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termination by atomic absorption spectrometry. Analyt- Berman SS (1989) Sequestration of volatile element
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MacLaughlin RL and Brindle ID (2002) A new sample in- furnace atomic absorption. Spectrochimica Acta 44B:
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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 pro-

Principles and duction control of both raw materials and finished
Instrumentation products. Finally, emission spectrometry allows the el-
ements present in the sun and stars to be identified,
helping us to understand better the nature of the
R M Twyman, University of York, York, UK
universe. These are only a few examples of scientific and
& 2005, Elsevier Ltd. All Rights Reserved. technical disciplines in which the technique of emission
spectrometry has made a significant contribution.

Introduction Theory and Signal Generation

Atomic (or optical) emission spectrometry (AES, OES)
Atomic Spectra
is an important technique for the multielement analysis
of a wide range of materials. Many elements have been AES involves the measurement of electromagnetic
discovered using emission spectrometry and it is the radiation emitted from atoms. Both qualitative and
most commonly used procedure for the measurement quantitative data can be obtained from this type of
of trace elements in rocks, water, soil, manufactured analysis. In the former case, the identity of different
goods, and biological specimens. The technique is used elements reflects the spectral wavelengths that are
to monitor the levels of different chemicals and trace produced, while in the latter case, the intensity of the
elements in the environment and to determine the com- emitted radiation is related to the concentration of
positions of solids, liquids, and gases. In geoanalysis, each element. Atomic spectra are derived from the
emission spectrometry has been instrumental in the transition of electrons from one discrete electron or-
exploration of economic mineral deposits. In metal- bital in an atom to another. These spectra can be
lurgy and in the semiconductor industry, emission 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 nu- energy levels and vertical lines depict permissible tran-
cleus surrounded by discrete electron orbits, each sitions between them. The arrows show the direction
associated with energy of the order hn. Every atom of energy input or output (ascending arrows show the
has a certain number of electron orbitals, and each absorption of energy while descending arrows show
electron orbital has a particular energy level. When energy radiation). When an electron in a quantum
all the electrons are present in the orbitals, the atoms level j is captured by an ionized atom, energy is lib-
are in the most stable form (the ground state). When erated according to the following equation:
energy (either thermal, resulting from collision, or
radiational, resulting from the absorption of elect- hn ¼ hnj þ mn2 =2 ¼ Ej þ mn2 =2
romagnetic radiation) is applied to an atom and is
sufficient to lift an electron from a shell with energy The wavelength for the emitted radiation due to a
Ei to one with Ej, the atom is said to be in the excited transition Ej
Ei is
state. The state of excitation is unstable and decays l ¼ hc=E
rapidly. The residence time of the unstable excited
where E is the energy difference and l is the wave-
state is very short, in the order of 10
8 s. When
length of the emitted radiation.
electrons return to the stable ground state, energy is
Spectra of neutral excited atoms are denoted as I,
emitted and that energy is equal to the difference in
and correspond to those deexciting to the ground state
the energies between the ground and excited states.
(resonance lines) or close to the ground state (near-
The energy is released in the form of electromagnetic
resonance lines). They are observed in low-energy
radiation and defines the wavelength of the transi-
sources such as flames. Spectra of singly ionized atoms
tion. The relationship between the energy and
are denoted as II, and they are observed in high-
wavelength is described by the Planck equation:
energy sources such as electrical sparks, inductively
Ej
Ei ¼ hn ¼ hc=l coupled plasmas (ICPs), and glow discharges. Every
element has a characteristic emission spectrum, which
is the basis of spectrochemical analysis.
where Ej
Ei is the energy difference between the two
levels (and Ej4Ei); h is Planck’s constant, 6.624 
Molecular Spectra
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; Molecular spectra consist of numerous densely
and l is the wavelength of the radiation in meters. grouped lines. These are called band spectra because
If enough energy is absorbed by the atom, electrons they appear as luminous bands. The fine structure can
may escape completely, leaving the atom in the ionized only be observed with high-resolution instruments.
state. The energy required for ionization is called the Molecular spectra of excited molecules are related to
ionization potential. Ions also possess ground and ex- the energy states of a molecule rotating around the
cited states, through which they can absorb and emit principal axes of inertia. Band spectra in the near-
energy by the same processes described for an atom. infrared are produced by energy transitions related to
Figure 1 illustrates the electron shell configuration oscillatory vibrations of individual molecules.
in terms of energy levels. Horizontal lines represent
Continuum
This is radiation distributed continuously over the
Excitation Emission wavelength range and can be attributed to recombina-
Ion excited state
e
4 tion processes and other background factors. The in-
Ion ground state tensity of the background increases with temperature.
Energy

