OPTICAL EMISSION SPECTROSCOPY AS AN ANALYTICAL TOOL*

Edward L. DeKalb, Richard N . Kniseley, Velmer A. Fassel Institute for Atomic Research and Department o f Chemistry, Iowa State University, A mes, Iowa

Introduction
For many years the characteristic line spectra emitted by the elements in flames and arc, spark, or gaseous discharges have provided a relatively simple, convenient, and objective means for the detection and determination of trace impurities. Since no other analytical technique provides so much information with so little effort, these spectra are destined to find increasing application in trace or micro analyses. t T h e principles and practices of optical emission spectroscopy and its analytical applications have been adequately discussed in several books and chapters in treatise~,~. reviewslR2 2 on recent developments have and appeared a t regular intervals. We will, therefore, not concern ourselves with details of various standard operating procedures, techniques, and experimental facilities. Rather, we will focus our attention on special problems encountered in expanding the scope of application of these spectra to the quantitative determination of trace impurities a t ever decreasing concentration levels. Before considering these special problems, it is appropriate to note a few general characteristics of optical emission spectroscopic methods which directly affect their present and potential scope of application. These spectra are capable, under optimal excitation conditions, of detecting trace amounts of all the elements in solids, liquids, or gaseous samples. I n most instances, these detection limits are as low as a few parts per million, and, under ideal conditions, the limits may be as low as a few parts per billion. These detection limits can normally be obtained on samples weighing only a few milligrams with little or no prior chemical treatment. T h e advantages inherent in the latter are often not readily apparent, but it must be remembered that impurities in chemical reagents may contaminate the original sample to such an extent that the trace impurity content is completely masked. Also, the possibility that trace impurities may be lost during chemical processing is ever present.
*Contribution No. 1788. Work was performed in the Ames Laboratory of the U. S. Atomic Energy Commission. t I t is important t o draw a distinction between trace and micro analysis. In our frame of reference, trace analysis involves the determination of impurities . a t or below the part per million level, whereas micro analysis involves the analysis of very small or micro samples. Many optical emission spectrometric analytical techniques for trace analysis are directly applicable t o micro analysis as well, by simply making a few obvious changes in the analytical procedure.

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Unlike chemical analytical procedures which are usually less precise a t lower concentration levels, optical emission spectrometric methods tend to show a uniform precision over most of the applicable concentration range. In general, their precision is superior to chemical methods a t very low concentration levels, about equal a t concentration levels near one per cent, and inferior at higher concentration levels. This statement must, of course, be modified depending on the nature of the problem and the amount of sample available for analysis. Under ideal conditions, a precision of I 1-2 per cent of the amount present can be attained by optical emission procedures but values of i 5-10 per cent are more typical. With the exception of qualitative or semiquantitative analyses, a specific procedure or method must be devised for each analytical problem. Since optical emission methods are not absolute, they must be carefully standardized against synthetic or chemically analyzed standards. This calibration is usually dependent on both the general composition and the past history of the sample. Thus, the standards must be carefully selected or prepared to correspond as closely as possible, both chemically and physically, t o the samples t o be analyzed. When the sample type or composition changes significantly, restandardization or complete revision of a method may be necessary.

General Comments on Detection Limits

Unless restricted by the amount of sample available, emission spectrometric detection sensitivities are limited by the signal-to-noise or the lineto-background ratio. Were it not for this limitation, the analyst could obtain any desired sensitivity by simply integrating longer and longer exposures. When the level of radiant energy emitted by a trace element a t a particular wavelength cannot be distinguished from the noise or from the background radiation at that same wavelength, the limit of detection has been attained. Additional exposure or integration of the signals will be of no avail. Several authors' ' '' have proposed different criteria for defining spectral detection limits. Whatever criterion is used, the definition of detection limit is dependent upon which of the two basic methods of recording spectral line intensities is employed. When intensities are measured photoelectrically as in a scanning spectrometer with little or no integration by the associated electronic equipment, the signals are presented on an oscilloscope, oscillograph, or strip-chart recorder. With such a system, the fluctuations in the measured intensities necessarily set the lower limit which can be attained. These fluctuations are produced both by short period variations in light emission as well as electronic noise within the measuring system itself. Under these conditions, the most meaningful and convenient measure of the detection limit is the ratio of the line intensity to the fluctuations in the total background. The concentration of an element necessary to produce a line intensity equal to twice the standard deviation of the background intensity is commonly defined as the detection limit for that element.

