaction of collisional ionization occurs, resulting in the formation of the ICP. In practice, the plasma impedance is monitored along with the tube grid current, grid voltage, plate current, and voltage. These data are fed back to a loop to control the plasma power. The conguration of an ICP-AES system is shown in Figure 4.
Glow Discharge Sources

Anode

Anode

Sample
Figure 3 A schematic design of a direct current plasma source.

Glow discharge is based on a phenomenon called sputtering, where atoms ejected from the surface of the analyte by high-energy argon atoms and ions achieve the excited state in the resulting plasma. A copper tube lled with argon is juxtaposed with the sample and a potential difference applied across the gap, with either a direct current or a RF alternating current. Electrons jump from the negatively charged

194 ATOMIC EMISSION SPECTROMETRY / Principles and Instrumentation

sample toward the positively charged copper electrode and collide with argon atoms, creating positively charged argon ions that are attracted toward the sample surface. En route, they collide with other

Tailflame Fireball Induction coil Spectrometer

Radio frequency generator Coolant gas Auxillary gas Sample capillary Peristaltic pump Injector gas Sample solution To drain Coating gas Nebulizer Spray chamber

Torch

argon atoms and ions, and then strike the analyte surface with sufcient energy to displace electrons and atoms from the sample (sputtering). These analyte atoms also collide with the electrons and highenergy argon atoms/ions, causing them to be excited to higher energy states. As they deexcite, they emit photons resulting in a glow extending 23 mm from the sample (Figure 5). Glow discharge sources are based on three principal designs. The Grimm source, which consists of a copper cathode block in direct contact with the metal sample, is used with DC voltage. The Renault source is based on the Grimm source, but utilizes a ceramic cathode block that allows the use of RF voltages. The most recent development is the Marcus source, which also operates in RF mode. It has a ceramic cathode block and a very short anode tube to facilitate rapid plasma expansion. Although DC and RF plasmas are similar, RF plasmas are more stable and show a greater sputtering depth. The most important difference is that RF glow discharges can be used to analyze both conducting and nonconducting analytes, while DC glow discharges are restricted to conductors.

Instrument Design Sample Introduction

Some of the emission sources discussed above are designed for use with solid samples, which can be

Figure 4 Schematic of an inductively coupled plasma source for atomic emission spectrometry.

Window Anode

D Argon

Electrons Cathode block Ions

O-ring

Sample

Figure 5 Principle of glow discharge atomic emission spectrometry. D diameter of the anode and d distance from anode to sample.

ATOMIC EMISSION SPECTROMETRY / Principles and Instrumentation 195

attached to or used as electrodes. For plasma sources, solid samples can be converted into slurries if the particle size is small, but an alternative is to use spark ablation or laser ablation to explode the sample, generating a small amount of vapor that is carried into the plasma in a gas stream. Gaseous samples can be analyzed directly, but liquid samples are rst converted into aerosols, so that they can desolvate and atomize completely. The most common sample delivery system consists of a peristaltic pump and capillary tube to deliver a constant ow of analyte liquid into a nebulizer. The nebulizer turns the analyte liquid into ne droplets, which are carried by gas into the plasma. Larger droplets (45 mm) are captured in the spray chamber, and are drained from the instrument.
Analysis of Solids in Plasma Sources

Spark ablation In this method, conducting samples are vaporized with an electrical discharge, while nonconducting samples are rst modied by mixing with copper or carbon powder. The dry aerosol is carried by an argon stream into the plasma. The system is calibrated with samples of similar physical and chemical composition. Slight differences can be compensated through the use of internal standards. Large particles can be eliminated using traps, as long as internal references are available. Laser ablation This method is used as a microchemical sampling procedure for localized determinations. A pulsed neodymiumyttrium aluminum garnet (NdYAG) laser is used to ablate material from solid samples. Repetitive laser pulses and sample translation can be used to improve the precision and accuracy of the analysis. Refractory materials and geological samples can be analyzed for trace and major elements. Powdered samples can be pelleted under high pressure for bulk analysis.
Nebulizers