Excited h
3
states

2 Instrument Design – Overview
a b c d f g
1
Ground State A spectrometer consists of three main parts: (1) an
Figure 1 Electron shell configurations in terms of energy levels. emission source, which produces the spectrum; (2) an
Arrows depict permissible transitions by absorption and excitation optical system, which scatters the spectrum; and (3) a
(ascending) or radiation and photon emission (descending), a and device to measure the emitted lines. The two major
b represent excitation, c is ionization, d is ionization plus excitation,
types of instrument for the analysis of emission spec-
e is ion emission, and f, g, and h are atom emissions. (Reproduced
with permission from Boss CB and Freeden KJ (1989) Concepts, tra are sequential and simultaneous spectrometers,
Instrumentation and Techniques. Inductively Coupled Plasma although there are many variants of each in terms of
Atomic Emission Spectrometry, Perkin Elmer Corp.) mechanical and optical characteristics. The spectral
192 ATOMIC EMISSION SPECTROMETRY / Principles and Instrumentation

wavelength range of interest is B160–900 nm, but Flame Sources

not all instruments are capable of covering this
In flame emission spectrometry, the sample solution
range, and the resolution may vary with wavelength.
is sprayed or aspirated into a flame as a fine mist or
Oxygen and water vapor absorb short-wave UV
aerosol. The sample is vaporized in the flame, and
emissions (o190 nm) and this obscures the emission
atomized by a combination of heat and the action of
lines of some common and important elements (e.g.,
a reducing gas. The atoms are excited into higher
hydrogen, carbon, oxygen, nitrogen, chlorine, phos- electronic states by the heat, and as they revert to the
phorus, and sulfur). Therefore, oxygen and water
ground state they emit photons, which are measured
vapor must be eliminated from the instrument, either
by the detector. The layout of a flame photometer is
by evacuation or by flushing with nitrogen or argon.
shown in Figure 2.
Nitrogen flushing does not interfere with the analysis
of samples containing nitrogen compounds since Discharge Sources (Arcs and Sparks)
molecular nitrogen (N2) does not obscure the emis-
sion lines from atomic nitrogen in the sample. The first 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 tempera-
Instrument Design – Emission ture of the arc plasma varies from 4000 to 5000 K.
Sources The limits of detection are good and the entire sam-
In spectrochemical analysis, atomization and excita- ple can be consumed. However, due to variations
tion can be achieved using various different emission in the volatilization process, the accuracy is usually
sources. The spectra derived from low-energy sourc- poor. Reproducibility can be improved by using
es such as flames are simpler than those from elec- internal references and optimizing the conditions of
trical discharges, although the temperature of flames vaporization (graphite electrode designs, addition of
and furnaces (2000–4000 K) is inadequate to excite modifiers). The spectral range of the source is limited
many of the elements. Nevertheless, flame emission due to the presence of cyanogen bands with heads at
spectrometry is widely used for the determination of 421.6, 388.3, and 359.0 nm when graphite is used.
the alkali elements (lithium, sodium, and potassium), Argon can be injected into the arc to minimize these
whose excitation states are low enough to be pop- effects. In the so-called cathode region, intensity is
ulated at flame temperatures. Higher-energy sources relatively higher (10–50 times) than in the central
produce higher temperatures and therefore more and anode regions of the arc.
emission lines. In electrical discharges, arcs and Spark sources produce lower average temperature
sparks are created by applying currents and poten- than arcs, but the local temperature can be as high
tials across conducting electrodes, and a large quan- as 40 000 K. Like arc sources, sparks produce ato-
tity of the sample surface is evaporated in this mic lines, but also more pronounced lines for ions,
process. Better quantitative analysis is achieved using which are known as spark lines. The emission source
plasma sources: ICP, direct current plasma (DCP), consists of a sparking stand and a spark generator.
and microwave induced plasma (MIP), which gene- A spark forms between the cathode and the sam-
rally achieve temperatures of 7000–8000 K. Glow ple (which acts as the anode). The adjustable gap
discharge sources, which use high-energy argon at-
oms 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 Mirror
Lens Slit Filter Photodetector
N0 is the number in the ground state, then the excited
fraction is given by Aerosol
enters flame
N1 =N0 ¼ ðg1 =g0 Þ expð
E=kTÞ
Fuel
where E is the energy difference between the ground Air from
compressor
and excited states, T is the absolute temperature (K),
k is the Boltzmann constant (1.38  10
23 J K
1),
Sample Drain
and g1 and g0 are quantum statistical weighting
factors. Figure 2 Schematic of a flame emission spectrophotometer.
 ATOMIC EMISSION SPECTROMETRY / Principles and Instrumentation 193