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Long-term integration techniques can be used to average the noise and thereby improve the signal-to-noise ratio. I n the case of photoelectric detection and electronic integrating systems with unlimited scale expansion, the ultimate detection limit is still governed by the signal-to-noise ratio. Photographic plates also perform a long-term integration and consequently minimize t h e noise but lack t h e zero suppress and scale expansion features present in electronic readout systems. Thus, when this method of recording spectra is used, a convenient measure of the detection limit is the ratio of t h e line-plus-background to the background alone. The numerical value of this ratio a t the detection limit is governed by the ability of the readout system to accurately determine small signal differences. Values of 1.1 to 1.3 are most often used for this ratio. T o improve the detektion limits, the analyst must therefore strive to reduce the noise and the continuous background while increasing the net line intensity to its maximal value. The primary sources of background are: the black-body and other extraneous radiations in t h e source; scattered light in the spectrometer; and fogged plates or dark current in the detector. Noise originates primarily from: fluctuations in the excitation source; electronic noise in t h e readout system; and grain in the photographic plate or thermal noise in the detector. Methods of minimizing these sources of background and noise have been described in considerable detail by Mitteldorf.28Black-body radiation from incandescent electrodes may be effectively prevented from entering the spectrometer by focusing the arc or spark column on a n aperture located between the discharge and the entrance slit. This system should be so designed that the aperture blocks all the radiation from the incandescent electrodes while a t the same time allowing the transmitted radiation t o completely fill the optical aperture of the spectrometer. I n this way, the scattering of unwanted radiation inside the spectrometer is minimized as well. Further reduction in extraneous background radiation can be achieved by opening t h e spectrometer shutter only while the elements of interest are present in the analytical gap. This procedure, also known as the fractional or selective volatilization method, takes advantage of t h e differences in the rate of volatility, particularly in d. c. carbon arc excitation of chemical compounds and elements. A very substantial reduction in the recorded background level can thus be obtained, and in fact the lowest detection limits for some elements have been obtained by employing this p r o c e d ~ r e . ~ . ~ Time-resolution spectroscopic techniques may similarly be used to reject the high background pulses emitted a t the initial phases of each spark train.31 Thus, it has been possible to obtain greatly improved sensitivities while a t the same time retaining the superior precision of spark excitation. T h e use of a spectrometer with a narrow entrance slit, high dispersion and excellent resolution will minimize the effect of black-body radiation. As t h e dispersion is increased, the continuum intensity will be spread over a greater area, whereas the spectral line, being a n image of the slit will remain approxi-

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mately the same size. However, when the dispersion is increased to such an extent that the natural line width, rather than the entrance slit, governs the width of the spectral line at the focal curve, any further increase in dispersion will not improve the line to background ratio. Air a t one atmosphere of pressure is not necessarily the optimum environment in which to carry out spectral determinations. Much of the extraneous radiation originating in an analytical gap operated in air consists of emission from molecular species, such as cyanogen, and the so-called air lines. Changes in the nature of the supporting atmosphere and its pressure can niodify the environmental conditions in order to minimize these sources of background. Additional benefits are obtained when this is done. The rate of vaporization of material into a n analytical gap can be controlled by these changes in the supporting atmosphere. Also the line intensity for many elements are enhanced over the intensities observed in air.32 When spectra are recorded photographically, the background level has an additional significance because of the nature of the photographic process. For best sensitivity, it is usually beneficial to have enough background to supply the threshold exposure a t which the blackening of the image first becomes perceptible. For maximum sensitivity, this threshold exposure should be provided by the natural, but minimal background inherent in the emitting source, not by prefogging the plates. Since photographic emulsions have no scale expansion or zero suppression features found on many photoelectric detection systems, it is always essential to keep the overall background level as low as possible. Thermal and electronic noise in the detector and readout system can best be controlled by proper selection, operation, and maintenance of the entire electric system. Cooling of t h e detector is useful in providing an optimum signal-to-noise ratio when the noise level of the detector is a limiting factor. Integration techniques are useful for improving the signal-to-noise ratio when the noise is random and utilization of these techniques can often produce a factor of 10 improvement in detection limits. Optimum line intensity and a good overall signal level are advantageous in providing a high line-to-background ratio. Many conditions, including the instrumental factors and the sample vaporization and excitation system, can influence greatly the net line intensity. Modern commercially available spectrometers can be expected to provide the necessary dispersion and resolution, and are not easily modified or improved. The proper choice of t h e detector is important in maintaining a signal level compatible with the readout system. The detector should have its maximum response near the wavelengths of the lines to be measured and should have a minimum of noise and dark current (or fog). High resolution is of major importance in detecting a weak line which is adjacent to a stronger matrix line and is achieved by t h e use of narrow slits. If photographic readout is used, a photographic emulsion with high resolution and high contrast is very desirable.

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The most sensitive, interference-free spectral line should be chosen for the analysis. The type of excitation employed will influence the particular line chosen. For example, in a flame, the temperature is only sufficient to populate the low exicted Higher-temperature excitation sources, such as arc and spark discharges, are capable of exciting a well developed spectrum of most elements. I n general, however, the resonance lines of the neutral atom or the singly ionized atom exhibit maximum detection sensitivity. Many tables listing the most sensitive spectral lines have been published. One of the most recent and useful listing is the two-volume set published by t h e National Bureau of Standards.34

Vaporization and Excitation

The proper selection and control of the vaporization and excitation processes provide the analyst with the greatest opportunities of improving detection sensitivities. To obtain a spectrum the sample must first be volatilized and transported to the analytical gap, where dissociation of molecular species and excitation of the free atoms occurs. The objective of the volatilization and transportation steps are to place the maximum number of atoms of the elements to be determined into that part of t h e emitting source viewed by t h e spectrometer, and to keep them there until emission of characteristic radiation can occur. Any atom which does not traverse the effective portion of the source or which does not emit radiation while doing so, contributes nothing toward t h e detection of that element. I n most of the standard excitation procedures, both of these steps are performed by flames or by an electric arc or spark discharge struck between a pair of electrodes. However, source parameters which are optimal for excitation may be less than ideal for the volatilization process. Consequently, some degree of compromise is often unavoidable. Efforts to separate t h e two steps have included t h e use of double arcs3' small induction and t h e evaporation method developed by Mandelstam and Zaide1,38%39 which will be described presently. An examination of the spectrochemical literature reveals t h a t a limited number of excitation procedures have been utilized repeatedly when trace constituents are to be detected or determined. These procedures can be conveniently grouped into four classifications: arc and spark excitation and excitation of liquid and residue samples.