Many different types of nebulizer are available, some of which are suitable for general analytical purposes while others have more specialized uses. Pneumatic nebulizers are general-purpose devices in which the aerosol is formed by the shattering effect of a highvelocity jet of gas. The most commonly used pneumatic nebulizer is the Meinhard glass concentric nebulizer, in which the sample is introduced along a narrow capillary tube located within a larger glass or quartz tube. The outer tube contains argon gas, which ows to a 1020 mm gap surrounding the sample capillary. The aerosol is formed by the

venturi effect produced by the gas stream as it is forced through the annulus, which fragments the liquid into ne droplets. The Meinhard nebulizer is sensitive to clogging, so particulates and solutions with high salt concentrations should be avoided. Cross-ow nebulizers consist of a capillary tube that directs a stream of argon gas at 901 to the sample delivery tube, creating an aerosol due to its shearing effect over the sample tube. Again, these nebulizers are designed for general-purpose use, although they are less prone to blockage where the sample has a high salt concentration. Parallel ow nebulizers, such as the Burgener nebulizer, consist of parallel sample and gas capillaries with adjacent exits, so that the liquid sample is drawn into the gas stream. These are designed specifically to deal with inert samples with a high concentration of dissolved solids. In the Babington nebulizer, the liquid sample ows over a smooth surface containing a small orice, through which argon ows at a high velocity, shearing the liquid into tiny droplets. As above, this device is not susceptible to clogging and can handle viscous solutions and suspensions. Another nebulizer designed for these difcult samples is the V-groove nebulizer, a special type of Babington nebulizer in which the liquid ows down a vertical V-shaped groove toward the gas orice, from which argon ows at a pressure of 2101050 kPa. A further Babington-type nebulizer, the Frit nebulizer, produces very ne aerosols but has very long washout times. Ultrasonic nebulizers offer enhanced sensitivity in detection limits by using a vibrating piezoelectric transducer to set up standing waves in the liquid to produce uniformly sized droplets. The efciency of nebulization is so high that the solvent loading of the aerosol needs to be reduced by thermal desolvation, otherwise cooling of the plasma takes place. Direct injection nebulizers (DINs) are effective devices for introducing liquids directly into the plasma when ows are slower than 0.1 ml min 1. By avoiding the use of a spray chamber, DINs allow 100% transport into the plasma. However, solvent loading in the plasma can exceed the optimum level and can cause a reduction in the plasma temperature, resulting in lower intensities.

Instrument Design Optical Systems

Once the sample has been introduced into the emission source, atomized, and excited, the emitted photons are diffracted by an optical system consisting of slits, mirrors, and gratings, which focus the spectral lines onto a detector. This section discusses the types of gratings and spectrophotometer designs that can be used in AES.

196 ATOMIC EMISSION SPECTROMETRY / Principles and Instrumentation Gratings

Gratings are reective surfaces containing parallel, equally spaced lines. Their resolving power is proportional to the number of lines, which in turn depends on the line spacing. For radiation arriving with an angle of incidence a, the angle b at which it will be diffracted by a grating of N lines per millimeter depends on the wavelength l of the radiation, and is dened by the equation
sin a sin b kNl

The resolving power of a grating is a measure of its ability to separate to the baseline two adjacent spectral wavelengths l1 and l2. The resolution R is expressed as
R l=l1 l2

Monochromators

In this equation, k is the order of diffraction, meaning that constructive interference occurs at wavelength l (rst order), l/2 (second order), l/3 (third order), and so on. The spectrum produced by a grating thus consists of several superimposed orders, with the rst and second orders carrying most of the energy. The blaze angle of a diffraction grating is the mirroring angle of each line. The blaze angle is not arbitrarily selected; radiation can be concentrated into the rst order, rather than in multiple orders and the performance of the grating for a particular spectral range can be optimized by varying the blaze angle. To cover the entire analytical spectral range, two gratings may be employed, or the spectra can be observed in several orders. Ruled gratings have been replaced by holographic gratings produced from the interference patterns generated by two synchronous lasers. The interference pattern is etched into a photosensitive lm, and replicas of these gratings can be manufactured readily. The grating pattern created in this way is greatly superior to those produced mechanically, being much more accurate, having higher linearity, and being free from imperfections and distortions that can give rise to ghosts and stray light. However, the brightness achieved by the conventional holographic gratings is not as high as that of ruled gratings because of the sinusoidal groove prole. The echelle grating is designed to operate in multiple orders to produce high-resolution spectra. In contrast to normal gratings, echelles are ruled at 30 300 grooves per millimeter by ion bombardment, and are frequently in the range of 30120 orders. The grating consists of saw-like grooves varying in height and 613 mm in depth. The echelle grating is designed to separate one order of diffraction from another. This is achieved by inserting a quartz prism, which acts as an order sorter, in front of the grating. Successive spectra are diffracted to different degrees, so that the various orders appear as a two-dimensional array of wavelengths. These gratings are installed in polychromators, sequential systems, and in charge-injected and charge-transfer detector instruments (see below).

