INDUCTIVELY COUPLED PLASMA AND ITS USE IN

EMISSION SPECTRAL ANALYSIS (Review)

UDC 533.9.082.5:543.42

G. N. Gerasimov, M. A. Kartasheva,
and S. Ya. Petrov

The development of the productive forces of contemporary society, based on progressive

technology and the use of a wide class of new materials requires constant improvement of the
methods of analysis of the elemental composition of substances.
At present one of the basic methods of control is the method of emission spectral analysis (ESA).
Emission spectral analysis methods are used in practically all branches of industry, in
ecology, geology, agriculture, medicine, biology, etc. The furthest progress in spectral
analysis is connected with, in particular~ the development and application of new types of
sources of excitation of spectra.
Electric discharge sources of excitation of the spectrum, used in ESA, serve for atomization of the analyzed sample and its effective excitation. Such sources must be stable in
their parameters (current and voltage of the discharge gap): the parameters must not vary
depending on the concentration of atoms present in the discharge; when performing analysis
such sources must guarantee the maximum possible dynamic range of measurements of the concentration of the analyzed atoms, high reproducibility of analysis, and low detection limits.
In recent years in the practice of spectral analysis sources of excitation of spectra
(SES) have become widely used based on the use of an electrodeless high-frequency plasmotron
- the so-called inductively coupled plasma (ICP).
The technical features of design of such sources provide unique possibilities for their
use in ESA of water solutions.
In this connection the use of sources based on ICP for analysis of biological and medical objects, and also for ecological investigations acquires special significance.
General Characteristics of an ICP. In comparison with traditional electric-discharge
sources, sources based on ICP have a number of fundamental technical features connected with
the specifics of supply of the analyzed sample to the analytical region. Therefore in this
review, along with an examination of the fields of application of the new source, great attention was devoted to the design part and to methods of supply of the sample.
In ICP sources discharges of toroidal shape are most often used, blown by a flow of
plasma-forming gas, directed along the axis of symmetry of the discharge. The discharge is
excited by a source of power 0.3-10 kW, generating high-frequency vibrations in the 0.3-80
MHz region. Different researchers have used sources differing in the geometry of the inductor, the size and configuration of the plasma burners, the number of gas flows, the sort of
plasma forming gas, etc.
Among the basic advantages of the analytical characteristics of ICP sources the following parameters can be mentioned:
multielement analysis under fixed conditions of operation of the source;
the absence of interelement effects;
high reproducibility of analysis;
wide dynamic range of determination of concentrations, comprising 5-6 orders;
low detection limits of elements (0.i-i0 ng/ml);

S. I. Vavilov State Optical Institute, Leningrad. Translated from Zhurnal Prikladnoi

Spektroskopii, Vol. 55, No. i, pp. 7-30, July, 1991. Original article submitted July 17,
1990.

0021-9037/91/5501-0623512.50

9 1991 Plenum Publishing Corporation

623

Fig. i.

Greenfield's (a), Fassel's (b), and

Sukach's (c) plasma burners.

absence of contamination caused by sputtering of the electrodes;

convenience of introduction of sample into the analytical gap.
The most widely used fields of application of SES-ICP are connected with analysis of
liquid samples, but publications are encountered reporting on the use of such sources for
analysis of solid, powder, and gaseous samples.
The use of three basic types of high-frequency induction plasmotrons is well known:
Greenfield's [1], Fassel's [2], and Sukach's [3]. Greenfield's plasma burner operates on
nitrogen, cooling an external tube (gas expenditure 20-70 liters/min), and the plasma-forming
gas argon is supplied along the central tube, it does not transport the aerosol (Fig. la).
The power of the generator is 2-7 kW, the diameter of the external tube 30 mm. In Fassel's
burner (diameter of external tube 18 mm) only argon is used, its expenditure is 15-20 liters/
min, the expenditure of gas in the plasma forming jet 0.6-1 liter/min, which corresponds to
velocities of the jet of i0 ~ cm/sec, and in this case the velocity of the flux transporting
aerosol is 1.2 times the velocity of the plasma forming flux (Fig. Ib). The power of the
generator is 1.0-2.5 kW. In both cases generators of frequency 27-50 MHz are used.
Usually complete vaporization and atomization of the substance in a burner of Fassel's
type are achieved at a height of 5-10 mm above the inductor. This region is also used for
spectroanalytic purposes (up to 25 mm above the inductor).
Britske et al. [3] proposed and developed an original type of induction discharge (Fig.
ic). In it in all two argon fluxes are used - the plasma-forming and the transporting
fluxes. The total expenditure of gas does not exceed 4 liters/min, the power of the generator is 2 kW, and water is used to cool the walls of the quartz tube. Observation is performed along the axis of the discharge or through a special side window.
One of the most important characteristics of sources based on ICP is the ratio of the
intensities of the analytical lines to the background near these lines. Optimization of the
sources and their comparison with each other in the majority of cases is performed specifically using this parameter [4-10]. The chosen characteristic of the sources is a function
of no less than five parameters (power of the generator, zone of observation, velocity of
each of three fluxes), which are not independent. It is necessary to take into account that
in analysis the researcher also chooses the wavelength of observation [7, 11-13].
An important characteristic of an ICP is its clearly expressed spatial inhomogeneity.
It is necessary to know the intensity distributions of the lines of atoms and ions of the
sample over the radius and height of the analytical zone in choosing the optimum conditions
of analysis, which change, depending on what element is analyzed.
In [7, ii, 12] it was
shown that the spectral lines radiated by the ICP burner can be divided into two large
groups: "soft"lines, with energy of excitation ~5 eV (their intensity strongly depends on
the power conducted to the plasma, the velocity of the gas flux transporting the aerosol,
the ionization potential, and excitation energy of the atoms of the sample). The second

624

group of lines (so called "hard" lines [7] with excitation energy ~7 eV) are less sensitive
to a change in the parameters of the source.
The intensity maxima of the hard lines with
respect to the height of the plasma burner are closely situated and as a rule are always
higher than for the soft lines [Ii, 12].
In [12] it was proposed to divide the plasma
burner into two zones:
of "thermal" and "nonthermal" excitation.
The first zone is located
near the inductor, the second at a distance of more than 15 mm from the inductor (for the
Fassel burner, operating at 1.5 kW power).
The soft lines are excited in the thermal zone; on an increase in power the position
of the intensity maxima shift closer to the inductor and the temperature of excitation increases.
In the nonthermal zone the hard lines are excited.
Ionic lines excited in this
region are among the most sensitive in an ICP [12].
Despite the obvious successes of the empirical method of optimization of operation of
the source, the insufficiency of knowledge of the basic physical processes in the source,
which permit more effectively performing the search for the optimum conditions of analysis
is felt.
The use of formal statistical methods of optimization on a simultaneous change in
all the parameters often leads to finding optimum conditions [8-10] beyond the limits of the
physicotechnical possibilities of the analytical apparatus.
For this reason the study of
the physical properties of the analytical zone is an essential problem.
Knowledge of the basic physical processes in the source permits explaining the spatial
and other characteristics and laws of the emission spectra of ICP and thus more effectively
optimizing operation of SES-ICP, avoiding the analytics from unnecessarily cumbersome work
on a consequent choice of the optimum parameters, and also guaranteeing the correctness of
giving the boundary conditions and limits of change of the parameters using statistical
methods, which accelerates the process of optimization and practically leads to the need to
control the reproducibility of the conditions of analysis before the beginning of work.
One of the most effective methods used in spectroanalytic practice to improve the reproducibility of the results of measurements is the method of an internal standard.
As internal standard lines are chosen, the intensity of which vary as far as possible identically
with the lines of the atoms of the sample on a change of conditions in the discharge.
The method of an internal standard is widely used in the practice of quantitative emission spectroscopy to improve the accuracy and reproducibility of results of measurements
due to the decrease in the effect of noises and drifts on them. The basic difficulty in
using this method consists in finding comparison lines, which duplicates the behavior of the
analytical lines.
Emission spectral analysis with an SES-ICP is at present one of the most
important analytical methods for determination of low and trace contents of elements.
However, as in other methods, the reproducibility of the results of measurements and the detection limits (DL) are limited by the signal/noise ratio.
The characteristics of the noises
for sources of optical spectrometry were examined, for example, in [14]. Two basic types
of noises were examined in it: shot noise and flicker noise (fluctuation noise).
The first
is explained by the statistical nature of photons reaching the detector, emission of electrons and electronic amplification; it obeys the law of the Poisson distribution with a
standard deviation proportional to the square root of the number of events.
The second type
of noise - low-frequency - is called fluctuation noise (flicker noise).
It arises due to
changes induced by slow drift of the analytical signal as a result of nonuniformity of entry
of the investigated substance (element) and drift of the radiation intrinsically of the
light source.
Analysis of the limiting accuracy of noise for an ICP [15, 16] showed that
the contribution of flicker noise predominates and limits the reproducibility of the results
of measurements to 1%. This limitation in principle is also applicable to other methods of
spectroscopic investigations.
As was already said above, the well known method of a decrease in the effect of fluctuations is the method of the internal standard [17], which has been successfully applied,
for example, in working with a constant current arc in [18, 19], the authors of which developed the criteria of a correct choice of the internal standard for each analytical line.
These criteria are the following requirements:
the concentration of the internal standard must be negligibly small;
the internal standard must be chemically very pure in comparison with the determined
elements;