A rc Excitation
The d. c. arc has attained the reputation for being the most sensitive source for the excitation of spectral lines for most elements. However, this source often suffers from a lack of precision, an error of * 30 per cent of the amount present not being at all uncommon. The major portion of the current in this type of discharge is carried by the electrons and the impact of the accelerated electrons upon the anode heats the electrode surface to such high temperatures

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that a sample contained in the anode is rapidly converted into a vapor. A high density of emitting atoms in the analytical gap is thus produced, which in turn contributes to the observed superior sensitivities. The amount of sample consumed by d.c. arc excitation is usually greater than other excitation processes by a factor of 10 to 100. The poor precision of the d. c. arc can be traced to nonrandom fluctuations in the arc current and to the tendency of the discharge to localize itself a t one or only a few spots on the anode. Varying degrees of selective volatilization are thus obtained, with resulting fluctuations in line intensities. Adequate compensation for these fluctuations can often be achieved through the use of internal ~tandardization.~ The annoying tendency of arc discharges to localize themselves poses additional problems when metal self-electrodes are employed. Even high melting point metals will melt a t the localized spot, and lower melting point metal electrodes will collapse. I n addition, the molten globules are very reactive, often forming a nonconducting layer of oxide, causing the arc to be extinguished or to wander even more. I t is with particulate samples that the great sensitivities of d. c. arc excitation are usually achieved. This type of sample, typically a powdered oxide or other compound, but also including metal turnings, chips and powders, must be supported in a n electrode. Carbon or graphite rods are ordinarily used for this purpose because they are electrically conductive, readily obtained at high purity, easily machined or shaped, and do not melt but rather sublime slowly a t high temperatures. Carbon has a n ionization potential equal t o or greater than the elements commonly determined by emission spectroscopy. Therefore, carbon vapors in the arc will not depress the excitation characteristics of the arc below those required for most elements. The size and shape of the sample-supporting electrode and the counter electrode may play a significant role in the observed sensitivities. Over 100 different electrode designs are commercially available in this country, and the spectrochemical literature contains descriptions of hundreds more. The rate of volatilization, the opportunity for chemical reactions in t h e electrode cup, and the amount of wandering of the anode spot are among the many variables which may be controlled or at least influenced by electrode configuration. There are several major variations of the standard d. c. arc technique, one or more of which must be employed if maximum sensitivities are t o be obtained. They include: 1) the open arc with or without the use of buffers and selective volatilization; 2) the carrier distillation method; 3) the use of controlled atmospheres; 4) the cathode layer method. Each of these will be described in general terms, with references provided for those interested in more comprehensive treatments. Open Arc. An arc operating in air may be designated a n open arc, as opposed to one operated in an atmosphere other than air. Such an arc can be manipulated in several ways to enhance the lines of certain elements. The

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quantity of current flowing through t h e arc is of major importance in determining t h e amount and rate of volatilization. A low current may be optimal for easily vaporized materials, but completely unsuited for refractory compounds. Conversely, a high current will vaporize low boiling point materials so rapidly t h a t only a small percentage of the atoms are excited within t h e analytical gap. Increased amperages do not, however, have much effect on the temperature of the plasma nor on the excitation efficiency of the discharge. As the current is increased, the cross-sectional area of the plasma also increases, so t h a t t h e energy available for excitation in a given volume is maintained a t a fairly constant level. The fractiohal or selective volatilization method, in which the spectrometer shutter is opened only while elements of interest are in the analytical gap, was mentioned earlier as a means of reducing background. Since t h e exposure is made only while the impurities are volatilizing, the overall exposure level is reduced considerably so t h a t a larger sample size may be used. In addition, the reduction in intensity of matrix and some other impurity lines may free more sensitive lines from interferences, so that they become analytically useful. The fractional volatilization method has a degree of versatility which may be easily overlooked. A volatile matrix can often be converted into a much less volatile compound, or the impurity elements into more easily volatilized constituents, by the application of a little chemistry. T h e required reactions can sometimes be accomplished within the electrode cup during the arcing period. For example, tungsten and molydenum have very volatile oxides, but the addition of graphite powder to the sample charge results in the formation of refractory carbides, so that impurity elements can be easily distilled from a . ~ another instance, the addition of bits matrix of tungsten or m o l y d e n ~ m I n ~ of Teflon to a sample charge converted the oxides of some elements to more volatile f l ~ o r i d e s . ~ Spectroscopic buffers have long been used to modify arcing conditions. Elements with low ionization potentials, such as the alkalies and alkaline earths are most commonly employed. The buffer material, by reducing the effective excitation temperature of the arc, increases the population of neutral atoms and thus enhances spectral lines originating from such atoms. Also, interfering lines originating from ionized atoms may be minimized, thus making a more sensitive line analytically useful. Finally, buffers provide for a more steady and reproducible burning of the arc. Carrier Distillation. T h e carrier distillation method, first described by Scribner and Mullin in 1946,4Jcombines selective volatilization with use of a buffer into a very sensitive technique. A sample of about 100 mg. is blended with a carrier and loaded into a deeply cratered electrode, which is then subjected to d. c. arc heating and excitation. The volatile impurities distill away from the more refractory matrix, and are swept into the analytical gap with the aid of the carrier, which is ordinarily either gallium oxide or silver