between the cathode and the sample is sometimes water-cooled discharge tube inserted in a reentrant-
termed the entrode, and is filled with argon. The type cavity that does not require tuning. It is generally
generator initially produces a brief low-energy dis- considered that a laminar flow torch is more suitable
charge that ionizes the argon and creates the plasma. than tangential flow for GC detection. In its usual
A second, high-energy discharge then causes the form, the MIP operates with a low helium flow rate
sample to vaporize at the sparking point, exciting the (1 l min
1). MIPs are very suitable for the determina-
atoms and generating the emission spectrum. A large tion of halides and other nonmetals. A microwave
number of sparks is generated, each lasting only a plasma torch (MPT) has been developed consisting of
few microseconds. Due to the lower sample con- concentric copper tubes. The carrier gas and aerosol
sumption, the limits of detections are poorer than in enter the inner tube while the outer tube serves as the
the arc. The high-voltage alternating current (AC) microwave cavity. The plasma is formed at the top of
arc is intermediate in analytical performance be- the MPT and extends out like a flame, but with a
tween the DC arc and the high-voltage spark. These central channel for the introduction of the aerosol. The
sources are used mainly in the metallurgical industry. MPT is superior to the conventional MIP since it al-
lows the introduction of wet aerosols at lower power.
Direct Current Plasmas
The DCP evolved from DC arcs and can be classified Inductively Coupled Plasmas
into two types: discharges confined within a chamber ICP sources have brought about a revolution in multi-
(wall-stabilized) and unconfined plasmas. Various element analysis. ICPs are generated from radiofre-
designs and configurations of the electrode exist for quency (RF) magnetic fields induced by a water- or
injecting the sample aerosol-carried gas into the air-cooled copper coil looped around a quartz tube.
plume, one of which is shown in Figure 3. Magnetic The RF magnetic field oscillates at 27.12 or
fields can be used to enhance the coupling of the 40.68 MHz, at incident powers ranging from 0.5 to
sample into the plasma, as is useful for the analysis of 2.5 kW. Higher powers are usually applied when
very complex materials. It is characterized by ease of organic solvents are aspirated. Argon gas flows
operation, robustness, and optimization for a great through a torch, which consists of three concentric
variety of complex matrices. Analyte signals are tubes usually constructed from fused silica. The plas-
observed in the tail flame or close to the region where ma is initiated by seeding the argon stream with
the sample is injected into the discharge and where electrons provided from a Tesla coil. The electrons,
the density of excited species is greatest. The dis- detached from the argon atoms, collide with further
charge has been shown to be suitable for the analysis argon atoms and populate the coil region with po-
of slurries and solutions containing very high salt sitive and negative charges. Because of the magnetic
concentrations. field, the particles flow in a closed annular path. Due
to the conductance of the gases in the coil region, the
Microwave-Induced Plasmas charged particles are heated by inductive coupling to
MIPs have been used widely in gas chromatography a temperature equaling the ionization temperature of
(GC) detection. Low-power MIPs (50–150 W) do not the support gases B– 7000–8000 K in the case of
accept liquid aerosols efficiently. One way of over- argon. A chain reaction of collisional ionization oc-
coming this disadvantage is to desolvate the sample curs, resulting in the formation of the ICP. In prac-
solution or to employ electrothermal vaporization. tice, the plasma impedance is monitored along with
A commercial system is available consisting of a the tube grid current, grid voltage, plate current, and
voltage. These data are fed back to a loop to control
the plasma power. The configuration of an ICP-AES
system is shown in Figure 4.
Cathode