625

in the case of the use of photographic methods of recording both lines must have close
wavelengths;
both the lines of the internal standard and the analytical line must have the same excitation energy;
the rates of vaporization must be close (practically the same);
the ionization energies must also be practically the same;
the atomic masses of both elements must be close;
both lines must not be subject to reabsorption;
both lines must be close in intensity, especially in the case of photographic recording.
The first applications of the method for an ICP [20] were unsuccessful, since the convergence of the results of measurements using an internal standard did not improve. On examination of this result Duursma et al. [20] concluded that it is necessary to find an internal standard for each analytical line. In a later work [15] it was proposed to choose
a parameter which as far as possible duplicates the behavior of fluctuations of the analytical signal. The authors of this work propose that such a parameter might be the intensity
of the spectral line, the gas flow or pressure, or the acoustical signal.
In a number of works [21-24] positive results were obtained. With the correctly chosen
procedure of internal standardization the reproducibility and accuracy of analysis on SESICPiapparatus can be improved by 2-20 times. However, the choice of internal standard is a
far from solved problem for SES-ICP. For example, in [23] changes in the correlation of the
ratios of the radiation intensity were studied for 12 pairs of lines as a function of the
change in the conditions in the discharge and the height of observation.
It turned out that
although the intensity fluctuations of all (both the ionic and atomic) lines of the sample
are determined principally by fluctuations in the system of sample supply (sputtering) the
conditions of excitation and the time of vaporization change differently for different spectral lines with the change in distance from the inductor, the expenditure of gases, and the
output power of the generator. From this it follows, for example, that the internal standard chosen for one height of observation, is unsuitable for another, i.e., as for optimization of the conditions of analysis, it is necessary to solve a multiparametric problem,
which requires considerable expenditure of time, connected not only with the search for
suitable conditions in the discharge, but also in connection with the cumbersomeness and
duration of the sample preparation procedures. Knowing the basic physical processes in an
SES-ICP!would permit systematizing the selection of analytical pairs of lines without performing prolonged empirical searches. This, besides, would permit broadening the analytical
possibilities of the source for solving the problems of emission spectroscopy.
Physical investigations of an ICP performed in recent years have shown that the parameters of the plasma - the concentration of electrons ne, the electron temperature Te, etc. are stable relative to the fluctuation of parameters of the setup (the power of the generator,
the velocity of the gas flows) and are well reproduced, while limitations on the reproducibility of the intensities are due to fluctuations of the sample supply.
This circumstance along with the noted spectroanalytical advantages permit hoping that
with SES-ICP!an approach ne~ in principle to emission spectral analysis will be accomplished
on using fast computers. The essence of this approach consists in the fact that for setups
with SES-ICP lit makes sense to synthesize and calculate spectra for the choice of analytical
lines and preliminary study of spectral superimpositions in analysis of complex matrices.
In this case it is necessary that the spectra created and calculated take into account the
parameters of the concrete setup: the power introduced into the plasma, the velocity of the
gas flows, the zone of observation, the transmission band of the spectrometer and the spectral sensitivity of the receiver. The advantage of the given method in comparison with the
use of special table of spectral lines consists of the fact that the intensity of the lines
and their shape, i.e., accounting for spectral superpositions, may be obtained for the most
diverse conditions of operation of the source and different matrices, while the existing
tables [25-27] are based either on well known classical tables [28, 29] giving inaccurate
representation of the spectra of ICP, or on a set of experimentally recorded ICP spectra,
but under some concrete conditions of operation of the source.
TPe basic problems arising in realization of this approach, besides difficulties con-

626

nected with computerization of the setup, have a physical character:

either problems common for physics, connected with the insufficiency of knowledge of the probabilities of radiative transitions, the rate constants of elementary processes, etc., the solution of which
is stimulated by the needs of diverse branches of physics and its numerous applications, or
relating to the physics of ICP and consists of the establishment of the connection between
the intensity of the spectral lines and the parameters of the plasma:

h~ = hvi~A~ni,

( 1)

where h is Planck's constant,

~ i k , h i k a r e t h e f r e q u e n c y and p r o b a b i l i t y
of a transition
from the i-th excited level to the k-th, h i is the population of the i-th level, dependent
i n a c o m p l e x way on t h e p a r a m e t e r s o f t h e p l a s m a - t h e c o n c e n t r a t i o n
of atoms in the ground
s t a t e and t h e e l e c t r o n c o n c e n t r a t i o n
and t e m p e r a t u r e ,
etc.
The e s t a b l i s h m e n t
of the explicit
form of this dependence is connected
o f t h e ICP p a r a m e t e r s and w i t h i n v e s t i g a t i o n
of the mechanisms of excitation
in it.

with diagnostics
of the sample

Below we r e t u r n t o t h i s q u e s t i o n , b u t m e a n w h i l e n o t e , t h a t t h e f i r s t a t t e m p t t o c r e a t e
artificial
s p e c t r a i n an a r g o n ICP was u n d e r t a k e n i n [ 3 0 ] . I n t h i s work t h e o r e t i c a l l y
and
experimentally
obtained spectra of a single-element
s o l u t i o n o f i r o n and a m u l t i e l e m e n t
solution of silver in a complex geochemical mixture were compared.
The i n t e n s i t i e s
obtained
in the calculations
and m e a s u r e m e n t s d i f f e r by s e v e r a l (up t o f i v e ) t i m e s , w h i c h i s e v i d e n t l y
due t o e r r o r i n t h e v a l u e o f t h e t r a n s i t i o n
probabilities
u s e d and t o t h e s i m p l i f i e d
(based
on l o c a l t h e r m o d y n a m i c e q u i l i b r i u m - LTE) d e s c r i p t i o n
of the populations of the levels.
The
r e s u l t s o f t h e work a g a i n show t h e n e e d f o r a d e q u a t e d e s c r i p t i o n
of the plasma.
P h y s i c a l P a r a m e t e r s o f ICP.
E m i s s i o n s p e c t r a l a n a l y s i s i s b a s e d on a c o m p a r i s o n o f t h e
spectral
line intensities
o f t h e a n a l y z e d e l e m e n t , c o n t a i n e d i n t h e a n a l y z e d s a m p l e and i n
the standard sample with a previously given content of the determined element.
In this case
the Lomakin-Shaube equation is used [31], connecting the intensity
of the studied spectral
line with the concentration
o f t h e a t o m s o f t h e e l e m e n t by t h e r e l a t i o n

I=ac~,

(2)

where a and p are constants dependent on the conditions of excitation of the analyzed element, determined empirically in each spectroanalytical experiment on the basis of the use
of standard samples.
The use of relation (2) allows us to formalize the procedure of analysis, optimizing it for one concrete source of excitation used in analysis.
However, the above-indicated causes make the use in working with ICP of an expression
of the type of Eq. (i) attractive, which in turn requires knowing the parameters of the
plasma.
In the analytical zone an induction plasma is a variety of "flow" afterglow, i.e., a
decaying plasma, which exists after exiting from the discharge gap. The fact that the ICP
exists at atmospheric pressure and high (i014-i01s) cm -a concentrations of charged particles
means a high rate of relaxation processes in it, in particular, the time of Maxwellization
of the particles in establishment of a single temperature for the atoms and electrons does
not exceed 10 -7 sec, while the characteristic times of transport of the plasma from the active zone to the analytical are not less than 10 -4 sec. This means that those nonequilibrium features (breakoff of the electron temperature T e from the temperature of the atoms
T a and the consequences connected with it) which occur in the active zone, must be absent in
the analytical zone, and the plasma in it may be described using LTE.
In this case the connection between the population of the excited levels is given by the Boltzmann formula

Ill

IZ;gi exp [-- (Ei - - Ej)/kT],

g]

while the connection between the concentrations

formula

u~'

(n+)

n:
where n~

n~

are the concentrations

n~ are the concentrations

of charged and neutral particles by the Saha

g~G+ ( 2an@T )3/2

6~

~-~

exp ( - - E+/kT),

of atoms in the i-th and j-th excited states; n~,

of electrons,

(3)