A monochromator measures a single wavelength, but can be scanned through a wide wavelength range. Polychromatic light passes through an entrance slit and is dispersed by diffraction gratings. These instruments are used in sequential mode, element determinations being performed one after the other. Two designs are usually employed in commercial instrumentation: CzernyTurner and echelle. CzernyTurner monochromators Two mirrors are used to reect and focus the polychromatic and diffracted beams. Wavelengths are selected by using a computer to rotate the grating in various ways. This design is shown in Figure 6. As the grating rotates, a different wavelength is focused onto the exit slit. Echelle monochromators These are high-resolution instruments that readily achieve resolutions of 5 pm in contrast to the 1020 pm that is normal for conventional sequential instruments. Because the spectra are recorded one above the other, such instruments can be very compact.
Simultaneous Spectrometers

There are several types of simultaneous instruments, which carry out elemental determinations in parallel rather than in series. They differ in optical design and the type of detector that is used. Polychromators These instruments can measure numerous spectral lines simultaneously, and several approaches can be used to achieve this. In the classical PaschenRunge design, light is directed onto a diffraction grating that diffracts the polychromatic radiation into its individual wavelengths. Exit slits are located at predetermined positions on a Rowland circle to focus the diffracted wavelengths onto a specific photomultiplier tube (PMT). In this design, the number of elements that can be determined simultaneously is limited by the geometric conguration of the exit optic area of the instrument. This is a disadvantage compared with the state-of-theart charge-coupled and charge-injection devices discussed below. Geometric alignment is also controlled by the space requirements of the PMTs, and as a

ATOMIC EMISSION SPECTROMETRY / Principles and Instrumentation 197

Source Variable entrance slit

ICP Direct drive Grating Focusing mirrors

PMT

Variable exit slit

Figure 6 CzernyTurner monochromator. ICP inductively coupled plasma and PMT photomultiplier tube. Reproduced from www.thespectroscopynet.com

result a series of mirrors is employed to direct the spectral radiation to the measuring surface of the detector. For the determination of the spectral lines in the low part of the UV spectrum (o190 nm), as is necessary in the detection of aluminum and phosphorus, the spectrometer must be contained in a vacuum or purged of oxygen using nitrogen or argon gas. Polychromators have several advantages, including high sample throughput, lower running costs, and the ability to measure more than 20 elements, in duplicate, with background correction in less than 5 min using only 5 ml of solution. However, disadvantages include the high costs associated with the individual electronic systems required for each spectral line measurement, and the inexibility of the instrument due the static optical system.

typically 12 ns for a 1090% change in signal. The main inconvenience of photomultipliers is their cost. There are several types of photomultipliers, which differ in the nature of the entrance window, either crystal or uoride, and in the nature of the sensitive layer on the photocathode. Some are only sensitive in the far-UV while others are more sensitive in the visible. The type of photomultiplier to be used is selected according to the wavelength of the line to be detected. A fatigue lamp (a small incandescent light source) is often used with photomultipliers to keep the temperature of the tube and its associated electronics constant. The fatigue lamp is switched on when the emission source is off and vice versa. Charge-injection devices (CIDs) CIDs can be used in combination with an echelle spectrometer to produce a exible detection system for multielement analysis using a direct current arc, AC spark, or inductively coupled or direct current argon plasmas. The CID consists of a two-dimensional array of detector elements and when it is coupled to a polychromatic dispersive system, simultaneous multielement analysis is provided over the spectral range 170 800 nm. In addition to the multielement capability and large dynamic range (eight orders of magnitude), the system allows random access integration, where each detector element can be nondestructively processed until an appropriate signal-to-noise ratio is attained. Background can be read simultaneously, and alternate spectral lines can be selected for the analysis of spectrally complex materials. The detection limits are similar to those obtained by conventional

Instrument Design Detection

Photomultiplier Tubes

Photons emerging from the exit slits of the spectrophotometer are detected by one of two types of device, a PMT or a solid-state component. Photomultipliers are often used as detectors in AES. Incident photons emerging from the exit slit fall on the photocathode, liberating electrons, and the current is amplied by a set of dynodes. The nal anode current is proportional to the incident photon signal received by the photocathode. The measurement dynamic range is very broad, i.e., 1015, and sensitivity is high. These detectors allow the detection of low intensities emitted by trace elements, as well as strong signals from major elements. They have very fast response times,