Glow Discharge Sources

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 ac-
Anode Anode hieve the excited state in the resulting plasma. A
copper tube filled with argon is juxtaposed with the
sample and a potential difference applied across the
Sample
gap, with either a direct current or a RF alternating
Figure 3 A schematic design of a direct current plasma source. current. Electrons jump from the negatively charged
194 ATOMIC EMISSION SPECTROMETRY / Principles and Instrumentation

sample toward the positively charged copper elec- argon atoms and ions, and then strike the analyte
trode and collide with argon atoms, creating po- surface with sufficient energy to displace electrons
sitively charged argon ions that are attracted toward and atoms from the sample (sputtering). These anal-
the sample surface. En route, they collide with other yte atoms also collide with the electrons and high-
energy argon atoms/ions, causing them to be excited
to higher energy states. As they deexcite, they emit
Tailflame photons resulting in a ‘glow’ extending 2–3 mm from
the sample (Figure 5).
Fireball
Glow discharge sources are based on three princi-
Induction coil
pal designs. The Grimm source, which consists of a
Spectrometer
copper cathode block in direct contact with the metal
sample, is used with DC voltage. The Renault source
Radio frequency is based on the Grimm source, but utilizes a ceramic
generator cathode block that allows the use of RF voltages. The
most recent development is the Marcus source, which
Coolant gas Torch also operates in RF mode. It has a ceramic cathode
Auxillary gas block and a very short anode tube to facilitate rapid
Coating gas plasma expansion. Although DC and RF plasmas are
Sample
capillary similar, RF plasmas are more stable and show a
Nebulizer Spray chamber greater sputtering depth. The most important differ-
Peristaltic
ence is that RF glow discharges can be used to analyze
pump both conducting and nonconducting analytes, while
Injector DC glow discharges are restricted to conductors.
gas

Sample To drain Instrument Design – Sample

solution Introduction
Figure 4 Schematic of an inductively coupled plasma source Some of the emission sources discussed above are
for atomic emission spectrometry. designed for use with solid samples, which can be

Window
Anode

Argon

Electrons
Cathode
block
Ions

O-ring

d Sample

Figure 5 Principle of glow discharge atomic emission spectrometry. D ¼ diameter of the anode and d ¼ distance from anode to
sample.
 ATOMIC EMISSION SPECTROMETRY / Principles and Instrumentation 195