(4)
(n+) ~

ions, and atoms; the circle above the concentration

627

symbol means that they correspond to LTE; gi, gj are the statistical weights of the i-th and
j-th levels; ge = 2, G G a are the statistica ! sums of the electron, atom, and ion; E i, Ej
are the excitation energies of the i,th and j-th levels; E is the ionization energy of the
atom; k is Boltzmann's constant; m e is the mass of the electron.
These two equations along with the condition of quasineutrality of the plasma n e = En +
and the basic kinetic equation p = kT(Zin ~ + n e + Eini+) allow us to completely describe the
plasma, if one of the parameters n e or T is known
It would seem that an ICP must be in LTE. However, for a number of reasons, the principal of which are, first, the presence of a central channel, in which the aerosol with the
sample enters, and second, the output of radiation, deviations from LTE may exist in it.
Physically this means, in particular, that the temperatures (or n e) determined experimentally
using Eqs. (3) and (4) are not equal.
The temperature obtained from Eq. (3) is called the
excitation temperature Tex, and that from Eq. (4) the ionization temperature T i. Besides, it
may turn out that different groups of levels have different Tex and the T i obtained by different procedures do not coincide.
Thus, the question of whether the representation of LTE
may be used in description of an ICP or whether another approach is required is answered by
investigations of the physical parameters of the plasma.
Results of Diagnostics of ICP.
In ICP Tex, Ti, Te, Ta, the electron concentration n e
and concentration of metastable argon atoms n n were measured.
The results of these investigations, performed up to 1985, are given in [32]; here we discuss works published in recent
years.
We will talk about the analytical zone of an argon ICP with generator frequency 27
MHz, power (1.0-1.5) kW operating with a Fassel burner.
The excitation temperature was determined from Boltzmann plots, constructed using the
line intensities of different elements, in particular Fe [33-36].
In this case Tex increases
with an increase in the excitation energy of the levels and as a function of the spatial coordinates comprises (4500-7000 K); the error in determination of Tex comprises 20-30% and is
due to the error in Aik. All the distributions obtained on side recording of the line intensities are Abelized to radial.
The ionization temperature T i was determined from the ratio of the intensities of the
ionic and atomic lines in the assumption of LTE, and also from the independently obtained
electron concentration [33-38] not connected with the assumption of LTE. The spatial distributions obtained here Ti(r , h) lie within the limits (6000-8500) K.
The electron temperature T e was determined from the ratio of the intensities of lines
corresponding to transition from a highly excited level to the intensity of the continuum
in the assumption of equlibrium of these levels with the continuum [39].
In this case
Te(r, h) of 7000-9000 K were obtained.
The temperature of the atoms T a was determined from the Doppler widths of the contours
of the emission lines of different elements at different heights, but without Abelization
[40-42].
In this case T a ~ (4000-8000) K. In [43] results are given of an interferometric
study of the plasma burner.
Figure 2 gives the interference pattern of the burner and the
results of its processing.
Such investigations allow visualizing the distribution of the
gas fluxes in the plasma and by that selecting burners, and also fixing the temperature
fields in the peripheral zone of the burner.
The electron concentration n e was determined basically from the Stark broadening of the
H~ line [33, 37-38, 45] and in this case the error of the determination was 2-10%.
Despite the high accuracy, this method is rather cumbersome, and therefore in a number
of works n e was determined from the recombination continuum [41, 44] with an error of 20% or
from Eq. (4) with T = T i with an error of ~25-30%.
In [44] a comparison of these three
methods was performed, and in this case it turned out that the discrepancy in absolute values
of n e does not exceed 50%, while the behavior of the spatial distribution may differ qualitatively.
The latter may be connected with the different spatial distribution of the atoms
of the sample and the plasma-forming gas.
The absolute values of ne(r, h) comprise 0.84.0"10 Is cm -3, and for those determined from the Saha formula in the assumption of LTE with
T = Tex, n e ~ (0.1-1.0)'10 -14 cm -3. Figure 3 gives examples of the spatial distribution of
n e obtained by different methods.
The concentration of metastable argon atoms obtained in [45] comprises nm(r , h) ~ (0.88.0).i0

628

zz cm- a

Fig. 2. Interferogram of burner of the

working zone of an ICP [43] (a) and distribution of the temperature of argon
atoms over the cross section of the burner
of the source, obtained as a result of
processing the interferogram at the height
of observation (b): i0 (i) and 1 mm (2),
generator power 1.0 kW, basic flux 15
liters/min, transporting flux 0 liter/min.
The results of diagnostics of ICP showed that Tex increases with an increase in the
excitation energy; T i > Tex ; Tex ~ Ta; T e ~ T i. All this indicates deviations from LTE and
shows that to establish the connection between the parameters of the plasma and the populations of the levels, an analysis of elementary processes in ICP and the composition and solution of the balance equations are necessary.
In this case we note that for estimates of the intensities and spectral superpositions
the LTE representation may be used by choosing the parameter most accessible to measurements
- Ti, Tex, ne, but necessarily by obtaining its spatial distribution.
Elementary Process in ICP.
In the first works on modeling of ICP (see [32]) it seemed
that allowing for some kind of single process, for example Penning ionization or trapping of
resonance radiation could explain the observed deviations from LTE.
Later this tendency was
confirmed by subsequent works [39, 46-48], the number of processes accounted for by one or
another method increases, but the desired result - a correct description of emission of the
plasma by an expression of the type of Eq. (i) - has so far not been achieved.
In composition of the balance equations for excited atoms and ions, the electron concentration, and their temperatures, it is necessary to select those from a huge number of
processes which may occur in a plasma, whose rates under the given conditions (n e ~ i0 Is
cm -3, T ~ 8000 K) will prevail.

629

ne

FIB; I/]

10/~cm-3

cm-

d ~d

t
2_

i~ i .

"'~20
2

r, =

r,~

Fig. 3. Spatial distribution of electron concentration in an

ICP burner [144]: a) determination from the contour of the
~I line; r distance from burner axis, h height above inductor;
radial distribution of n e at the height 15 mm above the
inductor (the burner section) obtained from the contour of
the H~ line (i) from the Saha equation (2) and from the recombination continuum (3). The generator power was 1.2 kW,
the basic, auxiliary and transporting fluxes 12.1 and 0.5
liter/min respectively.
An analysis of the processes leading to excitation of atoms and ions of the sample, and
also modeling of the analytical zone were performed in [32, 39, 46-48]. We limit the examination to setting forth the basic conclusions obtained in these works.
The nonequilibrium character of the ICP burner is due to the output of radiation from
the plasma, which leads, for example, to an unequal weight of the process of nonresonance
charge transfer from the atoms of the sample to argon ions [48], and also to ambipolar diffusion of charged particles into the channel with the aerosol, as a result of which the
electron concentration in the central channel turns out to be overstated.
The basic mechanism of excitation of atoms and ions in an ICP is collision with electrons. Along with excitation of ions by a direct electron impact in the analytical zone
nonresonance charge transfer processes (NCT) may comprise a considerable fraction of the
excitation. When using argon as the plasma-forming gas, ionic levels can be directly excited as
a result of NCT to the argon ions. The excitation energies lie in the range 13.7-16.9 eV.
An analysis of the periodic table shows that in this interval fall the first excited levels of the ions: BiII, CdII, CoII, CuII, GeII, HfII, HgII, NiII, OsII, PbII, PtII,
PdII, ReII, RhII, SnII, WII, and ZnII. For Bi and Sn the corresponding transitions lie in
the VUV spectral region, and for the rest in the UV, the most sensitive analytical lines of
these elements from the tables given in [25, 27] corresponding to them. For levels whose
population may occur directly in the PI process at excited argon atoms, the energy interval
lies within 9.5-12.8 eV. In this interval fall the first excited levels of the ions: AIII,
CaII, CeII, CrII, DyII, ErII, EuII, GaII, GdII, LaII, LuII, MgII, MnII, NbII, ScII, SmII,
TaII, ThII, TIII, TmII, VII, YII, YbII, and ZrII, transitions from which lie in the 200-350
nm range (an exception is TIII at 190.864 nm).
For a number of elements (FeII, MoII, SiII, BeII) the first excited levels lie in an
intermediate interval (12.8-13.7 eV) and may be populated as a result of nonradiative transitions from higher-lying levels (formed on NCT) on collisions with electrons.
Introduction of Sample into Analytical Zone of ICP. In distinction from traditional
electric discharge sources of excitation of spectra used in emission spectral analysis, the
ICP source requires for its use a special system of sample supply. In this case the quantity
of the sample and the tempo of its introduction into the analytical zone of the burner is
dictated by the need to completely vaporize and atomize it during the time of passage of the
analyzed substance through the active zone of the discharge. A review of the presently existing approaches to an explanation of the physical processes determining entry of the investigated substance into the ICP burner is given in [49, 50]. In the case of the use of
an SES-ICPlsetu p for analysis of liquid samples the principal component becomes the quantity
of aerosol created by the dispersion system. It should, however, be noted that in questions
of the theory of formation of the aerosols from the moment of publication of the work of
Nakayama Tanasava, given in the work of L'vov [51], no substantially new !ideas have appeared.
To connect the quality of the aerosol with the analytical possibilities of the source it is

