UW-Madison Geoscience 777 Electron Probe Microanalysis EPMA Quantitative

UW-Madison Geoscience 777 Electron Probe Microanalysis EPMA Quantitative Analysis and Matrix Corrections Revised 1/10/2016

Raimond Castaing (1921 -1999) • Advisor Andre Guinier studied defects (Cu-Al inclusions) in Al metals (for airplanes) • Defects too small to define by optical microscope • Guinier famous X-ray crystallographer • He suggested Castaing try to find inclusion compositions--measure Xrays generated by electron beam, using war-surplus TEM • Castaing succeeded, Ph. D 1951 “Application of Electron Probes to Local Chemical and Crystallographic Analysis”

Raimond Castaing (1921 -1999) His thesis laid out the basics of EPMA which have remained constant for the past 64 years Key concept: where K is the “K ratio” for element i, I is the X-ray intensity of the phase and subscript i is one element.

Using K-factor simplifies analysis • counts acquired on BOTH unknowns and standards on the same instrument, under the same operating conditions, • All physical parameters of the machine that would be needed in a rigorous physical model cancel each other out

UW- Madison Geology 777 Castaing’s First Approximation Castaing’s “first approximation” follows this approach. The composition C of element i of the unknown is the K-ratio times the composition of the standard. In the ‘simplest’ case where pure element standards can be used, Cistd = 1 and drops out. …So how close are these K-ratios to the true composition?

Examples: some minerals Fo 90 Olivine Hafnon Hf. Si. O 4 Zircon Zr. Si. O 4 Notice the “differences” (between K-ratio and true compositions…. So we need a MATRIX CORRECTION

UW- Madison Geology 777 Raw data needs correction This plot of Fe Ka Xray intensity data demonstrates why we must correct for matrix effects. Here 3 Fe alloys show distinct variations. Consider the 3 alloys at 40% Fe. X-ray intensity of the Fe-Ni alloy is ~5% higher than for the Fe-Mn, and the Fe-Cr is ~5% lower than the Fe. Mn. Thus, we cannot use the raw X-ray intensity to determine the compositions of the Fe-Ni and Fe-Cr alloys. (Note the hyperbolic functionality of the upper and lower curves)

UW- Madison Geology 777 Absorption and Fluorescence • Note that the Fe-Mn alloys plot along a 1: 1 line, and so is a good reference. • The Fe-Ni alloys plot above the 1: 1 line (have apparently higher Fe than they really do), because the Ni atoms present produce X-rays of 7. 278 ke. V, which is greater than the Fe K edge of 7. 111 ke. V. Thus, additional Fe Ka are produced by this secondary fluorescence. • The Fe-Cr alloys plot below the 1: 1 line (have apparently lower Fe than they really do), because the Fe atoms present produce X-rays of 6. 404 ke. V, which is greater than the Cr K edge of 5. 989 ke. V. Thus, Cr Ka is increased, with Fe Ka are “used up” in this secondary fluorescence process.

UW- Madison Geology 777 Theoretical approach to corrections One can write an equation showing the relationship between x-ray intensity IA and elemental concentration CA, using fundamental physical parameters*: Rearranging the equation and solving for CA is not that easy! So the material scientists, chemists and geologists who took up the electron probe as a crucial tool came up with some alternatives… *Merlet and Llovet….

UW- Madison Geology 777 Actual approaches to corrections Heinrich* summarizes the 4 actual types of models used for matrix corrections in EPMA: 1. Empirical: simplest, based on known binary experimental data; 2. ZAF: 1 st generalized algebraic procedure; assumes a linear relation between concentration and x-ray intensity; 3. Phi-rho-Z: based upon depth profile (tracer) experiments; 4. Monte Carlo: based upon statistical probabilities of electronsample interactions, particularly for unusual specimen geometries. *Heinrich, 1991, Strategies of electron probe data reduction, in Electron Probe Quantitation, Ed. Heinrich and Newbury, Plenum, New York, 9 -18.