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chloride. This method can provide a n enhancement of three orders of magnitude or more, particularly when the matrix element has a complex spectra of numerous interfering lines. Controlled Atmospheres. Some of the advantages of using an atmosphere other than air, including the reduction of background and the slower volatilization rates, were mentioned previously. Of equal importance is the higher energy distribution available in an argon or helium atmosphere. Mochalov and Raff, Vallee and coworker^,^^^^^ and Stoneli have shown t h a t if neutral atom lines are used for analytical purposes, excitation in argon or helium does not appear t o be beneficial except for reduction in background intensity. But if ion lines or neutral atom lines requiring high energies are employed, and especially if the constituent to be determined is relatively volatile, then excitation in a n argon atmosphere reaps three benefits: a ) prolongation of volatilization; b ) greater efficiency in populating the excited states; and c) lower background. Additionally, the excitation of spectra which cannot be excited in air, such as the halogens, sulfur, oxygen and nitrogen, may be readily accomplished in a n atmosphere of argon or helium. The atmosphere surrounding the analytical gap may be controlled by the use of devices ranging from a completely enclosed, evacuable arcing ~ h a m b e r , ~ to a simple tube blowing a stream of gas across the gap.49The Stallwood and similar devicesblow a sheath of gas up and around the gap, thus almost completely blocking the diffusion of air into the arc. Cathode Layer. All of the preceding d. c. arc methods utilize the anode for containing the sample. If the sample is placed in the cathode instead, and only light emitted very near the cathode is utilized, a n enhancement of certain lines is observed. This is the cathode layer method described by Strock and OtherS.~~4.h~ the enhancement is greatest for elements with low ionization Since potentials, it is thought that the enhancement mechanism involves an increased density of such atoms, resulting from the migration of positively charged ions to the vicinity of the cathode. Since the cathode is cooler than the anode, refractory samples may not be vaporized satisfactorily with this method of excitation. An additional limitation of cathode layer enrichment i s the small amount of sample which can be used. If the sample exceeds a few milligrams, ionization in the arc is depressed which in turn lessens the enrichment effect. Although the method provides excellent absolute sensitivities for many elements, conventional anode excitation is often superior when an unlimited sample size is available. Sustaining A . C. Arc. The self-sustaining a. c. arc excitation technique possesses characteristics very similar to the conventional d. c. arc except that the electrode polarity is constantly being reversed. Because of the high current flux, the electrodes remain hot enough for thermionic emission to maintain the arc without reignition by a high voltage pulse a t the beginning of each half cycle. There have been scattered reports that there is a gain in precision with little or no loss in sensitivity for this type of excitation.

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The best detection limits, as obtained with each of the methods described above, are summarized in TABLE 1 for seventy-one elements. The data were collected primarily from the permanent literature published within recent years. No effort was made to record the matrix element from which these sensitivities were obtained, although it is recognized that the matrix can have a controlling influence on the obtainable detection limits. The definition of detection limit, t h e type of equipment available, the exact parameters used, and the effort expended to obtain the maximum possible sensitivities will vary widely with various analysts. Therefore, a comparison such as this provides only a general indication of the relative merits of the several procedures. An indication of the present status of trace analyses by emission spectroscopy can be seen. Only one element (silver) has been detected at a relative concentration of one part per billion, but nearly half of the elements can be detected a t less than one part per million. I n general, the lowest detection limits are obtained in a controlled atmosphere.

Spark Excitation
I n the following discussion, the term spark excitation will refer t o those excitation conditions in which the flow of energy across the analytical gap varies rapidly and regularly, usually with a change of polarity each time the energy floC drops t o zero. These discharges have been identified by descriptive names such as low-voltage a. c. arc, high voltage spark, condensed spark, high frequency spark and interrupted arc. The characteristics and circuit parameters of the various types of spark discharges have been adequately described by others.68 I n general, spark excitation provides improved precision and decreased sensitivity as compared with arc excitation, and is usually employed in those situations where t h e greater precision is required, or where other limitations of arc excitation, such as the high anode temperature, preclude its use. Since the discharge is constantly being extinguished and reignited, there is little tendency for the discharge t o dwell on a restricted portion of the sample. Improved precision results from the better sampling which is thus obtained, and from the greater control which may be exercised over spark exeitation source units. When spark excitation is used with direct reading spectrometers, which provide better precision than do photographic instruments, it is possible to develop analytical procedures with coefficients of variation as low as * 1 per cent or even less. Indeed, for routine production control analyses, this combination of photoelectric detection and spark excitation has been widely accepted, not only for the better precision, but also because the analyses may be completed rapidly. During spark excitation, the electrodes remain relatively cooler and less sample is consumed than in d. c. arc discharges. The smaller quantity of sample vaporized and excited is largely responsible for the observed poorer sensitivity. The cooler electrodes provide an advantage for several types of samples. Metal

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TABLE 1 REPORTED DETECTION LIMITS I N PPM USING ARC EXCITATION

Element Ag A1 As Au B Ba Be Bi Ca Cd Ce co Cr

Carrier Controlled Cathode Sustaining arc distillation atmospheres layer (29y 56-63) (43,62,64,65) (30,57,60,66,67) (56-58) (62) Open a r c

cs

cu D Y Er Eu F Fe Ga Gd

Ge
Hf Hg Ho In Ir K La Li Lu Mi3

Mn
Mo Na Nb Nd

Ni 0s
P Pb

.1 .5 10 5 .2 1 .1 .4 1 .2 10 3 .5 2 .1 5 5 5 100 .05 3 10 1 1 .5 5 1 50 1 .5 .5 5 .01 .05 3 .5 10 20 1 50 20 .02

.5 0 1 10 .3 .08 1 .1 .5 1 .3 300 .5 1 30 .3

. 2

12 .
1 10

.001 .1 .1 .5 . 4 2 .005 .03 .01 .08 5 .04 .5 500* .1 2 2 2

.5 5 5 100 .5

.5 .5 1 1 10

8 1

. 4 .1 2 .1 10 .3 2 -1 4 1000* 2 500* 2 .1 .03 10 500* 5 5 .1 80 .15 .3

*Most sensitive line not used.