630

useful to have some characteristics of the dispersion system. The most widely used of them
is its efficiency - the ratio of the quantity of the analyzed substance at the input of the
injector of the burner to the total quantity of substance entering into the dispersive channel (the atomizer, atomizer chamber, injector) [49]. However, a much more important characteristic is the mass of substance W [50] entering the plasma per unit time. It is related
directly to the analytical signal
W-

~QC

100
where Q is the consumption of sample; C is the concentration of analyte; ~ is the efficiency.
Since W can be measured by an independent method; the system of sample supply is more conveniently characterized specifically by this value [50].
The aerosol with particles of different sizes enters the plasma. Along the way to the
zone of observation in the plasma only particles with sizes less than some definite size,
connected with the dwell time of these particles in the plasma from the instant of their
entry into it to their reaching the analytical zone, and also with the electric characteristics of the discharge, are dried and atomized. Specifically these particles lead to the
appearance of the analytical signal. The principal requirements envisioned on the entire
system of introduction of a liquid sample are the acquisition of a finely disperse aerosol
of the solution of the investigated substance. From the literature data [49-53] it is known
that in this case the diameter of the drops must be no more than i0 Dm. In [50] proceeding
from estimates made of the dwell time of the particles in the plasma, it was shown that the
value of the analytical signal and the signal/noise ratio basically correlate with the particle size. This also relates to the case of analysis of solutions, and to analysis of solid
samples without their preliminary solution. For typical conditions of performing analysis
using a Fassel burner the value of the analytical signal (or signal/background ratio) correlates with the total number of particles with average diameter less than 8 ~m, the value
of the signal/noise ratio with the width of the size distribution of the particles (usually
the distribution function with respect to the average diameter is given). Thus, for example, entry into the plasma of drops of large size increases flicker noise. To optimize the
characteristics of the system of sample supply to the ICP it is necessary to have not only
a finely disperse aerosol, but also as far as possible particles homogenous in size. On
the other hand, investigations of ultrasound systems of dispersion of solutions showed that
an increase in the mass load of the plasma by the aerosol of the solution higher than a definite level does not give the required effect, especially in the presence of easily ionized
elements. Large gains in the signal/background ratio can not be obtained simply on account
of the introduction of a large quantity of the analyzed substance, especially without drying
(desolvation) of the aerosol, since loading by the solvent strongly cools the plasma. In
this case higher powers may be required and the spectra of the base may be displayed to a
large degree. Questions of optimization of the particle distributions of the aerosol with
respect to the size and the mass load of an induction high frequency discharge have not been
completely studied and in each concrete case require special examination [54]. For example,
in analysis of liquid samples using a generator of average power 1-2 kW the attainable mass
load comprises -0.5 mg/sec [54].
It should be noted that supply of the sample to the ICP is the basic cause affecting
the noise characteristics of analysis. Therefore improvement of the methods of introduction
of the analyzed substance to the analytical zone is an essential problem.
We will dwell on the most widely used methods of introduction of the sample.
Introduction of a Liquid Sample. The basic scheme of a typical system of sample supply
is given in Fig. 4. An important element of the apparatus is the atomizer.
In analytical
practice pneumatic and ultrasonic methods of dispersion are used. Ultrasound atomizers in
comparison with pneumatic permit obtaining an aerosol of the investigated liquid with more
uniform sizes of the particles and with a higher density. For this reason there is a basis
to propose that the use of ultrasound atomizers will permit achieving lower detection limits.
Experiments in a number of cases confirm this conclusion. A disadvantage of this method of
atomization in comparison with pneumatic is the large "memory" of the system of sample supply, since in this case it contains supplementary apparatus (for example, a system of desolvation and a peristaltic pump). In addition to the indicated advantage pulsations in the
sample supply due to the use of the peristaltic pump should be noted.

631

o
o

J~

Fig. 4. Traditional supply of liquid

sample to analytical zone: i) atomizer, 2) burner, 3) peristaltic pump,
4) sample, 5) chamber, 6) settling
basin.
b,

12
Fig. 5.

Pneumatic atomizer with concentric (a) and mutually

perpendicular (b) arrangement of channels.

All of the listed reasons are responsible for the wide practical use of pneumatic atomizers.
Figure 5a shows a pneumatic atomizer with a concentric arrangement of the channels of
supply of the solution and the gas carrier, used in many plasma spectrometers of different
foreign firms [49]. Atomizers of the given type have a substantial disadvantage - clogging
of the aperture of the capillary by particles of the sample in operation with large salt
concentrations. Different varieties of angular atomizers have been developed and made by
industry in which the axes of the channels are arranged mutually perpendicular [7, 55] (Fig.
5b).
A new principle of dispersion was proposed in [56, 57]. It is based on obtaining an
aerosol directly from the liquid (without preliminary fractionation of it into drops). The
basic idea of such an atomizer consists of the fact that an aerosol is obtained on blowing
of the solution flowing along an inclined plane or hemisphere with an aperture, above which
on account of surface tension a thin film i is formed and through which a stream of gas is
supplied (Fig. 6). The atomizer of such a type (Babbington atomizer) exceeds the usual
pneumatic atomizers and allows the use of solutions with a high content of salts (up to
30%). However, it requires a forced sample supply (for example, using a peristaltic pump)
which involves the disadvantages already mentioned.
Measurements of the size distribution function of the particles [56] show that the
Babbington atomizer produces particles not exceeding i0 pm in diameter (i.e., below the
threshold of passage of the atomization chamber), as a result of which 2-3 times more aerosol passes through the chamber than in the case of using a concentric atomizer.
Analytical experience of the Babbington atomizer is in favor of its use instead of traditional atomizers.

632

~2

Fig. 6. Babbington atomizer:

i) argon
flow, 2) analytical sample.

I Ar

to burne~r

Fig. 7. Sample supply in the case of analysis of microvolumes of liquid: i) depression with dosed microvolume of
solution, 2) doubly distilled water, 3) flexible fluoroplastic tube, 4) atomizer, 5) atomizer chamber.
In recent years attempts have been made at using atomizers with regeneration of the
aerosol [58]. This procedure permits achieving lower detection limits in the process of
analysis, but has a large memory in comparison with ordinary pneumatic methods of atomization.
A variety of Babbington atomizer is an atomizer where instead of a single aperture microslits of porous material are used. The efficiency of such a method of atomization approximates the efficiency of ultrasound atomization.
In the literature attempts are described to supply an aerosol formed by the vapors of
a solution passing through a heated capillary to an ICP plasma [59]. As a result a high
efficiency of sample supply is obtained, close to the ultrasound method, and it becomes
necessary to use desolvation, involving the disadvantages mentioned in description of ultrasound atomizers.
Special methods of sample supply are used in analysis of microsamples.
Investigations
of the possibility of analysis of microvolumes by ICP methods give good results in prelimiinary experiments, but these works are still in the initial stage and it is impossible to
draw final conclusions about their practical use [60].
Figure 7 clarifies the principles of operation of one such method.
In depressions on a
fluoroplastic glass dosed microvolumes (10-30 ~i) of the analyzed solutions and comparison solutions are placed using a microsyringe. A flexible tube, constantly lowered into
the glass with especially pure water, directly entering the atomizer, is sequentially conveyed into the depressions with the microvolume of solution. Immediately after sucking up
the solution the tube is lowered into the glass with especially pure water. Thus, the drop
of solution turns out to be included in a flow of water, but not dissolved in it, being protected from the water by bubbles of air. The proposed procedure of introduction of the sample guarantees independence of the rate of pulsed supply of the microvolumes of solution to
the plasma of the viscosity of the solutions, since this rate is determined practically by
the rate of entry into the atomizer and into the plasma of pure water.
An original method of sample supply was proposed in [61]. Figure 8 explains the principles of its operation. A powder microsample is placed near the burner. The method is
based on shooting the analyzed powder by a pulse communicated to it by laser radiation. For
now this method has not received sufficient development, but preliminary analytical tests
give good results.
633

00o
o ii.j/o

Fig. 8. Laser method of sample supply:

i) flexible light pipe, 2) powder microsample, 3) laser, 4) burner.
/

[////////////////////A

I I ,

Fig. 9.