attached to or used as electrodes. For plasma sources, venturi effect produced by the gas stream as it is
solid samples can be converted into slurries if the forced through the annulus, which fragments the
particle size is small, but an alternative is to use spark liquid into fine droplets. The Meinhard nebulizer is
ablation or laser ablation to explode the sample, sensitive to clogging, so particulates and solutions
generating a small amount of vapor that is carried with high salt concentrations should be avoided.
into the plasma in a gas stream. Gaseous samples can Cross-flow nebulizers consist of a capillary tube
be analyzed directly, but liquid samples are first that directs a stream of argon gas at 901 to the sam-
converted into aerosols, so that they can desolvate ple delivery tube, creating an aerosol due to its
and atomize completely. The most common sample shearing effect over the sample tube. Again, these
delivery system consists of a peristaltic pump and nebulizers are designed for general-purpose use, al-
capillary tube to deliver a constant flow of analyte though they are less prone to blockage where the
liquid into a nebulizer. The nebulizer turns the ana- sample has a high salt concentration. Parallel flow
lyte liquid into fine droplets, which are carried by gas nebulizers, such as the Burgener nebulizer, consist of
into the plasma. Larger droplets (45 mm) are cap- parallel sample and gas capillaries with adjacent ex-
tured in the spray chamber, and are drained from the its, so that the liquid sample is drawn into the gas
instrument. stream. These are designed specifically to deal with
inert samples with a high concentration of dissolved
Analysis of Solids in Plasma Sources solids. In the Babington nebulizer, the liquid sample
flows over a smooth surface containing a small or-
Spark ablation In this method, conducting samples ifice, through which argon flows at a high velocity,
are vaporized with an electrical discharge, while shearing the liquid into tiny droplets. As above, this
nonconducting samples are first modified by mixing device is not susceptible to clogging and can handle
with copper or carbon powder. The dry aerosol is viscous solutions and suspensions. Another nebulizer
carried by an argon stream into the plasma. The designed for these difficult samples is the V-groove
system is calibrated with samples of similar physical nebulizer, a special type of Babington nebulizer in
and chemical composition. Slight differences can be which the liquid flows down a vertical V-shaped
compensated through the use of internal standards. groove toward the gas orifice, from which argon
Large particles can be eliminated using traps, as long flows at a pressure of 210–1050 kPa. A further Ba-
as internal references are available. bington-type nebulizer, the Frit nebulizer, produces
very fine aerosols but has very long washout times.
Laser ablation This method is used as a micro- Ultrasonic nebulizers offer enhanced sensitivity in
chemical sampling procedure for localized determi- detection limits by using a vibrating piezoelectric
nations. A pulsed neodymium–yttrium aluminum transducer to set up standing waves in the liquid to
garnet (Nd–YAG) laser is used to ablate material produce uniformly sized droplets. The efficiency of
from solid samples. Repetitive laser pulses and sam- nebulization is so high that the solvent loading of the
ple translation can be used to improve the precision aerosol needs to be reduced by thermal desolvation,
and accuracy of the analysis. Refractory materials otherwise cooling of the plasma takes place. Direct
and geological samples can be analyzed for trace and injection nebulizers (DINs) are effective devices for
major elements. Powdered samples can be pelleted introducing liquids directly into the plasma when
under high pressure for bulk analysis. flows 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
Nebulizers
plasma can exceed the optimum level and can cause a
Many different types of nebulizer are available, some reduction in the plasma temperature, resulting in
of which are suitable for general analytical purposes lower intensities.
while others have more specialized uses. Pneumatic
nebulizers are general-purpose devices in which the
aerosol is formed by the shattering effect of a high-
Instrument Design – Optical Systems
velocity jet of gas. The most commonly used pneu- Once the sample has been introduced into the emis-
matic nebulizer is the Meinhard glass concentric ne- sion source, atomized, and excited, the emitted pho-
bulizer, in which the sample is introduced along a tons are diffracted by an optical system consisting of
narrow capillary tube located within a larger glass or slits, mirrors, and gratings, which focus the spectral
quartz tube. The outer tube contains argon gas, lines onto a detector. This section discusses the types
which flows to a 10–20 mm gap surrounding the of gratings and spectrophotometer designs that can
sample capillary. The aerosol is formed by the be used in AES.
196 ATOMIC EMISSION SPECTROMETRY / Principles and Instrumentation