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TABLE 1 (Continued)

245

Element
Pd

Carrier Controlled Cathode Sustaining distillation atmospheres layer arc (29 56-63) (43,62,64,65) (30,57,60,66,67) (56-58) (62) Open arc
1 20 5 1 50 1

Pr Pt Rb Re Rh Ru

1 5

10

10
100

5 4

S
Sb sc Se Si Sm Sn Sr Ta Tb Te Th Ti T1 Tm U

.5

5 1 20 .5
20

2 3 1

1 5 30
50 10 100 1 .05

.3

4 1000* 10 . 6 . 4 . 3 .1 .5 500* .4 5 .1 5

50

V W Y Yb
Zn
Zr

5 100 5 20 5 1 1 10

1
10

5
8 10

10 40 500 1 .3 2 500 5 100 2

10 60 2

. 5

50

5 -

. 5

.5 .1
10

100

*Most sensitive line not used. self-electrodes can be used, which is not only convenient, but also contributes to the development of rapid analytical procedures, since these samples can often be analyzed with little or no preparation. In the metal-producing industries, samples can be cast as rods or pins which may be analyzed as quickly as the metal has solidified. Bulk samples are machined to provide the pins, or a smooth surface for the point-to-plane technique. Metal turnings, when formed into solid briquettes, may also serve as self-electrodes. The cooler electrodes are an important factor in the application of spark excitation to liquid samples. The excessive heating of the d. c. arc tends to vaporize, ignite, or otherwise prematurely expel solutions or other liquid

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samples from their supporting electrodes before they can be transported into the analytical gap. Methods for analyzing liquid samples are discussed in the following section. Spark discharges are also used with the copper and graphite spark excitation techniques. These techniques, which are primarily employed for the analysis of residues and concentrates, are also described in a later section. Powdered samples may be ejected from supporting electrodes by spark discharges. T h e mechanism appears to be a n electrostatic repulsion of the individual particles. The material ejected into the spark column does not appear t o be excited efficiently; consequently this technique has found little application for trace analysis. I t has been shown, however, t h a t particulate samples can be subjected t o spark excitation provided t h e sample has been In pressed into a relatively solid briquette prior to analy~is.~ the case of electrically nonconductive powders, such as oxides, a conductive binder must be added to the sample. Flake graphite is frequently used as the binder. Alternate methods of introducing powdered samples into the analytical gap include the sifting electrode, which has been described by Czakow in a and a variety of schemes series of papers,7o7 2 Danielssons tape for blowing the powdered sample through the discharge 2 0 n e . ~ ~I-n ~ Czakows procedure, the upper electrode contains the powdered sample, which sifts down into the analytical gap through small holes. With the tape machine, an adhesive tape, onto which the powdered sample has been deposited, is drawn between the two electrodes of a spark discharge a t such a rate that each spark encounters a fresh supply of the sample. In TABLE 2, the various types of spark excitation have been rather arbitrarily grouped into three broad classifications. The first group, identified as AC ARC, refers to a n alternating current arc with an open circuit potential of a few hundred volts, which must be reignited by a higher voltage spark pulse on each half cycle. The second group, High Voltage AC Spark, includes those discharges which have an open circuit potential of up t o 20,000 volts, and are self-igniting. T h e third group, Mixed Discharges, comprises sources which combine spark and arc excitation, such as the over-dampedcondenser discharge77 and the U n i a r ~ . ~ ~ Much of the data contained in TABLE 2 was obtained from the book A S T M Standard Methods for Emission Spectrochemical Analysis (1964). Many of the procedures in that book list only the lower limit of a particular procedure as determined by the lowest standard prepared, rather than detection limits. Therefore, unless otherwise identified, the data in this table are the reported determination limits.

Analysis of Liquid Samples

There are several advantages to be gained from the use of samples in the liquid state. Dissolution of solid samples eliminates the past metallurgical and physical characteristics of the sample which are so difficult to duplicate

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TABLE 2 REPORTED DETERMINATION LIMIT IN PPM USING SPARK EXCITATION

Element
Ag A1

AC arc (57,61,79,80) .3 .5 30

WAC spark (57, 61) .3 10 10 10 2" 2 la 1 .4" 1 30 10a 5"

Mixed discharge (57,611

As Au
B Ba

30
.4 3 3 1 .5 1 100
.4 1

Be Bi Ca Cd Ce

co
Cr

cs
cu D Y Er Eu F Fe Ga Gd Ge Hf

.1 100 100 100 1

100

2 10a

H g
Ho In Ir K La Li Lu Mg Mn Mo Na Nb
Nd Ni 0s

3 100 10

50

100

10

100 .4 .1 3 50*

.6a 2a 1000

.4a

60 1.5

100 2

10

(a) Detection limit. *Most sensitive line not used

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TABLE 2 (Continued)

Ac arc (57,61,79,80)
Pb Pd Pr
2

W A C spark (57,61)

Mixed discharge (57,61)

10a 50

100

P t
Rb Re Rh Ru

20

10

S
Sb

10 30

sc
Se Si Sm Sn Sr Ta Tb Te Th Ti T1 Tm U

10 5a

1 50 6 4

-,.
-

40

.8a

10a

100

6 10 10

50 3a 10 1Oa

5a 1
10a 50

2
8 10
20

W Y
Yb

-<

5a 10a

Zn Zr

50

10a 6a

(a) Detection limit. *Most sensitive line not used.

in the calibrating standards, and thus minimizes some of the matrix effects. The preparation of valid calibrating standards is simplified, and internal standards may be easily added to such samples. If samples are received as liquids, or if solid samples are dissolved in the preparation steps, direct analysis of the solutions should be considered because of the simplified preparation of the sample, the reduced amount of time required for the analysis, and the decreased opportunity for contamination. In many of the procedures for concentrating or enriching trace constituents, the resulting concentrate is obtained as a solution, and direct analysis of the liquid sample is often reported.