Electric-discharge atomizer:
i) sample, 2) anode.

A special place among new methods of sample supply is occupied by a method based on introduction of volatile hydrides into the ICP burner [62]. The method is suitable for analysis for the content of the following elements:
lead, tin, selenium, arsenic, antimony, bismuth, and tellurium. This method has lower (by an order) detection limits in comparison
with traditional methods. The majority of contemporary foreign ICP apparatus are furnished
with this comparatively simple capability, the only disadvantage of which is its suitability
for a limited number of elements.
Introduction of a Solid Sample. For now there are no fully developed methods of introduction of a solid sample. Nonetheless the prerequisites for use of such a method of sample
introduction are fully grounded. The most widely used method of analysis of a solid sample
is the use of electrothermal vaporizer (ETV) [62]. Optimum for ICP from the viewpoint of
Zil'bershtein et al. [63] are electrothermal vaporizers with a graphite rod. In that work
it was shown that in comparison with introduction of solutions the gain in the detection
limits may be ~120 times. The most promising use of ETV is for analysis of organic liquids.
Another part of the method is based on preliminary dispersion of a solid sample using
arc and spark discharges, laser radiation with subsequent introduction of the forming particles of the sample into the ICP by the flux of working gas [63]. Figure 9 gives an example
of such a method. This method has been tested on platinum alloys, bronzes, and nickel-based
alloys. Better reproducibility of the results of analysis is obtained in comparison with
other SES. From the most recent literature data the most promising sources for two-step
methods of analysis with excitation in SES are spark sources. However, this does not free
the methods themselves from their inherent disadvantages - the two-step nature, complexity
in obtaining results in practice, and insufficiently low detection limits (10-2-10-4%) as a
result of the small mass of the analyzed substance selected and entering the substance and
the insufficient reproducibility of this quantity, and also the problem of memory.
There are works in which methods of direct spectral analysis of a solid sample are examined, based on direct introduction of the sample into the plasma burner. However, these
works have a research character and have not yet received wide analytical application [61].
Introduction of a Sample in the Form of Suspensions. One of the least developed methods of sample supply to ICP is based on the use of suspensions [62]. Suspensions are prepared based on xylene or doubly distilled water. The technique of introduction of the sample into the analytical zone of the discharge in this case consists in the fact that the
suspension is subjected to the action of ultrasound "stirrers" and further is supplied by
one of the methods already!described above. Investigations of this method of sample intro-

634

[rel

-r--

/ '!

Jso

z>0

z,

Fig. i0. Spectrum of argon plasma at different heights of

the burner:
near the inductor (a) and on the periphery of
the burner (b).
duction showed that they are most suitable for analysis of food products, coal, soil, and
leaves.
In [64] introduction of a sample in the form ofja suspension is used for analysis
of zeolites for the content of silicon, potassium, and sodium. Besides the fact that the examined method broadens the possibilities for analysis of substances, it has rather weighty
prerequisites for effective use in calibration of instruments for emission analysis using
water solutions.
Spectral Apparatus for an ICP Source.
The physical parameters realized in the analytical zone of the source induce specific requirements on the spectral instrument used in
spectral analysis with an SES-ICP. As was said above the spectral composition of the radiation of the source includes the spectral lines of atoms and ions of elements present in its
analytical zone and excited both by electron impact, and as a result of other processes, for
example, nonresonance charge transfer.
Analysis of the spectra radiated by the analytical
zone of an ICP shows that along with the atomic lines in it, extended molecular spectra of
hydroxyl, diatomic nitrogen molecules, and oxygen, rather complex in structure are present,
the appearance of which is due to the specifics of sample supply.
Figure i0 gives the shape
of the ICP spectrum at different distances from the inductor.
The molecular fragments of
the spectrum are most intense in the peripheral parts of the burner of the source.
In the
entire range of wavelengths, most important from the viewpoint of analytical applications,
the continuous recombination spectrum of argon is observed.
The high values of the temperature and concentration of charged and neutral particles in the plasma of the source induce
broadening of the observed spectral lines on account of Doppler, Lorentz, and Stark mechanisms.
The requirements on resolution of the spectral instrument used with ICP may be formulated in correspondence with the minimum values of the spectral line widths observed in an
ICP source.
Let us perform a brief analysis of the shape of the spectral line contours and their
half-widths for various atoms under ICP conditions.
The width of the Doppler contour can be
estimated

A~D=7.17.10-~I///-T--~-,
where X is the wavelength in cm, T is the temperature of the gas in K; ~ is the atomic weight
of the element.
From the formula it follows that the half width of the spectral lines of atoms with
mass ~ ~ 40 in the 250 nm region at the temperature 6000 K has the value AX D ~ 0.002 nm,
while in the 500 nm region it is 0.004 nm. The width of the Lorentz contour under the same
conditions estimated from the formula [65]

635

AhL=

6'6"105 ~2p ~2
133 ~ - - ~ ^ '

where p is the pressure in Pa; o is the effective cross section for collisions in cm 2, equal to
0.0005 and 0.001 nm respectively. As seen from the estimate the width of the Lorentz contour is less than the Doppler, but specifically it determines the broadening of the contour
in the wings of the spectral lines. Collisions lead to broadening of the spectral lines,
also described by a Lorentz contour. The widths of the spectral lines undergoing Stark
broadening on account of the high density of charged particles reach considerable values.
The Stark broadening of different elements in absolute value may differ by several orders,
in some cases it may give widths of the lines exceeding the Doppler contour by 100 times,
while in other cases the Stark broadening may be less than the Doppler. For example, the
Doppler half width of the H~ hydrogen line under ICP conditions ~10 -2 nm, the Stark broadening for an electron concentration ~1015 cm -3 reaches the value ~0.1 nm. This circumstance
is used in determination of the electron concentration - broadening of the spectral lines in
this case is determined only by the Stark mechanism.
In ICP broadened spectral lines may
be observed, radiated as a result of dielectron recombination (a process, inverse to autoionization). Figure ii gives the contours of the spectral lines observed in ICP [66].
The given examples of possible widths of broadening of the spectral lines and the
abundance of processes occurring in different zones of the burner give a representation of
the complexity of the spectrum of the source and of the diversity of the processes determining the structure of the spectral lines. The high density of the lines in the ICP spectrum
and the need to separate them at the output of the spectral instrument make definite demands
on the spectral instrument used with ICP. An analysis of the spectral apparatus used in
setups with ICP [67] shows that in worldwide practice at present polychromators and monochromators with inverse linear dispersion 0.2-0.6 nm/mm (in the region 200-600 nm) are used,
and in this case schemes of polychromators with concave diffraction gratings, monochromators
constructed according to the Cherni-Turner scheme, and instruments with crossed dispersion
are used. The parameters of the spectral instruments [67] used in analysis are given in
Table i; they satisfy the requirements envisioned on spectroanalytical setups for mass spectroanalytical setups for mass spectral analysis.
However, it should be noted that for solution of the majority of spectroanalytical
problems an increase in the resolving power of the spectral instrument above the value which
is necessary for resolution of the Doppler contour of the analyzed element is not required.
In the majority of practically important cases the Doppler broadening always will determine
the minimum width of the spectral lines. In the case of superimposed contours to guarantee
resolution of lines in correspondence with the Rayleigh criterion the minimum resolved interval must be approximately equal to the width of the line. This means that use of a spectral
instrument with resolving power 5(2-3)-105 is not useful. Table 1 gives the parameters of
TABLE i. Characteristics of Spectral Instruments Suitable
for Use with a Source Based on an Inductively Coupled
Plasma
Instruments of
Quantometers subsequent
analysis

