Mikrochim.

Acta 132, 145151 (2000)

Quantitative Trace Analysis by Wavelength-Dispersive EPMA

Stephen J. B. Reed
Department of Earth Sciences, University of Cambridge, Cambridge CB2 3EQ, England

Abstract. ``Trace'' elements may be dened as elements whose concentrations are of a similar order to the detection limit. In WD analysis the detection limit is a function of the `gure of merit' P2 /B, where P is the pure-element peak intensity and B the background intensity. With normal analysis conditions detection limits of $100 ppm are typical, but substantial improvements can be achieved by using higher values of accelerating voltage and beam current. Long counting times are also advantageous, but should preferably be divided into relatively short alternating peak and background measurements to minimise the effect of instrumental drift. Using separate routines for trace and major element analysis is desirable owing to their different requirements. As the statistically dened detection limit is reduced, errors due to background nonlinearity and interferences (overlaps) from other elemental peaks become more probable. Spectrum simulation is useful for optimising background offsets and choice of crystal to minimise interferences, and estimating interference corrections when these are necessary. `Blank' standards containing none of the trace elements of interest are also useful for quantifying background nonlinearity.
Key words: Trace analysis; WDS; EPMA.

In EPMA the presence of the X-ray continuum limits the detectability of small peaks as dened by statistical criteria. Other microprobe techniques which are comparatively free of background have substantially lower detection limits, but EPMA is more widely available and has better spatial resolution. For `trace element' EPMA, ED spectrometers are handicapped by their relatively poor resolution, which not only is insufcient for relevant lines in the spectrum to

be resolved in some cases, but also results in low peak-to-background ratios, owing to the greater width of the band of continuum recorded with the peak. The limited pulse throughput rate (which applies to the whole spectrum) is a further drawback. As well as their better resolution, WD spectrometers have the additional advantage that they record only one wavelength at a time and thus are not swamped by major-element peaks when a high beam current is used to maximise the intensity of trace-element peaks. Microcalorimeter spectrometers [1] have resolution comparable to WDS but are even more severely limited in throughput rate than conventional EDS and are thus uncompetitive for trace analysis at present. The following discussion therefore refers solely to WD analysis. The minimum measurable peak size (and hence the elemental detection limit) is ultimately governed by counting statistics. By using appropriate conditions, such as high beam current and long counting times, peaks representing concentrations of the order of 10 ppm are detectable in favourable cases (higher gures apply for L and M lines and samples of high mean atomic number). However, such peaks typically correspond to as little as $1% of background, and careful attention to possible errors in the background correction is essential. Linear interpolation from measurements made with the spectrometer offset on each side of the peak may sometimes be subject to errors caused by curvature of the continuum and discontinuities related to absorption edges. Also, when the presence of a neighbouring peak rules out background measurement on one side, and only the background on the other side is used for the correction, errors can arise if no allowance is made for slope. In trace analysis it is, in addition,

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particularly important to beware of inter-elemental interferences due to overlapping lines, which can cause serious errors. These may be avoidable by choosing a spectrometer crystal giving higher resolution or an alternative X-ray line, but some loss of trace element detectability is entailed owing to the reduced intensity. Interferences, if present, must be taken into account by means of a correction reecting the degree of overlap and the concentration of the interfering element. In such cases, trace-element analysis capability is impaired by increased errors from counting statistics and uncertainties in the correction. Counting Statistics The statistics of counting random events is covered in standard textbooks and for present purposes it is only necessary to quote the following conclusions, which refer to the measurement of a small peak superimposed on a relatively large background. 1. The detection limit, dened as the minimum concentration required for the peak to be just detectable at a specied condence level for a given counting time, is proportional to (P2 /B)0.5, where P is the number of counts recorded for the pure-element peak and B the number of background counts for the specimen. 2. The time required to achieve a specied detection limit is inversely proportional to the `gure of merit', P2 /B. 3. The maximum precision in the determination of the background-corrected peak intensity with a xed total counting time is obtained with equal times for peak and background. Other Random Fluctuations Fluctuations from other sources can be detected by comparing the scatter in a series of repeated measurements with that predicted from counting statistics (standard deviation square root of number of counts). In practice the difference is usually insignicant. As a precautionary measure, peak and background measurements in trace analysis may be subdivided into a series of relatively short counting times (which is also advantageous in counteracting drift, as discussed below) and the results analysed statistically in the course of the measuring routine. This allows outliers to be rejected; also counting