Gratings The resolving power of a grating is a measure of its

ability to separate to the baseline two adjacent spec-
Gratings are reflective surfaces containing parallel,
tral wavelengths l1 and l2. The resolution R is ex-
equally spaced lines. Their resolving power is pro-
pressed as
portional to the number of lines, which in turn de-
pends on the line spacing. For radiation arriving with R ¼ l=ðl1
l2 Þ
an angle of incidence a, the angle b at which it will be
diffracted by a grating of N lines per millimeter de-
pends on the wavelength l of the radiation, and is Monochromators
defined by the equation
A monochromator measures a single wavelength, but
sin a þ sin b ¼ kNl can be scanned through a wide wavelength range.
Polychromatic light passes through an entrance slit
In this equation, k is the order of diffraction, meaning and is dispersed by diffraction gratings. These in-
that constructive interference occurs at wavelength l struments are used in sequential mode, element de-
(first order), l/2 (second order), l/3 (third order), and terminations being performed one after the other.
so on. The spectrum produced by a grating thus con- Two designs are usually employed in commercial in-
sists of several superimposed orders, with the first and strumentation: Czerny–Turner and echelle.
second orders carrying most of the energy. The blaze
angle of a diffraction grating is the mirroring angle of Czerny–Turner monochromators Two mirrors are
each line. The blaze angle is not arbitrarily selected; used to reflect and focus the polychromatic and dif-
radiation can be concentrated into the first order, rath- fracted beams. Wavelengths are selected by using a
er than in multiple orders and the performance of the computer to rotate the grating in various ways. This
grating for a particular spectral range can be optimized design is shown in Figure 6. As the grating rotates, a
by varying the blaze angle. To cover the entire analyt- different wavelength is focused onto the exit slit.
ical spectral range, two gratings may be employed, or
the spectra can be observed in several orders. Echelle monochromators These are high-resolution
Ruled gratings have been replaced by holographic instruments that readily achieve resolutions of 5 pm
gratings produced from the interference patterns in contrast to the 10–20 pm that is normal for
generated by two synchronous lasers. The interfer- conventional sequential instruments. Because the
ence pattern is etched into a photosensitive film, and spectra are recorded one above the other, such in-
replicas of these gratings can be manufactured read- struments can be very compact.
ily. The grating pattern created in this way is greatly
superior to those produced mechanically, being much Simultaneous Spectrometers
more accurate, having higher linearity, and being free
from imperfections and distortions that can give rise There are several types of simultaneous instruments,
to ghosts and stray light. However, the brightness which carry out elemental determinations in parallel
achieved by the conventional holographic gratings is rather than in series. They differ in optical design and
not as high as that of ruled gratings because of the the type of detector that is used.
sinusoidal groove profile.
The echelle grating is designed to operate in mul- Polychromators These instruments can measure
tiple orders to produce high-resolution spectra. In numerous spectral lines simultaneously, and several
contrast to normal gratings, echelles are ruled at 30– approaches can be used to achieve this. In the clas-
300 grooves per millimeter by ion bombardment, sical Paschen–Runge design, light is directed onto a
and are frequently in the range of 30–120 orders. diffraction grating that diffracts the polychromatic
The grating consists of saw-like grooves varying in radiation into its individual wavelengths. Exit slits
height and 6–13 mm in depth. The echelle grating is are located at predetermined positions on a Rowland
designed to separate one order of diffraction from circle to focus the diffracted wavelengths onto a spe-
another. This is achieved by inserting a quartz prism, cific photomultiplier tube (PMT). In this design, the
which acts as an order sorter, in front of the grating. number of elements that can be determined simulta-
Successive spectra are diffracted to different degrees, neously is limited by the geometric configura-
so that the various orders appear as a two-dimen- tion of the exit optic area of the instrument. This is
sional array of wavelengths. These gratings are in- a disadvantage compared with the state-of-the-
stalled in polychromators, sequential systems, and in art charge-coupled and charge-injection devices dis-
charge-injected and charge-transfer detector instru- cussed below. Geometric alignment is also controlled
ments (see below). by the space requirements of the PMTs, and as a
 ATOMIC EMISSION SPECTROMETRY / Principles and Instrumentation 197