Parameters

DFS-44 DFS-5i I JY-?0

Spectral range,
run
Inverse linear
dispersion, nm/~

!2, )--900 180--700

190--550

175--340

175--800

175--500

0,55

0,4

0,6
0,3
0,2

38-,64

0,52--

0,27
0,36

0,4

1,04

Relative aperture

1:35

:15

1:15

1:30

1:20

Focal length, ~m

2650

g07

1500

1000

500

640

4O
60

24

64

1300

1120

550

235

Number of channels
Weight, kg

636

JY-24

520

100

90

1:8

/!
J

f23

22f

221 220

'.1

219 A~r~

Fig. ii. Spectrograms of autoionization lines Zn 293.7 nm

(4p 2 3P2-4s4p'P ~ transition) (a) and Cd 221.1 nm (5p 2 3P 25s5p3P~) (b). The power of the generator is 1.2 kW, basic
flux 15 liters/min, transporting flux 0.7 liter/min, height
of observation 15 mm above the inductor.
the instruments used in contemporary spectroanalytical practice by foreign firms, and Soviet
instruments.
Practical Use of SES-ICP. Abroad spectral analysis with SES-ICP already from the beginning of the 1970's has been rather widely used in different fields of the metallurgical
industry. This method embraces practically the whole field of materials of ferrous metallurgy - ores and slags [68, 69], different types of steels and alloys [70-72].
As shown above [i, 5, 7] one of the basic advantages of the use of emission apparatus
with an SES-ICP is the possibility of simultaneous multielement determination of the contents of both the basic components, and individual elements at the level of low and trace
contents.
Questions of the use of the method for analytical control of the materials of ferrous
metallurgy [73] have been examined in detail. The use of multielement synthetic water solutions as calibration standards on performance of analysis by the ICP-ESA method creates the
possibility of successful application of the latter for independent control of standard samples and local standard samples (LSS). The authors of this review used a JI-38P
setup with an SES-ICP for participation in interlaboratory spectroanalytic measurements on
attestation of standard samples of instrumental steel [73]. The basic difficulties in analysis of materials of the metallurgical industry arise due to the complexity of the spectra of
the investigated materials, so that the use of instruments with high resolving power does
not always completely provide the possibility of eliminating spectral superposition of the
lines of the basic and other components on the most sensitive lines of the determined elements and excluding the background from the matrix elements. Recently a number of works
have appeared on the use for purposes of analytical control of the materials of the metallurgical industry of automated ICP quantometers with preliminary spark atomization of the
sample, which does not require putting it into solution before the beginning of analysis
and increases the speed of the method [74].
No less important and possibly more promising is the possibility of the use of the ICPESA methods for analysis of different lubricating oils [75]. The firm Zhoben-Ivon in 1981
proposed the use of an ICP quantometer JI-48P for analysis of oils of aviation engines [76].
At present the firm Baird produces a compact 15 channel MOA oils analyzer with an SES-ICP.

637

In a large number of cases the samples (liquid oils) may be directly dispersed in the plasma
of the source and analysis is successfully performed also in calibration of setups using
multielement synthetic water solutions. The basic difficulty in performing the analysis of
the processed oils is the presence in the samples of suspended metal particles. However, in
contemporary instruments ultrasound setups are used for mixing of samples and preservation
of their homogeneity. As regards atomizers, for these purposes atomizers of the Babbington
type or, as in instruments of the Zhoben-Ivon Firm, concentric pneumatic with an increase in
the diameter of the capillaries for sample supply can be successfully used. In [77] results
are given of automatic express analysis of oils in determinations at the level of large,
small, and trace contents of elements on apparatus with SES-ICP.
Let us dwell briefly on the use of ICP-ESA methods in the chemical industry. In this
case the use of such methods for control of the composition of different reagents and principally highly automated systems for direct analytical control of technological solutions of
the chemical industry is possible. One of the recent publications [78] is devoted to a development of the firm Baird of a system for direct control of the content of elements in industrial technological streams, based on the use of a spectrometer with an inductively
coupled plasma.
A rapidly developing direction of ICP-ESA is its use for purposes of analysis of especially pure substances. Although up to the present time the method has been inferior to
the arc in detection limits due to the smaller concentration factor [79] in the development
of well optimized methods of analysis of microvolumes on setups with an SES-ICP [80, 81] and
due to the multielement character and speed it may become one of the reliable and promising
methods of analytical control of the composition of especially pure substances.
One of the earliest uses of the ICP-ESA method is analysis of biological and medical objects. Already in [82] detailed investigations are given in the field of optimization of the
conditions of analysis and preparation of samples in determination of the contents of microelements in blood serum, whole blood, various tissues, and other medicobiological samples on
SES-ICP!apparatus. Kartasheva and Startsev [83] also performed methodological developments
on analysis of blood serum and average norms of content of five elements were obtained in it:
Ca, Mg, Fe, Cu, Zn (for a definite adult group of people) in calibration of the instrument
using a series of multielement synthetic water solutions. Determination of these elements
was also performed in [84] in an analogous way.
A simple method of analysis of microvolumes of liquid samples has been developed practically free from matrix effects and permitted performing an analysis, for example, of blood
fractions practically without preliminary sample preparation (without solution) [85]. At
the present time many medical diagnostic laboratories abroad are equipped with automated
high-productivity ICP apparatus for express analysis of medical-biological samples for the
content in them of microelements at the level of large, average, small, and trace contents.
There continue to appear an ever larger number of works with a constantly broadening class
of biological objects, successfully subjected to analysis on apparatus with SES-ICP [86].
Practically simultaneously with this field a direction on application of the ICP-ESA
method in geology and geochemistry has begun to be developed [87]. In this case, due to the
need to analyze a sample of unknown variable composition, substantial difficulties arise in
preparation of standard samples. The previously listed advantages of an SES-ICP to a considerable degree permit avoiding these difficulties and using multielement synthetic aqueous
standards for calibration of the analytical setups. The basic aspects of the use of ICP in
this field are reflected in [73, 62].
Emission spectral analysis methods have been fully successfully applied for purposes of
ecological control. Recently in this direction substantial progress has been noted due to
their guarantee bot h by computing technique, and by new sources of excitation of spectra,
for example SES-ICP. i
The use of SES-ICPiguarantees above all simultaneous multielement analysis, which
broadens the region of investigated elements and permits, thus, excluding the possibility
of admitting unexpected excursions of the concentrations of unusual contaminates. In [62]
in rather great detail the prospects of the use of the ICP method for analysis of the objects of the environments are given - natural and effluent waters, air, domestic, transport,
and industrial dusts, different biological objects for the content of toxic and other microelements, including at the level of trace contents. Abroad SED-ICP set ups begin to be used

638

for control of the composition of the environment already in the 1970's, i.e., from the beginning of intense industrial production of these apparatus.
Already since 1979 in the USA
geological control laboratories perform routine express analysis of natural waters in the
territory of four states using SES-ICP spectrometers [88].
A procedure has been developed for determination of 17 elements.
In the process of
performing analyses interlaboratory comparison of apparatus with each other and results with
results obtained by other methods occur.
In [88] results are given of serial interlaboratory comparison.
Analogously in the USA control over maintenance of industrial hygiene for
steel-laying undertakings is performed.
Up to 1979 on participation of 400 participants the
necessary procedures were created and 172 ICP quantometers were introduced into use [89]. The
firm ARL already in 1978 proposed an instrument intended for analysis of waters [90].
In
[91] procedural developments on analysis of effluents on a JI-38P spectrometer of subsequent
action were performed.
The number of publications devoted to the use of ESA using iSES-ICP
for control of the environment continues to indirectly increase.
Publications on this theme
are in practically all analytical journals.
In many works recently are reflected questions
of the determination of trace contents of elements in natural and effluent waters and the
necessary preliminary preparation of samples convenient for ICP spectrometry for this method

[92-94].
In the past 4-5 years the direction of the use of an inductively coupled plasma as a
source of ions for mass spectrometers has strongly developed [94]. At present abroad there
are more than i00 mass spectrometers (MS) with ICP in use. Among them more than half are
used directly in control of production or in research subdepartments of industry [95].
Larger possibilities for this method have appeared in the field of analysis of geological
and biological samples.
To the low detection limits peculiar to mass spectrometry are added
the multielement character of analysis at a low level of matrix effects, characteristic for
setups with ICP [96]. As is well known the ICP-ESA method guarantees DL at the level i0 -710-9%, while ICP-MS provides the possibility of lowering DL by one to two orders.
These results are given in [97], where ICP-ESA and ICP-MS were used to study chemical reactions, occurring in the process of circulation of waters of geothermal sources, and a number of nonbasic and trace elements were determined in more than 200 samples.
A large number of works
have appeared on the use of the ICP-MS method for purposes of control of the content of the
environment.
These, for example, are works on analysis of aerosols from city trash burning
apparatus, determination by the ICP-MS method of iodine 129 in objects of the environment,
etc. [98, 99]. A no less promising direction in ICP-MS is the use of this method in clinical analysis [i00].
For example, in [i01] a determination was performed of the total content of lead and isotopic ratios of lead in whole blood by the ICP-MS method.
The detection
limits comprise here about 15 ~g/liter.
It should be noted however, that the choice between
ICP-MS and ICP-ESA methods depends on the concrete analytical problem.
Besides, for ICP-MS
special requirements are envisioned on the hf generator, the system of sample supply, and
the design of the inductor; other types of spectral effects in comparison with ICP-ESA, etc.,
are possible.
Thus an hf generator intended for ESA cannot be directly transferred to MS
[102].
Among other uses of ICP in analytical practice, atomic-fluorescent analysis should be
noted.
The use of an ICP source in atomic-fluorescent analysis was examined in [103] and
tested in [103, 104].
Figure 12 shows the scheme of the use of an ICP source in atomic
fluorescent analysis, including an ICP source used as sample atomizer, a tuned frequency
high-frequency laser, and also a receiving-recording apparatus.
As a source of excitation
of fluorescence a hollow cathode lamp or second ICP source may also be used.
The advantage
of the method is the considerably greater freedom from spectral noises in comparison with
AES, but the DL turn out to be the best case only of the same order [50, 104] (see Fig. 12).
The lowest DL are obtained using a laser, however a tunable laser for achieving the necessary parameters of analysis must have high stability in the frequency of tuning and power.
For now this condition remains difficult to fulfill and therefore wide use in analytical
practice of this variant of the method of atomic-fluorescent analysis has not been obtained.
Of the nonanalytical purposes of the use of ICP one should mention two directions:
formation and precipitation (application of coatings) of finely disperse powders (in this case
very powerful ICP discharges of the order of 30-50 kW are used [105, i06]~ and also the
study of processes occurring in a low-temperature plasma.
The SES-ICP have been used also recently in a variant of ESA/o~ MS as a detector in gas
or high-efficiency liquid chromatography [107].
639