may be continued until a specied precision is achieved [2]. Detection Limit Various denitions of detection limit are used, of which the simplest is `3 standard deviations of background' (3sdbg), obtained by dividing 3 times the square root of the background count by the peak count for the pure element (corrected for absorption in the sample). The fraction of repeated determinations of the background count lying within this limit is 99.6% according to classical probability theory. However, the analytical procedure entails measuring the number of counts on the peak as well as background: assuming equal counting times the fraction of repeated determinations of peak minus background falling below the detection limit as dened above is 96.6%. The 3sdbg detection limit is thus the concentration for which the presence of the element can be afrmed with 96.6% condence. Adapting to an alternative condence level merely requires the substitution of a different standard deviation multiplier. Various more elaborate expressions exist, but there is little benet in attempting to quantify the detection limit with high precision. In the present context its main function is to compare different analytical conditions. Detection limits show an upward trend as the atomic number of the element concerned increases, owing to the lower intensity of the L and M lines used for heavy elements compared to the K line used for lower atomic numbers. The mean atomic number of the sample is also important, because of its effect on the continuum intensity. Detection limits approaching 1 ppm in favourable cases can be obtained by using extreme conditions (high accelerating voltage and beam current, and long counting times) [3]. However, for such results to be meaningful, close attention must be paid to possible errors caused, for example, by nonlinear background, or inter-element interferences. Optimum Conditions for Trace Analysis As stated above, trace element analysis benets equally from maximisation of peak intensity and peak-tobackground ratio, both of which increase with increasing accelerating voltage (V0), though in cases of high absorption the peak intensity passes through a

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Fig. 1. Calculated relative spatial resolution and detection limit as function of accelerating voltage; detection limit shown with and without absorption in the sample (assuming arbitrary values of mass absorption coefcients for illustrative purposes)

maximum and then decreases owing to the increasing depth of X-ray production (Fig. 1). However, electron 5a3 penetration increases approximately as V0 , with a consequent worsening of spatial resolution (see Fig. 1). Counting Strategy Optimum choice of counting times is important for trace element analysis. Prior knowledge of peak and background intensities enables detection limits to be predicted and counting times chosen to achieve the desired result. For this purpose stored or calculated intensity data may be used, or alternatively a selfadaptive procedure can be applied, whereby counting times are adjusted in the light of relatively rapid preliminary peak and background measurements [2]. To minimise errors due to beam current drift, contamination build-up, and specimen damage, it is desirable to divide the long counting times required for trace analysis into a series of alternating peak and background measurements. Where the operating software has no provision for this, a similar result can be obtained by repeating the normal analysis routine using relatively short counting times. Specimen Damage For some types of sample the allowable current is limited by specimen damage. Assuming this is determined by the energy deposited in the sample per unit volume (rather than by the energy of the

individual electrons), a higher current can be used with high V0 because the energy is deposited in a larger volume. The case for using a high V0 as stated above is thus enhanced for this type of sample. Other preventive measures commonly used, namely enlarging the beam, scanning the beam in a raster, or moving the specimen during the analysis, all incur a sacrice of spatial resolution. Beam-induced heating of poor heat-conductors can be reduced substantially by coating with a material of high thermal conductivity [4] (the choice between suitable metals such as aluminium, copper, silver or gold is inuenced by the need to avoid interference with the X-ray spectrum of the sample). By comparison with the thin carbon coat normally used for insulating samples (which has little protective effect), such relatively thick metallic coatings reduce the X-ray intensities signicantly, and this must be taken into account by using similarly coated standards or applying a correction factor. Pulse-Height Analysis Pulse-height analysis not only minimises the contribution of high-order reections of characteristic X-ray lines where these coincide with the analytical (rst-order) line, but may also reduce background by excluding the contribution of high-order continuum X-rays (especially for long wavelengths, where differential absorption by the counter window enhances the relative intensity of the high-order continuum). Background produced by scattered X-rays and electrons (especially at low Bragg angles) can also be reduced by suitable threshold setting. When pulseheight analysis is used, it is important to avoid excessive count-rates (e.g., ) 104 counts/s), where pulse shrinkage and broadening of the pulse-height distribution may occur. These effects can be minimised by using a reduced counter anode voltage (compensated by increased amplier gain). Choice of Line and Crystal For a given element there is sometimes a choice of analytical line: e.g., for atomic numbers 26 to 35 the K and L lines are both within the range of spectrometers equipped with the usual crystals (likewise the L and M lines for Z 7092). Furthermore, there is a choice of crystal when the wavelength concerned falls within the region of overlap between crystals. For trace analysis the optimum line/crystal