Source
Variable entrance slit

ICP

Direct Focusing
drive mirrors

Grating

PMT

Variable exit slit

Figure 6 Czerny–Turner monochromator. ICP ¼ inductively coupled plasma and PMT ¼ photomultiplier tube. Reproduced from
www.thespectroscopynet.com

result a series of mirrors is employed to direct the typically 1–2 ns for a 10–90% change in signal. The
spectral radiation to the measuring surface of the main inconvenience of photomultipliers is their cost.
detector. For the determination of the spectral lines There are several types of photomultipliers, which
in the low part of the UV spectrum (o190 nm), as is differ in the nature of the entrance window, either
necessary in the detection of aluminum and phospho- crystal or fluoride, and in the nature of the sensitive
rus, the spectrometer must be contained in a vacuum layer on the photocathode. Some are only sensitive in
or purged of oxygen using nitrogen or argon gas. the far-UV while others are more sensitive in the vis-
Polychromators have several advantages, including ible. The type of photomultiplier to be used is se-
high sample throughput, lower running costs, and lected according to the wavelength of the line to be
the ability to measure more than 20 elements, in detected. A fatigue lamp (a small incandescent light
duplicate, with background correction in less than source) is often used with photomultipliers to keep
5 min using only 5 ml of solution. However, di- the temperature of the tube and its associated elec-
sadvantages include the high costs associated with tronics constant. The fatigue lamp is switched on
the individual electronic systems required for each when the emission source is off and vice versa.
spectral line measurement, and the inflexibility of the
instrument due the static optical system.
Charge-injection devices (CIDs) CIDs can be used
in combination with an echelle spectrometer to pro-
Instrument Design – Detection duce a flexible detection system for multielement
analysis using a direct current arc, AC spark, or in-
Photomultiplier Tubes
ductively coupled or direct current argon plasmas.
Photons emerging from the exit slits of the spectro- The CID consists of a two-dimensional array of de-
photometer are detected by one of two types of tector elements and when it is coupled to a polychro-
device, a PMT or a solid-state component. Photomul- matic dispersive system, simultaneous multielement
tipliers are often used as detectors in AES. Incident analysis is provided over the spectral range 170–
photons emerging from the exit slit fall on the pho- 800 nm. In addition to the multielement capability
tocathode, liberating electrons, and the current is am- and large dynamic range (eight orders of magnitude),
plified by a set of dynodes. The final anode current is the system allows random access integration, where
proportional to the incident photon signal received by each detector element can be nondestructively proc-
the photocathode. The measurement dynamic range is essed until an appropriate signal-to-noise ratio is at-
very broad, i.e., 1015, and sensitivity is high. These tained. Background can be read simultaneously, and
detectors allow the detection of low intensities emit- alternate spectral lines can be selected for the ana-
ted by trace elements, as well as strong signals from lysis of spectrally complex materials. The detection
major elements. They have very fast response times, limits are similar to those obtained by conventional
198 ATOMIC EMISSION SPECTROMETRY / Interferences and Background Correction

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the visible region. The cross-disperser for the UV tion and fluorescence spectrometry, and related tech-
region (167–375 nm) is a grating (374 lines per milli- niques. Journal of Analytical Atomic Spectrometry 17:
meter) with a Schmidt correction incorporated into 622–651.
its surface. Aberration is also corrected for a 400 mm Evans EH, Day JA, Price WJ, et al. (2003) Atomic spect-
radius focal plane. The cross-disperser for the visible rometry update. Advances in atomic emission, absorp-
region is a fused 601 quartz prism. A segmented array tion and fluorescence spectrometry, and related
CCD consists of 224 addressable subarrays with over techniques. Journal of Analytical Atomic Spectrometry
18: 808–833.
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Analytical Atomic Spectrometry. New York: Wiley.
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(1992) Plasma emission spectrometry. Analytical Chem- Metals: An Introduction for Users of Arc/Spark Instru-
istry Reviews 64: 442R–467R. mentation. Ohio: ASM International.

Interferences and Background Correction

R M Twyman, University of York, York, UK happens, the measured intensity is a combination of
& 2005, Elsevier Ltd. All Rights Reserved. the intensities of the two emission lines and does not
give a true indication of the abundance of either ele-
ment. Spectral line interference in atomic emission
spectrometry (AES) can severely affect the accuracy
Introduction of trace and minor element determinations. There-
When a spectral line produced by one element is very fore, measurement of the analytical line of interest
close to a line produced by another element, inter- must take into account the possibility of interference
ference between the two lines may take place. If this from adjacent spectral lines and the interference