Fig. 12. Scheme of use of ICP in atomic-fluorescent analysis: i) tunable laser, 2) ICP burner, 3) spectral instrument.
The first industrial samples of instruments with ICP for purposes of ESA appeared not
much more than ten years ago. During this period they received wide usage and showed their
advantages in practical emission spectral analysis, in such fields as metallurgy, chemistry,
the food industry, geology, medicine, biology, analysis of the environment, i.e., practically
in all fields where matter is analyzed in the liquid phase.
Definite prospects are also being examined in analysis of powder samples, which is extremely important in connection with the development of new branches of industry, such as
powder metallurgy and creation of composition materials.
Physical investigations of the
ICP source performed in recent years permitted deep understanding of its characteristics
and provided a basis to hope to both to broaden its application, and for its more effective
use for solution of practical problems of emission spectral analysis.
LITERATURE CITED
i.
2.
3.
4.
5.
6.
7.
8.
9.
i0.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.

25.
26.

640

S. Greenfield, H. D. McGeachin, and P. B. Smith, Talanta, !, No. i, 1 (1976).

R. H. Wend and V. A. Fassel, Anal. Chem., 37, No. 7, 920 (1965).
M. E . Britske, Yu. S. Sukach, and L. N. Filimonov, Zh. Prikl. Spektrosk., 25, No. i, 5
(1976).
P. W. J. M. Boumans and F. de Boer, Spectrochim. Acta, 31B, No. 6, 355 (1976).
Kh. I. Zil'bershtein, M. A. Kartasheva, G. N. Moshkovich, and G. P. Startsev, Zh. Prikl.
Spektrosk., 36, No. 6, 885 (1982).
S. S. Berman and J. W. McLaren, Appl. Spectrosc., 32, No. 4, 372 (1978).
P. W. J. M. Boumans and M. CI. Lux-Stejner, Spectrochim. Acta, 37B, No. 2, 97 (1982).
S. P. Terblanche, K. Visser, and P. B. Zeeman, Spectrochim. Acta, 36B, No. 4, 293
(1981).
L. Ebdon, M. R. Cave, and D. J. Mowthorpe, Anal. Chim. Acta, 115, No. 2, 179 (1980).
P. J. Humphries-Cuff and A. E. Watson, Spectrochim. Acta, 39B, No. 7, 915 (1984).
M. W. Blades and G. Horlick, Spectrochim. Acta, 36B, No. 9, 861 (1981).
M. Furuta and G. Horlick, Spectrochim. Acta, 36B, No. i, 53 (1981).
Prominent Lines in ICP-AES, ICP Inform. Newslett., ~, No. 8, 416 (1980).
J. D. Winfordner, R. Avni, T. I. Chester, et al., Spectrochim. Acta, 31B, No. i, i
(1976).
R. M. Belchamber and G. Horlick, Spectrochim. Acta, 37B, No. i, 71 (1982).
P. W. J. M. Boumans and McKenna, Spectrochim. Acta, 36B, No. ii, 1031 (1981).
P. W. J. M. Boumans, Theory of Spectrochemical Excitation, London (1966).
W. B. Barnett and V. Fassel, Spectrochim. Acta, 25B, No. 2, 139 (1970).
S. Greenfield, ICP Inf. Newslett., 6, No. 2, 199 (1978).
R. P. Z. Duursma, H. S. Smit, and F. J. M. J. Maessen, Anal. Chim. Acta, 133, No. 3,
393 (1981).
G. J. Schmidt and W. Slavin, Anal. Chem., 54, No. 14, 2491 (1982).
A. Lorber and Zvi. Goldbart, Anal. Chem., 56, No. i, 37 (1984).
S. A. Myers and D. H. Tracy, Spectrochim. Acta, 38B, No. 9, 1227 (1983).
Kh. I. Zil'bershtein, M. A. Kartasheva, and G. N. Moshkovich, Zh. Prikl. Spektrosk.,
44, No. 4, 550 (1986).
R. R. Wing, V. J. Peterson, and V. A. Fassel, Appl. Spectrosc., ~, No. 3, 206 (1979).
T. A. Anderson and M. L. Parson, Appl. Spectrosc., 38, No. 5, 625 (1984).

27.
28.
29.
30.
31.
32.

33.
34.
35.
36
37
38
39
40
41
42.

43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.

57.
58.
59.
60.

61.
62.
63.
64.
65.

P. W. J. M. Boumans, Line Coincidence Tables for ICP-AES.

In 2 Vols., 2nd ed., Oxford,
etc. (1984), p. 896.
A. R. Striganov and N. S. Sventitskii, Tables of Spectral Lines of Neutral and Ionized
Atoms [in Russian], Moscow (1966).
A. N. Zaidel', V. K. Prokof'ev, S. M. Raiskii, and E. Ya. Shreider, Tables of Spectral
Lines [in Russian], Moscow (1962).
L. Barton and M. W. Blades, Spectrochim. Acta, 4!B, No. i0, 1063 (1986); 43B, Nos.
415, 305 (1988).
S. L. Mandel'shtam, Introduction to Spectral Analysis [in Russian], Moscow (1946).
G. N. Gerasimov, M. A. Kartasheva, and S. Ya. Petrov, High-Frequency Inductively
Coupled Plasma Discharge in Emission Spectral Analysis [in Russian], Leningrad (1987),
pp. 12-41.
M. A. Kartasheva and S. Ya. Petrov, Third All-Union Conference on New Methods of Spectral Analysis: Abstracts of Reports [in Russian], Moscow (1977), p. 12.
M. W. Blades and B. L. Coughlin, Spectrochim. Acta, 40B, No. 4, 579 (1985).
Z. Walker and M. W. Blades, Spectrochim. Acta, IB, No. 8, 761 (1986).
N. Furuta, Spectrochim. Acta, 40B, No. 8, 1014 (1985).
B. L. Coughlin and M. N. Blades, Spectrochim. Acta., 39B, No. 12, 1583 (1984).
B. L. Coughlin and M. N. Blades, Spectrochim. Acta, 40B, No. 7, 987 (1985).
T. Hasegawa and H. Haragachi, Spectrochim. Acta, 40B, Nos. 10-12, 1505 (1985).
T. Hasegawa and H. Haragashi, Spectrochim. Acta, 40B, Nos. 1/2, 123 (1985).
L. M. Faires, B. A. Palmer, and J. W. Brandt, Spectrochim. Acta, 440B, Nos. 1/2, 135
(1985).
P. W. J. M. Boumans and J. Vrakking, Spectrochim. Acta, 41B, No. 12, 1235 (1986); 42B,
No. 6, 553 (1987); 42B, No. 8, 819 (1987); 43B, No. i, 69 (1988).
S. Yu. Dudnikov, Opt. Mekh. Promst, ii, i (1988).
P. E. Walters, W. H. Gunter, and P. B. Zeeman, Spectrochim. Acta, 41B, Nos. 1/2, 133
(1986).
L. P. H a r t , S p e c t r o c h i m . A c t a , 41B, No. 12, 1367 (1986).
T. Hasegawa and H. H a r a g a c h i , S p e c t r o c h i m . A c t a , 40B, No. 8, 1067 (1985).
G. D. Rayson and G. M. H i e f t j e , S p e c t r o c h i m . A c t a , 41 B, No. 7, 683 (1986).
S. Ya. P e t r o v , P h y s i c a l Aspects o f Atomic Emission A n a l y s i s [ i n R u s s i a n ] , V i l n i u s
41988), pp. 34-47.
E. G. Chudinov, Atomic-Emission Analysis with an Induction Plasma. Summaries of Science and Technology. VINITI, Ser. Anal. Khimiya, Vol. 2, Moscow (1990).
P. W. J. M. Boumans, Inductively Coupled Plasma Emission Spectroscopy, New York (1987).
B. V. L'vov, Atomic-Absorption Analysis [in Russian], Moscow (1986).
Diane Weauchemin, Anal. Chem., 59, No. 5, 778 (1987).
Ramon M. Barnes, Twent$-Sixth CSI, Abstracts, Vol. 4, Sofia (1989), p. 14.
J. M. J. Maessen, Spectrochim. Acta, 41___BB,Nos. 1/2, 135 (1986).
R. M. Barnes, ICP Inform. Newslett., 6, No. 9, 459 (1981).
R. Anatanavichus, P. Serapinas, P. Shimkus, and A. Urbas, High-Frequency Inductively
Coupled Plasma Discharge in Emission Spectral Analysis [in Russian], Leningrad (1987),
pp. 62-74.
USA Patent No. 3421692, Class 239/8. Published 1989.
P. A. Vieira, H. Z. Zhuang, Sh.-K. Chan, and A. Montazer, Appl. Spectrosc., 40, No. 8,
1141 (1986).
M. T. C. de Loos-Vollebregt, Rounzhoig Pens, and J. J. Tiggelman, Twenty-Sixth CSI,
Vol. 4, Sofia (1989), pp. 29-35.
Kh. I. Zil'bershtein, M. A. Kartasheva, G. N. Moshkovich, and G. P. Startsev, HighFrequency Inductively Coupled Plasma Discharge in Emission Spectral Analysis [in Russian], Leningrad (1987), pp. 94-114.
Method of Introduction of a Powder Sample into a Discharge on Setups with an Inductively Coupled Plasma: Inventor's Certificate No. 1,492,247 SSSR: MKI a G 0 1 N 21/73.
M. Thompson and D. N. Walsh, Handbook of Inductively Coupled Plasma Spectrometry,
Methuen Inc., New York (1983).
Kh. I. Zil'bershtein, M. A. Kartasheva, G. N. Moshkovich, et al., High-Frequency Inductively Coupled Plasma Discharge in Emission Spectral Analysis [in Russian], Leningrad
(1987), pp. 140-157.
J. R. Mackey and W. Y. Murphy, Zeolites, 5, No. 4, 233 (1985).
S. E. Frish, Optical Spectra of Atoms [in Russian], Moscow-Leningrad (1963).