UW- Madison Geology 777 Two approaches to corrections In his 1951 Ph. D. thesis, Castaing laid out two of the approaches that could be used to apply matrix corrections to the data, using his brilliant construct of the K-ratio: • an empirical ‘alpha factor’ correction for binary compounds, where each pair of elements has a pair of constant a-factors representing the effect that each element has upon the other for measured X-ray intensity, and • a more rigorous physical model taking into account absorption and fluorescence in the specimen. This later approach also now includes atomic number effects* and became known as the ZAF correction. • This ZAF has been surplanted in many/most EPMA labs by the “phi-rho-Z” matrix correction (it can be a little confusing, discussed later, as the phrase is used in another context) * Atomic number effect only recognized in 1961 -3 (Scott and Ranzetta; Kirianenko; Archard and Mulvey), in samples with widely different atomic numbers

UW- Madison Geology 777 Z A F In addition to absorption (A) and fluorescence (F), there are two other matrix corrections based upon the atomic number (Z) of the material: one dealing with electron backscattering, the other with electron penetration (or stopping). These deal with corrections to the generation of X-rays. C is composition as wt% element (or elemental wt fraction). We will now go through all these corrections in some detail, starting with the Z correction, which has two parts: the stopping power correction, and the backscatter correction. Note that all these corrections require close attention to exactly what feature’s value is being input: the target (matrix), or the X-ray in question. Heinrich (1990) notes that this multiplicative scheme is not actually correct, as that assumes an ideal linear calibration curve, not justifiable on the physics involved… However, it still is used much (“gives close enough answers many times”. )

UW- Madison Geology 777 Stopping Power Correction Incident electrons lose energy in inelastic interactions with the inner shell electrons of the target. The “stopping power” (energy lost by HV electrons per unit mass penetrated) is not constant but drops with increasing Z. A higher number of X-rays will be produced in higher Z targets. Thus, if the mean Z of the unknown is higher than that of the standard, a downward correction in the composition must be applied. The stopping power correction factor is “S”, and can be approximated by: Reed, 1996, Fig. 8. 6, p. 135 Stopping power of pure elements for 20 ke. V electrons where J=11. 5+ Z and Emean= (E 0+Ec)/2 (J is the mean ionization energy; J, Z and A are of the target, Emean is of the X-ray)

$UW- Madison Geology 777 Backscatter Correction As we discussed earlier, the fraction of high$

UW- Madison Geology 777 Backscatter Correction As we discussed earlier, the fraction of high energy incident elections that are backscattered (h) increases with atomic number. There then will be relatively less incident electrons penetrating into higher Z specimens, resulting in a smaller number of X-rays. Thus, if the mean Z of the unknown is higher than that of the standard, a upward correction in the composition must be applied. The backscatter correction factor is “R”. Reed, 1996, Fig. 2. 11, p. 17 R can be approximated by where W = Ec/E 0 (the inverse of overvoltage), and Z is of the target, and W is of the X-ray

UW- Madison Geology 777 Z correction The total atomic number correction is formed by multiplication of the R and S of the unknown and standard thusly: Z = Rstd/Runk * Sunk/Sstd Overall the backscatter and the stopping power corrections tend to cancel each other out. But if there is a (small) correction, it is usually in the direction of the backscatter correction.

UW- Madison Geology 777 Beers Law The intensity I of X-rays that pass through a substance are subject to attenuation of their initial intensity I 0 by the material over the distance they travel within the material. The attenuation follows an exponential decay with a characteristic linear attenuation length 1/m, where m is the (linear) absorption coefficient. Beers Law can also be expressed in terms of mass, using density terms: I = I 0 exp -(m/r)(r Z) where (m/r) is the mass absorption coefficient (cm 2/g), r is the material density (g/cm 3), and Z is the distance (cm) Als-Nielsen and Mc. Morrow, 2001, Fig 1. 10, p. 19

UW- Madison Geology 777 Mass Absorption Coefficients Mass absorption coefficients (MACs) have been tabulated* for many X-rays through many substances (though some are extrapolations). They exist as a matrix of numbers: absorption of a particular X-ray line (emitter, e. g. Ga ka) by a absorber or target (e. g. As) will have one value (51. 5). Note that the absorption of As Ka by Ga is a totally different phenomenon with a distinct MAC (221. 4). Emitter = X-ray (here, Ka) Absorber = matrix material *See following discussion Goldstein et al, 1992, p. 750.

UW- Madison Geology 777 Mass Absorption Coefficients Emitter = X-ray (here, Ka) Terminology: “the mass absorption of Ga Ka by As” Question for you: Is the mass absorption of As Ka by Ga the same as the mass absorption of Ga Ka by As? Why or why not? Absorber = matrix material Goldstein et al, 1992, p. 750.