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combination is that which gives the maximum P2 /B. However, the presence of spectral interferences favours the crystal with smaller interplanar spacing (and therefore higher Bragg angle for a given wavelength, and better resolution). Using a narrow spectrometer slit increases P/B but this is outweighed by the decrease in P and is therefore of little benet, except occasionally for resolving interferences. Background Corrections X-Ray Continuum Background is attributable almost entirely to the continuous X-ray spectrum (`continuum') generated by the bombarding electrons. The continuum intensity I(!) (in photons per second per unit wavelength interval) is given by the Kramers expression: I(!) = const. Z!1 !1 !1 , in which !0 is the 0 Duane-Hunt limit as determined by the incident electron energy. The intensity rises to a maximum at 2!0 and decreases monotonically for ! b 2!0 (the usual region of interest). The observed background consists of the continuum integrated over the width, !, of the spectrometer response function. This is equal to the peak width for an effectively monochromatic X-ray line, and decreases with increasing Bragg angle, enhancing the effect of the downward trend in I(!) [5]. Other relevant factors are crystal reection efciency, window absorption, and counter detection efciency, but these affect background and peak intensities equally. Linear Background Interpolation The normal method for estimating background is to measure the intensity with the spectrometer offset on each side of the peak and interpolate linearly to the peak position. The offset required depends on the peak width (which increases at the low end of the Bragg angle range) and the presence of adjacent lines. Using large offsets may risk errors due to background nonlinearity, but it is not necessary to move so far from the peak as to completely avoid the tails: a moderate contribution from these is acceptable since it has no effect on the ratio of the sample and standard background intensities, provided the same offsets are used for both and there is no difference in the shape of the peak prole [6]. The presence of neighbouring lines on one side of the peak sometimes requires background to be

measured only on the other side (assuming this is interference-free). The factor required to allow for the slope of the continuum can be derived from a `blank' standard containing none of the trace elements concerned. This need not necessarily be closely similar with respect to major elements, since continuum shape is independent of composition, but must not have any absorption edges or interfering lines in the regions of interest. Background Curvature In trace-element analysis background nonlinearity requires consideration, because the amount which is acceptable (relative to other errors) is as little as 1%. Curvature is generally small over the relevant wavelength interval, but the correction required is not necessarily negligible. The effect depends on the size of the offsets used and, in terms of concentration, is a function of the pure-element peak intensity compared to the continuum. It is thus greatest for a sample of high mean atomic number and for a relatively weak X-ray line (see Fig. 2). Corrections can be derived from a blank standard satisfying the criteria described in the previous section. If required, the local shape of the continuum may be represented by an equation such as a parabola, the coefcients of which can be determined experimentally [7].