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Solution methods of analysis were reviewed by Young, and the relative merits of some of the procedures have been the subject of recent paper^.^*.'^ Several standard techniques for the excitation of liquid samples have been developed. Some are capable of being used for solutions containing as much as 10 per cent dissolved solids. Two such techniques are the porous cup and rotating disc. The porous cup method was first reported by Feldman in 1949.84,85 A graphite electrode, hollow except for a thin bottom approximately one mm. thick, serves as the upper electrode. The liquid sample is introduced into this electrode, and after the initial series of spark discharges have either porosified the floor or punctured it with micro-channels, the sample seeps through the thin bottom. The spark discharge then vaporizes and excites the spectra of those elements dissolved in the liquid. Excitation conditions must be carefully selected so that the sample electrode does not overheat and expel the sample. In the rotating disc method,49s86 a disc of graphite or some other electrically conductive material is slowly rotated on a horizontal shaft. The lower portion of the disc dips into the liquid to be analyzed, while the upper part and a counter electrode form the analytical gap. Thus, as the disc turns it carries a film of the liquid into the analytical gap to be vaporized and excited by a spark discharge. More energy may be employed than with the porous cup method, but care must be taken that the liquid reservoir is not overheated. Other procedures capable of utilizing relatively concentrated solution include the vacuum cup87 and the spray-in-spark88techniques. Methods requiring the atomization of the liquid sample are ordinarily restricted to solutions containing less than one per cent dissolved salts. More concentrated solutions have a strong tendency t o clog the atomization port, which may produce erratic results. Included in this classification are flame emission, atomic absorption, and plasma jet methods. Flame emission spectroscopy is nearly as old as the science of spectroscopy itself, and for the determination of some elements it remains unexcelled in sensitivity. Until a few years ago, however, flame methods were largely restricted to the alkalies and alkaline earths. Recent important discoveries related to burner design? appropriate solute and a n i ~ n : ~ . ~and optimal oxygen to fuel ratiosg1have combined to make it possible to detect nearly all elements except the permanent gases and the halogens. Because of the limited excitation energy available in a flame, the spectra obtained are relatively simple. Consequently, coincident interfering spectral lines are encountered much less frequently, and the use of small, comparatively inexpensive spectrometers with modest dispersion are practical. For example, the analysis of complex mixtures of the rare earth elements, using a flame emission method and a spectrometer with a reciprocal linear dispersion of only 16 A/mm., has been r e p ~ r t e d . ~ The atomic absorption method commonly utilizes an atomizer and a flame to transport and vaporize the sample. Instead of observing the emission of

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light from the flame, the amount of light which is absorbed by the atomic vapors in the flame a t a particular wavelength is determined. The primary light source is usually either a hollow cathode tube or a metal vapor lamp, either of which emit lines of discrete, isolated wavelengths t h a t are characteristic of the particular element contained in the lamp. Coincident line interferences are almost completely avoided, so t h a t small, inexpensive spectrometers can be used. This method was revived by Walsh in and has since become an accepted method of analysis. T h e previously mentioned advances in flame emission equipment and techniques, as applied to atomic absorption analyses, have made a substantial contribution toward its rapid adoption. The plasma j e t , perhaps more correctly called the gas stabilized d. c. arc, was developed in recent years primarily through the efforts of Scribner and mar go she^'^.'^ and Owen.96For plasma jet excitation, the solution is aspirated into a chamber, within which is located the anode of a d. c. arc discharge. A vortex of gas, usually either argon or helium, drives the vapors and plasma through a n orifice toward the external cathode. The resulting arc discharge not only has much of the sensitivity of the conventional d. c. arc and the simplicity of preparation of standards and samples of other solution analytical methods, but also is an exceptionally stable excitation source. T h e precision isexcellent; one laboratory has reported a precision of better than 5 per cent without the use of a n internal ~ t a n d a r d . ~ I n TABLE 3, the detection limits for t h e more common methods of solution analysis are compared. T h e values are reported in micrograms per milliliter, which is roughly equivalent to ppm in solution. However, it must be remembered that in t h e dissolution step, a sample is diluted by a factor of 10 t o 100 for the porous cup and rotating disc methods, and by a factor of 100 to 1000 for flame emission, atomic absorption and plasma jet methods. Nearly all of the flame emission and much of t h e atomic absorption data were obtained in the laboratories a t Iowa State University. I t can be seen that elements such as the rare earth elements, titanium, and tungsten, which until recently could not be detected by these procedures, are now measured at the trace level. It should also be noted t h a t the flame emission and atomic absorption methods are complimentary in a number of instances, with good sensitivity being reported for one or the other method in nearly every case.

Enrichment Procedures
Regardless of the ultimate limit of detection which can be achieved by spectrochemical methods of analysis, there will always be need for analyses a t even lower levels of concentration. The several advantages of spectral analysis, such as high sensitivity, the ability to simultaneously determine the concentration of a number of elements in a small sample, and the rapidity with which analytical results can be obtained, may make it desirable to retain this method

DeKalb et al.: Optical Emission Spectroscopy

TABLE 3 REPORTED DETECTABILITIES FOR LIQUID SAMPLES ABSOLUTE SENSITIVITIES (pgjml.)