UW- Madison Geology 777 Absorption X-rays produced within the material will be propagated in all directions, and will suffer attenuation in the process. Note that the path length of travel of the X-ray to the spectrometer is z cosecy, where y (psi) is the takeoff angle (cosec = 1/sin). Castaing’s approach was to integrate the Beer’s Law equation over the depth at the given y, producing the absorption correction factor f(c) where c is defined as m cosec y where m is the MAC. The absorption (A) correction is then defined as A= f(c)std / f(c)sample c = “Chi” Reed, 1993, , p. 219 “Photoelectric absorption” is an “all or nothing” process. When it occurs the photon energy kicks out an electron with lower binding energy, and said electron is ejected with the kinetic energy of the photon minus its binding energy.

UW- Madison Geology 777 Absorption To be able to correct for this absorption of the measured X-rays, we need to know how the production of X-rays varies with depth (Z) in the material. The distribution of X-rays generated as a function of depth is known as the f(rz) [phi-rho-z] function, where a “mass depth” parameter is used instead of simple z (bottom right). The f(rz) function is defined as the intensity generated in a thin layer at some depth z, relative to that generated in an isolated layer of the same thickness. This can then be integrated over the total depth where the incident electrons exceed the binding energy for that particular characteristic x-ray. Reed, 1993, p. 219

UW- Madison Geology 777 Absorption One commonly used simplified form (Philibert 1963) was where c = m cosec y , s is a measure of electron absorption and depends on effective electron energy, where The Philibert approximation breaks down, however, at the near surface, creating errors when dealing with low energy light elements, and we need to go to more complicated and accurate forms of the f(rz) function.

UW- Madison Geology 777 f(rz) [phi-rho-z] Curves To be able to correct properly for absorption -particularly for light elements, the exact shape of the f(rz) [phi-rho-z] curve must be known. Each X-ray has its own curve. There are 3 main parameters that affect the shape of the curve: • E 0 (accelerating voltage) • Ec (critical excitation energy of a particular element line • mean Z of the material Reed, 1993, p. 220

UW- Madison Geology 777 Tracer Method The f(rz) [phi-rho-z] curves are usually determined by the “tracer method”, where successive layers are deposited by vacuum evaporation. The tracer layer B is deposited atop substrate A, with successive layers of A deposited on top. Characteristic X-rays from the tracer element are measured (“emitted”) and then a generation curve is calculated by correcting each step for absorption and fluorescence effects Artistic license?

UW- Madison Geology 777 Fluorescence Correction The X-rays produced within a specimen have the potential for producing a second generation of X-rays: this is secondary fluorescence, generally shortened to fluorescence. This occurs when the characteristic X-ray has an energy greater than the absorption edge energy of another element present in the specimen. As we saw earlier, Ni Ka (7. 48 ke. V) is able to fluoresce Fe Ka (Ec 7. 11 ke. V). This effect is maximized when there is a small amount of the fluoresced element present, e. g. Fe in a Ni-Fe alloy. Reed gives an example where the Fe intensity is 142% of what it “should be”. Also, the continuum above an absorption edge also causes fluorescence, although this is generally weak. Reed, 1996, Fig. 8. 10, p. 139

UW- Madison Geology 777 Fluorescence Correction The form of the correction F is where If/Ip is the ratio of emitted X-rays from fluorescence, compared to the X -ray intensity from inner shell ionization. In a compound, this term is summed overall the elements that could fluorescence the element of interest.

UW- Madison Geology 777 Next Generation (>1980): Phi-Rho-Z models We saw above how Castaing, as early as the 1950 s, developed models of x-ray generation and absorption within the target material, and called these curves “phi-rho-Z” curves. Finding proper mathematical models, however, was hard and so simplistic approximations were used. Over time, and particularly with improvements in technology, people desired to use EPMA to measure the “light elements” (B, C, N, O, F) where absorption by the matrix is severe. Increased research as well as development of computing power, led to a new variant, where the “Z” correction is subsumed within the Phi-Rho-Z paradigm. Additionally, more experiments occurred to determine more correct mass absorption coefficients for the light elements.