198 ATOMIC EMISSION SPECTROMETRY / Interferences and Background Correction

detection systems. The system is ideally suited to semiquantitative screening analysis. Charge coupled devices (CCDs) and echelle polychromators CCDs and echelle polychromators are now available, and in such systems the high-energy echelle spectrometer utilizes two detector focal planes and two cross-dispersers. At 200 nm, the resolution is 0.007 nm but this degrades substantially in the visible region. The cross-disperser for the UV region (167375 nm) is a grating (374 lines per millimeter) with a Schmidt correction incorporated into its surface. Aberration is also corrected for a 400 mm radius focal plane. The cross-disperser for the visible region is a fused 601 quartz prism. A segmented array CCD consists of 224 addressable subarrays with over 6000 pixels on a 13 18 mm silicon substrate. One of the drawbacks of the CCD is the inability to read nondestructively. When the charge is read on a subarray, it is destroyed and cannot be monitored to adjust the integration time. Photodiode arrays (PDAs) A spectrally segmented PDA spectrophotometer has also been developed. Radiation from the plasma is predispersed and transmitted through an optical mask prior to dispersion by an echelle grating onto a PDA. Limits of detection are similar to those obtained by conventional detection systems, except at low wavelengths where degradation has been observed.
See also: Atomic Emission Spectrometry: Interferences and Background Correction; Flame Photometry; Inductively Coupled Plasma; Microwave-Induced Plasma.

Further Reading
Beauchemin D, Le Blanc JCY, Peters GR, and Craig JM (1992) Plasma emission spectrometry. Analytical Chemistry Reviews 64: 442R467R.

Bings NH, Bogaerts A, and Broekaert JAC (2002) Atomic spectroscopy. Analytical Chemistry 74: 26912711. Bogaerts A and Gijbels R (1998) Fundamental aspects and applications of glow discharge spectrometric techniques. Spectrochimica Acta B 53: 142. Cave MR, Butler O, Chenery SRN, et al. (2001) Atomic spectrometry update. Environmental Analysis. Journal of Analytical Atomic Spectrometry 16: 194235. Evans EH, Day JA, Price WJ, et al. (2002) Atomic spectrometry update. Advances in atomic emission, absorption and uorescence spectrometry, and related techniques. Journal of Analytical Atomic Spectrometry 17: 622651. Evans EH, Day JA, Price WJ, et al. (2003) Atomic spectrometry update. Advances in atomic emission, absorption and uorescence spectrometry, and related techniques. Journal of Analytical Atomic Spectrometry 18: 808833. Evans EH, Fisher A, and Hill S (1998) An Introduction to Analytical Atomic Spectrometry. New York: Wiley. Fisher A, Hinds MW, Nelms SN, Penny DM, and Goodall P (2002) Atomic spectrometry update. Industrial analysis: Metals, chemicals and advanced materials. Journal of Analytical Atomic Spectrometry 17: 16241649. Hill SJ (1999) Inductively Coupled Plasma Spectrometry and its Applications. Boca Raton: CRC Press. Marcus RK and Broekaert JAC (2003) Glow Discharge Plasmas in Analytical Spectroscopy. New York: Wiley. Montaser A and Golightly DW (1992) Inductively Coupled Plasmas in Analytical Atomic Spectrometry. Weinheim: VCH. Payling R (1998) Glow discharge optical emission spectrometry. Spectroscopy 133: 3648. Payling R and Larkins P (2000) Optical Emission Lines of the Elements. New York: Wiley. Taylor A, Branch S, Halls D, Patriarca M, and White M (2003) Atomic spectrometry update. Clinical and biological materials, foods and beverages. Journal of Analytical Atomic Spectrometry 18: 385427. Thomsen VBE (1996) Modern Spectrochemical Analysis of Metals: An Introduction for Users of Arc/Spark Instrumentation. Ohio: ASM International.

Interferences and Background Correction

R M Twyman, University of York, York, UK
& 2005, Elsevier Ltd. All Rights Reserved.

Introduction
When a spectral line produced by one element is very close to a line produced by another element, interference between the two lines may take place. If this

happens, the measured intensity is a combination of the intensities of the two emission lines and does not give a true indication of the abundance of either element. Spectral line interference in atomic emission spectrometry (AES) can severely affect the accuracy of trace and minor element determinations. Therefore, measurement of the analytical line of interest must take into account the possibility of interference from adjacent spectral lines and the interference