251

Porous cup Element Ag A1 As Au B

Rotating disc (8598-100) (82,98)

Atomic Flame emission absorption (98,99,101,102) (98)

Plasma jet (101,103)

.02 .3 3 20

.I
.1 .003 1
.01 .2 3

Ba
Be Bi Ca Cd Ce co Cr

cs

.5 .1
15

cu

D Y
Er Eu F Fe Ga G d Ge Hf Hg Ho

.05 2 2 .5

.3 .2 290 15 250 .03 76 . 410 .005 33 10 1.3 .1 84 . .005 .1 .3 .0025 .14 .07 2 45 . 75 100 .1 .03 110 .003 1 .000003 .2 .2 .03 .03 .0001 1 1 .6 10

.02 .5

.1

. 9 .05 .2 .01 .01 > 10,000 .15 .01 .05 .005 .5 1 . 4

.2

.05

In
Ir K La Li Lu Mg Mn Mo Na Nb Nd Ni
0s

.5 .5 .5 4 10 .5 3 10 200 .3 .1 .5 .003 .02 .3 35 2 5

.8

3
.5 25 . .1

.005

.004 53 .003 01 .2 .005 26 38

P Pb Pd

15 5 4 2

3.3 1.1

.15

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Annals New Y ork Academy of Sciences

TABLE 3 (Continued)

Element Pr Pt Rb Re Rh Ru
S

Porous cup Rotating disc (85'98-100) (82,98)

Atomic Flame emission absorption (98) (98,99,101,102)

Plasma jet (101,103)

2 1

.7

5
2 2
.05 70

2 190 .1 1 .3 .3

64 .5 .2 5 .3

.2 1.1 12 14 2 .02 26 .5 2 .2 .1

Sb sc Se Si Sm Sn Sr Ta Tb Te Th Ti T1 Tm
U V W

2.5

92
.07

1 3 2
.06 2 3 10 10 .1 3 2 100 .2 3 .1 .04 4 .2

74 .6 3.5 .004 20 1 1400 150 .5 .09 .2 10 .3 4 . 3 .05 1500 50

.25
-

Y
Yb

Zn Zr

.6 5 13 .2 .005

.25

of analysis. I t then becomes necessary t o preconcentrate the impurities by some chemical or physical means. The methods and problems of separation and concentration have been discussed a t length by Thiers,Io4 Pinta,lo5 Pijck et a1.Io6 and ~ t h e r s . ' ~ ~ ~ A primary consideration, when working at such low levels of concentration, must be the prevention of contamination of standards and samples. Exceptional precautions are required, with all reagents being carefully chosen or purified and all containers being selected for their corrosion and contamination resistant qualities. Laboratory ware made of organic molecules, such as plastics, are of particular value. Laminar-flow, clean-air work benches and fume hoods are recent developments which can aid in the prevention of contamination from the environment .""

DeKalb et al.: Optical Emission Spectroscopy

253

The listing below of the general classifications of enrichment procedures is undoubtedly incomplete, but does illustrate the wide range of procedures.

Enrichment Procedures
Evaporation Ashing Vaporization of matrix,' "-'16 of impurities.111~120 Precipitation of matrix,'21,'22 of i m p u r i t i e ~ . ' ~ ~ ' ' ~ ~ Liquid-liquid e x t r a ~ t i o n . ' ~ ~ " ~ ~ ~ ' ~ ~ Chromatography 13' Ion e ~ c h a n g e ~ ~ , ' ~ ' - * ~ ~ Electr~lysis'~~ EMF r e d u ~ t i o n ' ~ ~ ' ' ~ ~ Amalgamati~n'~~ Fire a ~ s a y ~ ~ ' . ' ~ ~ Zone r e f i r ~ i n g " ~ . ' ~ ~ Magnetic ~ e p a r a t i o n ' ~ ~

The first three procedures-evaporation, ashing, and vaporization-are in reality only variations of a single process. An application of the fourth procedure, vaporization of impurities, deserves additional comment. M a n d e l ~ h t a m ~ ~ Zaide13' developed a method utilizing the preferential and vaporization of impurities to improve detection limits. This method has been used by a number of spectroscopists in Russia and other East European countries, but only one Western sp,ectroscopist has reported its a p p l i ~ a t i o n . ' ~ ~ In this method, the sample is placed in an electrode and the more volatile impurities preferentially vaporized, with the aid of a carrier, from a more refractory matrix. Resistance heaters are used t o accomplish the vaporization. The impurities are condensed on a cooled graphite rod, which is subsequently used as one of the electrodes in a conventional spectrochemical analysis. The method is very similar to the carrier distillation method, which was described above, except that the vaporization and excitation steps are completely separated. The obvious advantage of this arrangement is that the conditions for each can be independently selected or adjusted for optimum results. Space does not permit a general description of the various applications of enrichment methods t o spectrographic analyses, but the references included with the above list will provide the interested reader with typical examples.

Spectrochemical Analysis of Residues

A distinction was drawn earlier between "trace" and "micro" analyses. "Micro" analysis was defined as the analysis of very small samples for their major or minor constituents. When residues obtained from separation or enrichment procedures are to be analyzed, it is often a "micro" analysis that is required. In this case, it is not the line-to-background ratio which determines detectability, but rather the total amount of radiation which can be collected and recorded during the brief period while the sample is being excited. Con-