UW- Madison Geology 777 Next Generation (>mid 1980 s): Phi-Rho-Z models Names you will see in regards to these models: “PAP” – Jean-Louis Pouchou and Francoise Pichoir (and ‘simplified’ version = XPP) “PROZA” – Guillaume Bastin “X-PHI” – Claude Merlet

UW- Madison Geology 777 How do EPMA theoriticians ‘prove’ their matrix correction is “correct”? Example: Here, use 826 “high quality” x-ray K-ratio data (element pairs) to show that a given matrix correction provides the correct answer (= the actual binary composition)

UW- Madison Geology 777 How do EPMA theoriticans ‘prove’ their matrix correction is “correct”? Here, in a 1991 book, Pouchou and Pichoir show compare their “PAP” matrix correction to a ZAF version. Note that both contain not an insignificant number of data >5% error, and a heck of a lot >2% error. And these are binary compounds.

UW- Madison Geology 777

UW- Madison Geology 777 Fluorescence Problems Secondary fluorescence is an important issue that must be appreciated. Generated X-rays are not scattered nearly as much as incident electrons, and thus the generated X-rays can travel relatively long distances (50 um in Fig 3. 49) within the specimen and produce a second generation of Xrays. If the specimen (and standards) are relatively large (=homogeneous), this is not a problem. However, if minor or trace elements are being analyzed in small grains (Phase 1 in Fig 16. 10) and the host phase (2) has high abundance, an error may be made in the EPMA analysis. Goldstein et al. p. 142; Reed 1993, p. 258

UW- Madison Geology 777 Fluorescence across boundaries Secondary fluorescence is a potential source of analytical error across linear boundaries, either horizontal (e. g. thin films) or vertical (e. g. , diffusion couples). In the example here of a vertical interface between untreated Cu and Co, there is NO diffusion. However, the resulting EPMA profiles clearly imply there is diffusion. There is NO diffusion – there is only secondary fluorescence across the boundary. Cu Ka X-rays can excite Co, to the extent that there is apparently 1 wt% Co about 15 um away from the boundary within the Cu. But Co Ka cannot excite Cu, so only the continuum X-rays can create secondary fluorescence, which is less – but certainly distinguishable, an apparent 0. 5 wt% Cu at 10 um from the boundary in the Co. Reed 1993, p. 259 -260 “false Co” Cu “false Cu” Co

UW- Madison Geology 777 An SF real story Another lab reported 10 wt% Nb (below) in what should have been Nb-free phase (by EDS at 30 k. V). The issue was small grain size and nearby Nb (right image) When I ran WDS (18 k. V) I found essentially zero Nb -- what is the problem? The original researchers used Nb Ka because, with EDS, it is impossible to resolve Nb La (it sits between Al Ka, Hf Ma and Pd La). Fournelle, Kim and Perepezko (2005) Above: EDS spectrum on Pd 2 Hf. Al 5 um away from Nb. Pd Ka is very efficient at traveling across the border and exiting the Nb

UW- Madison Geology 777 Secondary Fluorescence Correction A recent article (below left) reports an innovative approach to correcting the secondary fluorescence (SF) in diffusion couples and from adjacent phases. This utilizes a complex Monte Carlo program called PENELOPE (Penetration and Energy Loss of Positrons and Electrons) that permits complicated geometric models of electron and X-ray behavior in materials. SF can be simulated in a model that represents the actual specimen (e. g. Fig 1 below), and then subtracted from the observed data (right figure).

UW- Madison Geology 777 Matrix Correction Programs The raw X-ray intensities are first corrected for: • background contribution • beam drift (i. e. counts are normalized) • deadtime • interferences* (if appropriate) and then the K-ratios are input into an automated matrix correction program. To run, the correction calculations must assume an initial composition for the unknown -- because the magnitude of each factor is proportional to the abundance of the element times its correction in a pure end member. The assumed composition is a normalized (to 100%) value of the K-ratio. Based upon the first iteration with this assumed composition, the result gives a more truer composition, which then is the input for the second iteration. The process is iterated until convergence, usually 3 -5 times. * Probe for EPMA does the interference correction within the matrix correction, a far better approach compared to the normal (antiquainted) procedure of correcting the data after the matrix correction is completed.

UW- Madison Geology 777 ZAF options One currently widely used matrix correction program is CITZAF, developed by John Armstrong (then CIT, now at Carnegie Institution in DC) and implemented in our Probe for Windows software. There are several options, which we elucidate here, but that generally we do not modify them from the default values. Probably the only parameter you would ever modify would be mass absorption coefficients (there are different ones for the light elements).

UW- Madison Geology 777 Alpha correction In the early decades of probing when computer power was negligible, the alpha correction technique was widely used, as it required less number crunching and relied mainly on empirical data and less on complex physical models and physics. Today, however, there may be a rekindled interest in this approach, as it may “work better” in many cases.