Fig. 2. Background error expressed as concentration (ppm) caused by continuum curvature (LiF crystal, accelerating voltage 25 kV, sample atomic number 26) plotted against sine of Bragg angle. The effect of curvature is greater for L than for K lines owing to the lower intensity of the former

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Continuum Modelling Predicting background intensities by calculating the continuum intensity offers the attractive possibility of saving counting time and avoiding interpolation and interference problems associated with spectrometer offset measurements. The generated continuum intensity can be derived from Kramers' expression, but the observed intensity also depends on the spectrometer efciency. Since it is impracticable to derive this from rst principles, an empirical approach must be adopted. For example, intensities measured at the wavelengths of relevant lines using a blank standard containing none of the trace elements of interest can be scaled to allow for the atomic number difference. The uncertainty involved in this scaling should preferably be minimised by using a standard similar in mean atomic number to the analysed sample. A somewhat more complex function than the simple linear Z-dependence in the Kramers expression is required (except for small differences in Z): this can be derived from experimental measurements on samples of different mean atomic number [2, 8, 9, 10]. Corrections for absorption in the specimen should be applied. Limits to the accuracy obtainable by this method may inhibit its use for extreme trace-element analysis. Background Discontinuities The assumption that background varies smoothly and monotonically with wavelength is mostly valid, but discontinuities due to absorption edges need to be taken into consideration. For example, the Ar K absorption edge at 0.3871 nm causes an abrupt change in the efciency of an argon-lled proportional counter. Also, absorption edges of major elements in the sample cause steps owing to the change in the absorption of the emerging continuum X-rays. Background offsets should be chosen so that no such edges lie between the peak and the positions used for measuring background. A `hole' in the background for LiF occurs at 0.1271 nm, close to the Au L line, where about 10% of the intensity is lost owing to reection by the `wrong' planes in the crystal [11]. Allowance for the hole must be made if this line is used, or alternatively the M line may be used instead. Interferences The high resolution of the WD spectrometer ensures that characteristic X-ray lines are well resolved in

most cases. However, interfering peaks may cause either over- or under-estimation of element concentrations, depending on whether peak or background is affected most. It is common practice to adopt a `trial and error' approach in which normal analytical conditions are used initially and are modied if the presence of interferences is indicated, for example, by asymmetry in the background intensity recorded above and below the peak, or a negative concentration. It is preferable, however, to identify possible interferences in advance, for example, by spectrum simulation (see below). Interferences in complex spectra can be minimised by optimal selection of analytical line, spectrometer crystal and background offsets, but where unavoidable their effect needs to be corrected by deducting an appropriate amount from the measured peak and/or background intensities. To a fair approximation the overlap correction can be equated to the apparent concentration of the overlapped element in a standard containing the overlapping element, scaled in proportion to the concentration of the overlapping element in the sample. However, it is desirable to take account of the matrix-dependence of the relative line intensities involved by applying `ZAF' factors [12]. Traceelement analysis is inevitably affected adversely by interferences, on grounds of both statistical precision and uncertainty in the corrections. WDS Simulation The idea of spectrum simulation originated with the NIST `Desk-Top Spectrum Analyzer' for ED spectra. Modelling WD spectrometer characteristics is harder, hence experimentally recorded spectra are used in the `Virtual WDS' program [13]. This contains a database of experimentally recorded spectra, which can be scaled according to accelerating voltage and beam current, and combined in proportion to assumed element concentrations (using estimated values for `unknown' samples), thereby obviating the need for time-consuming `real' wavelength scans. A case where this approach is valuable is rare-earth element determination in minerals [14] (see Fig. 3). Another useful feature is the ability to predict precision and detection limits. Trace Element Quantication The principles of quantitative analysis are the same for trace and major elements: the concentration of

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Fig. 3. Spectra of Eu and other rare-earth elements (LiF crystal) produced by `Virtual WDS' program, illustrating interferences affecting both Eu L peak and potential background offset measurement positions

each element is derived from the ratio of the background-corrected peak intensity for the sample to that obtained from a reference standard (either a pure element or a compound of known composition containing the element concerned). There is little benet in using as the standard for a trace element a material in which the relevant element is present in a similarly low concentration: indeed, this has the disadvantage that the standard measurement is then subject to the inaccuracies associated with measuring small peaks. Also, homogeneous trace-element standards are hard to nd. It is therefore reasonable to use the same standards for trace elements as for major elements, though the beam current must be relatively low to avoid excessive count-rates. A secondary consideration is that uncertainty in the matrix corrections is reduced if the standard resembles the sample in composition. However, tests of matrix correction procedures for major elements show that errors are generally less than 5% (relative), which is usually smaller than the statistical errors for trace elements; compositional similarity of standards is thus less important than for major elements. Combining Major and Trace Element Analysis Optimum conditions for trace analysis tend to give excessive count-rates for major elements, as mentioned above. This can be overcome by conducting major-element analysis separately using `normal' conditions and then combining the results with trace-element data obtained with higher accelerating voltage and beam current. However, electron penetra-