641

66.
67.
68.
69.
70.
71.
72.

N. V. Afanas'eva, M. A. Kartasheva, and B. E. Krylov, Twentieth All-Union Congress on

Spectroscopy:
Abstracts of Reports [in Russian], Vol. i, Kiev (1988), p. 50.
V. B. Be!yanin , Analytical Instruments Based on an Inductively Coupled Plasma [in
Russian], Moscow (1986).
E. Yu. Panteleeva, N. I. Gul'ko, and V. M. Lur'e, Zavod. Lab., 47, No. ii, 33 (1981).
G. M. Russel and A. E. Watson, ICP Information Newslett., 6, No. i, 12 (1980).
J. Looke, Anal. Chim. Acta, 113, No. i, 9 (1980).
Kh. I. Zil'bershtein, M. A. Kartasheva, G. N. Moskovich, et al., Zh. Anal. Khim., 37,
No. 5, 794 (1982).
I. M. Dolgonyuk, N. N. Peikhvasser, E. T. Mikhailova, et al., Zavod. Lab., 54, Ii0

(1988).
73.
74.

V. P. Zamarev, O. D. Vernidub, and N. I. Gul'ko, High-Frequency Inductively Coupled

Discharge in Emission Spectral Analysis [in Russian], Leningrad (1987), pp. 158-172.
J. I. Marks, D. E. Ornwalt and R. E. Yungk, Spectrochim. Acta, 38B, Nos. 1/2, 107

(1983).
75.
76.
77.
78.
79.
80.
81.
82.
83.

84.
85.
86.

87.
88.
89.
90.
91.
92.
93.
94.
95.
96.

97.
98.
99.
i00.
i01.
102.
103.
104.
105.
106.
107.

642

M. P. Granchi, J. A. Biggerstaff, L. J. Hilliard, and P. Grey, Spectrochim. Acta, 42B,

Nos. 1/2, 169 (1987).
J. Houseauiand Y. Lang, Joben Yvon Instruments S. A., Fevrier (1989).
A. Decocq, J. J. Brocas, J. De Winlt, and C. Druon, Am. Lab. (Fairfield, Conn.), 18
(ii), 128, 130 (1986).
R. R. Comtois and F. Bulman, ICP Inf. Newslett., 14, No. 9, 569 (1989).
N. M. Kuz'min and V. V. Krasil'shchik, Zh. Anal. Khim., 43, No. 8, 1349 (1988).
Kh. I. Zil'bershtein, M. A. Kartasheva, and G. N. Moshkovich, Eleventh CANAS: Abstracts of Reports [in Russian], Moscow (1990), p. 221.
V. Z. Krasil'shchik, A. I. Sukhanovskaya, and M. S. Chupakhin, Vysokochist. Veshchestv.,
No. 4, 151 (1989).
R. L. Dalquist and P. Knoll, Appl. Spectrosc., 32, No. i, i0 (1978).
M. A. Kartasheva and G. P. Startsev, Second All-Union Conference on New Methods of
Spectral Analysis and Their Application:
Abstracts of Reports [in Russian], Irkutsk
(1981), p. 11.
P. Schramel and B. G. Klose, Fresenius Z. Anal. Chem., 307, 26 (1981).
Kh. I. Zil'bershtein, M. A. Kartasheva, and G. N. Moshkovich, Zh. Prikl. Spektrosk.,
64, No. 3, 359 (1986).
L. Starshinova, E. Sedykh, H. Wulfson, et al., ICP Inform Newslett., 14, No. 6, 494

(1989).
K. Govindarju and Gue Mevelle, Spectrochim. Acta, 38B, Nos. 11/12, 1447 (1983).
J. N. Barbarino, Appl. Spectrosc., 39, No. 3, 120 (1985).
R. Zimmerman, J a r e l l - A s h Plasma N e w s l e t t . , ~, No. 3, 6 (1979).
ARL Appl. Res. Lab. Report, No. 78001 (1978).
G. V. Varvanina and E. G. Chudinov, Zh. Anal. Khim., 41, No. 5, 798 (1986).
E. Devis, Spectrochim. Acta, 41B, No. ii, 1203 (1986).
R. Speer, P. Hoffman, and K. H. Lieser, Fresenius Z. Anal. Chem., 325, No. 6, 558
(1986).
J. Alan Gray, J. Atom. Anal. Spectrom., 1(6), 403 (1986).
D. Hausler, ICP Inform. Newslett., 14, No. 7, 426 (1988).
J. R. Dean, L. Ebdon, H. M. Crews, and R. C. Massers, J. Anal. Atom. Spectrom., ~, No.
2, 349 (1988).
D. L. M i l s , J. M. Cook, and M. T r a f f o r d , ICP Inform. N e w s l e t t . , 1__44,No. 7, 157 (1988).
G. A. Laing, D. E. Dobb, D. Cardens, et al., ICP Inform. Newslett. , 14, No. 9, 554
(1989).
R. M. Brown and A. Lister, ICP Inform. Newslett., 14, No. 9, 545 (1989).
D. L. Templton, A. Pavidy, and A. D. Bains, ICP Inform. Newslett., 1-4, No. 9, 529
(1989).
H. T. Delves and M. J. Cambel, J. Anal. Atom. Spectrom., 3, No. 2, 343 (1988).
J. M. Mermet, ICP Inform. Newslett., 14, No. 9, 536 (1989~.
M. A. Kosinski, H. Ushida and J. Winefordner, Talanta, 30, No. 5, 3939 (1983).
N. Omenetto and J. D. Winefordner, Induct. Coupl. Plasma Anal. Atom. Spectrom., New
York (1987), pp. 61-63.
M. Kagawa and M. Suzuki, ICP Inform. Newslett., i-4, No. 5, 272 (1988).
T. Husain and V. J. Ibberson, ICP Inform. Newslett., ii, No. 8, 533 (1986).
D. S. Buslu and J. R. Moody, ICP Inform. Newslett., 14, No. 9, 543 (1989).