Geology 777 Ziebold and Ogilvie binary a-factors In 1963 -4, Ziebold and Ogilvie* developed a corrections for some binary metal alloys, with an equation in the form = C 2 = K 2 where a 12 is the a-factor for element 1 in the binary with element 2, K is the K-ratio, and composition (fractional) is C. This equation can be rearranged in the form If experimental data exist for binary alloys, then a plot of C 1/K 1 versus C 1 is a straight line with a slope of (1 - a 12), leading to determination of a 12. Such a hyperbolic relationship between C 1 and K 1 was shown to be correct for several alloy and oxide systems, but it was difficult to find appropriate intermediate compositions for many binary systems. *Quantitative Analysis with the Electron Microanalyzer, Analytical Chemistry, Vol 35, May 1963, p. 621 -627; An Empirical Method for Electron Microanalysis, Analytical Chemistry, Vol 36, Feb. 1964, p. 322 -327.

UW- Madison Geology 777 Ziebold and Ogilvie ternary a-factors Ziebold and Ogilvie showed that a corrections could be developed for some ternary metal alloys, with an equation in the form where a 123 is the a-factor for element 1 in the ternary with elements 2 and 3, and is defined as This equation can be rearranged Similar relationships can be written for elements 2 and 3, and used to calculate a-factors for the 3 binary systems of the ternary. These a-factors were limited to a particular E 0 and takeoff angle.

UW- Madison Geology 777 Bence-Albee multicomponent systems Bence and Albee* in 1968 showed that this approach could be extended to silicates and other minerals, i. e. a system of n components, where for the nth component a b-factor could be found where an 1 is the a-factor for the n 1 binary. These factors were determined for a limited set of conditions, i. e. 15 and 20 ke. V, and take off angles of 52. 5° and 38. 5°. The 1968 Bence and Albee paper is one of the most highly cited papers in the geological literature (over ~20, 000 citations). * Empirical correction factors for the electron microanalysis of silicates and oxides, J. Geology, Vol. 76, p. 382 -403; also see Albee and Ray, Correction Factors for Electron Probe Microanalysis of Silicates, Oxides, Carbonates, Phosphates, and Sulfates, Analytical Chemistry, Vol 42, Oct 1970, p. 1408 -1414.

UW- Madison Geology 777 Evaluating matrix corrections In 1988, John Armstrong* reviewed the Bence-Albee (a-factor) correction scheme for EPMA of oxide and silicate minerals. He evaluated the old factors, and revised some, using a -factors calculated from newer ZAF and f(rz) algorithms, and showed “that with some modifications the a -factor corrections can be as accurate as any other correction procedure currently available and much easier and quicker to process. ” *Bence-Albee after 20 years: review of the accuracy of a-factor correction procedures for oxide and silicate minerals, in Microbeam Analysis-1988, p. 469 -76. Armstrong also reviewed† ZAF and f(rz) corrections and suggested that some of these correction algorithms “produce poorer results in the analysis of silicate and oxide minerals than some of the earlier corrections”. He specifically was referring to various corrections that were optimized for metal alloys † Quantitative analysis of silicate and oxide materials: comparison of Monte Carlo, ZAF and f(rz) procedures, in Microbeam Analysis-1988, p. 239+

UW- Madison Geology 777 Before we forget. . Unanalyzed elements The matrix corrections assume that all elements present (and interacting with the X-rays) will be included. There are situations, however, where either an element cannot be measured, or not easily, and thus the analyst must make explicit in the quantitative setup the presence of unanalyzed element/s -- and how they are to be input into the correction. Typically oxygen (in silicates) is calculated “by stoichometry”. Elements can also be defined in set amounts, or relative proportions, or “by difference” – although this later method is somewhat dangerous as it assumes that there are no other elements present.

UW- Madison Geology 777 Unanalyzed oxygen, carbon, etc Oxygen is a major part of many materials (e. g. silicate minerals and glasses). Carbon is a major part of carbonates. Oxygen and carbon are typically not “acquired” (measured directly) in many EPMA procedures, BUT THEY MUST BE SOMEHOW INCLUDED IN THE MATRIX CORRECTION. If oxygen (and say C in carbonates) is not included, there will be errors in the matrix corrections of some elements, as the presence these elements affects the electron (and x-ray behavior), e. g. , the backscattered % of incident HV electrons will be different, and there may be absorption of those x-rays by the oxygen (and C) present. In the next slides, we see the effect on a measurement of a carbonate sample: first, with just the cations; then with just Oxygen added; finally with both Oxygen and Carbon.