tion increases with the accelerating voltage, hence trace and major element data will refer to different volumes within the sample. Also, EPMA software is commonly not adaptable to this strategy, necessitating the use of a separate trace analysis program [15]. This approach is facilitated by the fact that trace elements need not be included in the iterative correction loop, since they have a negligible effect on the correction factors. Separate routines may be avoidable by selecting X-ray lines for major elements which are less intense than the normal choice: for example, K instead of K. (The spectrometer crystal can also be selected with this in view in some cases). An alternative possibility is to use an ED spectrometer with a small aperture (the concentration of high X-ray intensity on a limited area of the detector does not seem to have any ill effects). Errors in Trace Analysis The precision of trace element analysis is ultimately limited by counting statistics, but can be worsened by uctuations caused, for example, by instrument instability (though this is usually small). The most important potential systematic errors are connected with background subtraction and inter-element interferences. The effect of uncorrected continuum curvature is generally small. Larger errors (either positive or negative) can be caused by interferences. Avoidance by using an alternative analytical line usually entails poorer precision and detection limit, on account of the lower peak intensity and peak-tobackground ratio. Even if an interference correction is applied, there are residual errors due to uncertainties in the correction, and with large interferences trace analysis is effectively impossible. A detected peak may be real, while not truly reecting the presence of that element in the sample. For example, scattered electrons may excite X-rays from surrounding objects, or nearby parts of the specimen itself, though fortunately the focussing properties of WD spectrometers help to minimise such extraneous contributions. Surface contamination from polishing materials etc. is another potential cause of misleading results, but can be avoided by suitable choice of materials and thorough specimen cleaning. Fluorescence in a neighbouring phase excited by primary X-rays from the analysed spot can give rise to a spurious result where there is a high

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concentration of the element concerned in the adjacent phase. An example is $500 ppm Ca observed in a Ca-free silicate mineral adjacent to calcite (40% Ca) at a distance of 20 mm from the interface [16]. There is no way of preventing this, but corrections can be estimated. Alternatively, in some cases it may be possible to extract the grains of interest and analyse them in isolation. Conclusions To exploit the trace element capabilities of EPMA fully it is necessary to use conditions that maximise the statistical precision with which a small peak can be distinguished from background. The high accelerating voltage and beam current desirable on these grounds are, however, unsuitable for major element analysis on account of excessive count-rates, large ZAF corrections, poor spatial resolution, and specimen damage. Separate routines for major and trace elements are therefore preferable. The long counting times necessary for the latter should, if possible, be divided into alternating peak and background measurements to minimise the effect of instrumental drift. Ultimate detection limits approaching 1 ppm as dened by statistical criteria are obtainable in the most favourable cases, but for heavy elements which require the use of L or M lines (which are less intense than the K lines used for elements in the range Z 11 30) and for samples of high mean atomic number (and consequently high continuum intensity) attainable limits are considerably higher. For concentrations around a few ppm, the normal background correction method entailing linear background interpolation between offset spectrometer positions is questionable, the accuracy required in the background determination being of the order of 1%. Careful attention must therefore be paid to the possibility of nonlinearity, which may arise from

curvature of the continuum or absorption edges. A `blank' standard known to contain none of the trace elements of interest can be used to quantify these effects. Serious errors can occur when either peak or background measurements are affected by interfering peaks of other elements. Interference corrections can be applied when necessary, but in such cases the accuracy of trace element analysis inevitably suffers. Correction factors can be determined from measurements on pure elements (or other appropriate standards). A spectrum simulation program enables interference effects to be predicted and often avoided by choosing an alternative spectrometer crystal or X-ray line and saves instrument (and operator) time. References
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