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sequently, entirely different spectral parameters are employed, the primary objective being to obtain maximal optical speed. This is done by using a small, large aperture spectrometer, with a wide entrance slit. The external optics should be adjusted so that maximal radiant flux is incident on the prism or grating, and if a grating instrument is used, the grating should be blazed for maximum intensity at the wavelength to be observed. The detector should also have its peak response a t those wavelengths, and the detecting system should be of the integrating type. If photographic detection is used, prefogging the plates or film will improve the detection limit by overcoming the inertia of the emulsion. Direct current arc excitation, with the sample on or in t h e anode, has already been described as a very sensitive method for trace analysis work. This method of excitation has been applied t o residue samples with equal success and is perhaps the standard analytical procedure with such samples. Frequently the residues obtained from enrichment procedures are collected as solutions, or can be easily dissolved. I n such form they are conveniently transported and deposited on electrodes. However, electrodes which are porous, such as those made of graphite, are usually treated to limit the penetration of the dissolved sample. Oils, greases, waxes and various plastics have been used for this purpose. Several methods for the spectral analysis of residues have attained rather wide acceptance, and as such may be regarded as standard procedures. The cathode layer method, which was described earlier in the section on Arc Excitation, is particularly well suited to the analysis of small samples. The degree of ionization, on which the enhancement mechanism apparently depends, is not inhibited by such samples. This, i t is in absolute, rather than in relative, sensitivity that the method exhibits a substantial improvement over anode excitation. I n the copper spark method, described by Fred, Nachtrieb and tom kin^,'^^ a solution containing about one-tenth of a milligram of dry residue is deposited and dried on the end of a solid copper electrode, which is then subjected to condensed spark excitation. High absolute sensitivities are obtained, but only with small samples. Samples larger than 0.1 mg. tend to form a fragile crust on the copper electrode; these crusts are fragmented and dispersed without excitation by the spark discharge. Graphite spark excitation is similar except that a treated graphite electrode is substituted for the copper rod, a n obvious advantage being that copper can then be determined.'lg If a low current d. c. discharge a t a potential of several hundred volts is operated in an inert atmosphere of very low pressure, a glow discharge envelopes the cathode. I t has been observed that if the cathode is cratered or cupped, the glow discharge can be contained within the hollow cathode by appropriate adjustment of the pressure. The glow consists of radiation characteristic of the cathode or of a sample located within the hollow cathode."" This hollow cathode excitation has been applied to the analysis of small samples and

Dekalb et al.: Optical Emission Spectroscopy

TABLE 4 REPORTED DETECTABILITIES FOR MICRO SAMPLES ABSOLUTE SENSITIVITIES (mpg)

255

Element

Cathode layer (155)

Copper or graphite s p a r k (148,149,156)

Hollow cathode (153)

Reduced argon atmosphere (154)

Ag A1 As Au B

Ba Be
Bi Ca Cd Ce co Cr

cs

cu D Y Er Eu F Fe Ga Gd Ge
If

.5 .5 50 50 5 20 . 5 50 .5 200 3000 5 5 50 2 300 80 200

Hg Ho In Ir K La Li Lu
Mg

Mn Mo Na Nb Nd
Ni 0s P

Pb
Pd

2 5 300 10 50 100 90 10 50 5 400 .1 30 1 2 2 1 50 2000 10 10 500 10 5

. 5 2.5 100 20 .25 10 . 2 5 10 20 30 5 1 50 .5 20 10 2 10 25 . 100 10

1.5

20 4 2 .12

.4

.3 10

50 10 20 10 500 10 2
.2

20
1

1 1
.25 5 10 20 20 1

.2 1.3 1.6
7

10 5 50

30 1

256

Annals New Y ork Academy of Sciences

TABLE 4 (Continued)

Element

Cathode layer (155)

Copper or graphite spark (148,149,156) 20 2 20 200

Hollow cathode (153)

Reduced argon atmosphere (154)

Pr P t
Rb Re

Rh Ru S
Sb sc Se
Si

900 5 20 500 30 10
20 10 5 2000 5 5 400 300 50 2000 5 20 30 400 5 500 8 3 100 20

10 .5 10 20 50 10 100 50 20 2.5 50 5 100 1 10 .5 1 10 2.5

100

1
3
7

Sm Sn Sr Ta Tb Te Th Ti T1 Tm U

10

V W Y
Yb Zn

45

Zr

residues by depositing the sample, as a liquid or powder, within the cathode cavity. The cathodes are typically composed of graphite, steel, brass or some other metal.151'153 The sample is either vaporized or sputtered into the discharge, and there excited. Ion lines are observed to be relatively stronger than in conventional discharges. T h e particular advantage of this method of excitation is that the atoms do not readily escape from the cathode because they are attracted to the cathode whenever ionized. Thus, the process of vaporization, excitation and deposition may be repeated many times before the atom finally migrates away from the discharge zone. Long exposures with multiple excitation of the sample, therefore, provides very high absolute sensitivities. Furthermore, valuable samples, such as certain isotopes or elements of the actinide series can be reclaimed from the enclosed chamber following the analysis.

DeKalb et al. : Optical Emission Spectroscopy

257

Hollow cathode excitation has failed to achieve wide acceptance because of the considerable difficulty in accurately reproducing excitation conditions, and because the hollow cathode tube must be cleaned and the low pressure inert atmosphere reestablished for each individual sample. Gordon has recently reported an intermediate-pressure, argon-atmosphere method'54 which resembles hollow cathode excitation in some respects. Sensitivities are nearly equal to those obtained with the hollow cathode. Several samples can be loaded into the arcing chamber before the pressure is reduced, in this case to about half an atmosphere. Cathode excitation is used, but the pressure is too great for the development of a glow discharge. Also, a buffer is added to each sample to reduce ionization and thus enhance lines originating from the neutral atom. The absolute sensitivities of several of the residue analysis methods are compared in TABLE 4. The data are expressed in milli-micrograms, which is equivalent to parts-per-million on a sample weighing one milligram.

References
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Annals New York Academy of Sciences

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18: 1127. DSILVA, A. P., R. N. KNISELEY, V. A. FASSEL, R. H. CURRY & R. B. MYERS. 1964. Anal. Chem. 36: 532. WALSH, A. 1955. Spectrochim. Acta. 7: 108. MARGOSHES, M. & B. F. SCRIBNER. 1959. Spectrochim. Acta. 15: 138.

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