UW- Madison Geology 777 First: how you do it For a carbonate 1. Declare C and O as elements in the analysis (but not measured) 2. Tell it to calculate with stoichiometric oxygen 3. Create a rule so that there is 1 atom of C to every 3 atoms of O 4. Check: display results on basis of 3 atoms of oxygen (perfect result would be 5. 000 total atoms, and grand total of 100 wt%

UW- Madison Geology 777 Good, Bad, Ugly …. Carbonate by EPMA First, if only cations used for ZAF … If both O and C included in the ZAF Next, oxygen only included … Notice the differences in the final values of the elements (wt%)

UW- Madison Geology 777 Unanalyzed oxygen One complication for oxygen is variable valence states of elements such as Fe. Robust software will allow you to enter case by case different valence states. In some cases, if oxygen is not included, there can be errors in the matrix corrections of some elements, as the presence of O, OH, and H 2 O can affect the actually measured elements, as there may be significant absorption of those x-rays by the oxygen present*. * Tingle, T. N. , Neuhoff, P. , Ostgergren, P. , Jones, R. E. and Donovan, J. J. (1996) The effect of “missing” unanalyzed oxygen on quantitative electron probe microanalysis of hydrous silicate and oxide minerals. GSA Abstracts, 28, 212.

UW- Madison Geology 777 Impact of unaccounted for oxygen Consider: Apophyllite -- KCa 4 Si 8 O 20(F, OH) • 8 H 2 O Which has LOTS of oxygen which typically is “unanalyzed” and therefore not involved in the matrix correction Solution: Iterate a fixed amount of H 2 O (16 atoms of H = 1. 76 wt% H plus stoichometric O) per formula to achieve good results. As shown in the bottom analysis where the H 2 O is missing, there is up to 3% relative error for cations.

UW- Madison Geology 777 Physical Parameters Needed The ZAF corrections require accurate and precise knowledge about many physical parameters, such as • Electron stopping power • Mean ionization potentials • Backscatter coefficients • X-ray Ionization cross sections • Mass absorption coefficients • Surface ionization potentials • Fluorescent yields

UW- Madison Geology 777 “State of EPMA parameters” As David Joy points out in his 2001 article “Constants for Microanalysis”, there are problems in our knowledge of many parameters: • there are experimental stopping power profiles for 12 elements and 12 compounds, which raise questions about the traditional Bethe equation • only half of the elements whose K lines are used for EPMA have measured K shell ionization cross-sections ; only 6 elements have measured L shell cross-sections; there are zero M shell cross-sections • K shell fluorescent yields are the best documented parameters; there are gaps in the data for L shell yields; there are only 5 measured M shell yields • despite the fact that backscatter coefficients have been measured for 100 years, the data has many gaps and is of poor precision (i. e. 30%)

UW- Madison Geology 777 At the Eugene EPMA workshop in September 2003, John Armstrong reviewed the state of EPMA matrix corrections • Big problem with software/manufacturers, not documenting which corrections used. Some have picked "improved" parameters which do not fit with the other parameters, e. g. in some, where no formal fluorescence correction, the absorption correction was tweaked to take fluor into account, and then when later fluorescence corrections developed, to use this in addition to absorption correction, has an overcorrection for fluorescence. • Problem with researchers not stating in their publications which correction they used; NIST is trying to develop some protocols which people can reference (brief notation with pointer to NIST for full description). • There a few errors/typos in the long accepted X-ray tables (i. e. , Bearden) – 3 are major errors. • Actually measured mass absorption factors are rare! Measurements exist for Na Ka by Al; Si Ka by Al and Ni; Mg Ka by O, Al, Ti and Ni; and Al Ka by O, Na. . . • There is over 30% variation in published values of some macs for geologically relevant elements; they can’t all be correct!

UW- Madison Geology 777 “So what do we do? ” We have discussed various ways to correct the raw data, the goal being to come up with the most accurate and precise analytical procedures to give us the most trustworthy data. We have just mentioned that everything is not as rosy as one would hope. So, can we trust the numbers we get out of the probe? In many/most cases, given care, yes. But we cannot blindly look at the electron probe and computer as a black box! Stay tuned for an upcoming installment, where we discuss standards, accuracy and precision in EPMA.