Here's a good one: have you ever noticed that each time you "analyze" (calculate the composition of) a standard as an unknown the program takes extra time to reload all the drift arrays? It's because the standard probably has different elements from the previous analysis because the program automatically adds in elements that are present in the standard but not analyzed in the current setup. For example, a trace Pb in the REE stds when analyzing for REEs and P only.
You can eliminate 99% of that overhead by simply specifying all the unanalyzed elements in the standards to all standard samples from the Analyze! Elements/Cations button. Any element entered without an x-ray line is treated as a specified element.
Once this is done, when "analyzing" standard samples as unknowns, the program will automatically load the unanalyzed element concentrations as usual, but since the element setup will be the same for all standards, the calculations will proceed much quicker! 8)
We've had a rash of "flashovers" in our gun this week, each time killing the instrument electronics and vacuum. We've now tried cleaning the gun HV insulator and so far so good.
But when this event occurred, both the PeakSight and Probe for EPMA (and Thermo) software are locked up (because there's nothing for them to talk to I guess!), and we have to use the Task manager on both computers to kill the open apps. I also log out on each computer to make sure the driver instances get unloaded completely (but a full re-boot isn't necessary it seems).
Anyway, once we get the instrument electronics re-set and the PeakSight software started and the instrument has finished its self test, you might note that some buttons are "grayed out" in PFE. For example, the Faraday button may be "grayed out" if the stage was moving when the "flashover" occurred as seen here:
(https://smf.probesoftware.com/oldpics/i40.tinypic.com/2a6wc8w.jpg)
To reset these buttons, simply click the Free/Clear button in the Move window as seen here:
(https://smf.probesoftware.com/oldpics/i44.tinypic.com/wqopdi.jpg)
and all will be ok.
For those who enjoy details, this button press is equivalent to deleting the process.dat file, which is used for sharing information between the different Probe Software applications.
Here's a useful tip that some might not be aware of...
Everyone knows that one can display the acquired analysis positions on analog signal images captured in Probe for EPMA using the Run | Display, Annotate and Export Analog Signal Images menu. And that one can also label the analysis positions with the sample number and analysis number or just the analysis number as shown here:
(https://smf.probesoftware.com/oldpics/i39.tinypic.com/9k5co8.jpg)
Note that the size of the circles depicting the analysis positions are drawn to show the beam size of the analysis points. In this case 5 um.
But did you also know that one can determine the distance from objects visible in the image by simply clicking and dragging the mouse on the image as seen here?
(https://smf.probesoftware.com/oldpics/i42.tinypic.com/9k2cgk.jpg)
Here's a handy trick.
If you only want to output a few selected samples- or even just one sample- using one of the output formats, for example the User Specified Format Output, simply select the sample (standard or unknowns) and right click the Analyze! sample list and you will be presented with this menu:
(https://smf.probesoftware.com/oldpics/i44.tinypic.com/r0zcw9.jpg)
Here's another right click feature, but this time from the Automate! window. Simply select the position sample or samples and right click the Automate! position list and you can perform a number of interesting functions.
For example, edit a position sample name!
(https://smf.probesoftware.com/oldpics/i44.tinypic.com/2qxxez4.jpg)
You can get similar functionality from the Position Database window:
(https://smf.probesoftware.com/oldpics/i41.tinypic.com/2evdfr7.jpg)
This isn't so much a tip or trick post as it is an "under the hood" tutorial, so here goes.
If you've ever wanted more details about your quantitative analysis, the first thing to utilize is the List Report button in the Analyze! window, which nicely summarizies the standard intensity acquisition sets for your run. This is explained further in this post:
http://smf.probesoftware.com/index.php?topic=168.msg725#msg725
But for even more details, simply click the Output | Debug Mode menu in PFE and try some data or analysis functions. Here is an example of the Data button in "DebugMode". Most of the output is self explanatory I think, but with some explanation in red:
St 467 Set 2 Hornblende (Arenal) USNM 111356
(Magnification (analytical) = 20000), Beam Mode = Analog Spot
(Magnification (default) = 2524, Magnification (imaging) = 736)
Image Shift (X,Y): -2.00, 3.00
Analysis (wet chemistry) by Gene Jarosewich
Number of Data Lines: 5 Number of 'Good' Data Lines: 5
First/Last Date-Time: 11/26/2013 03:43:20 PM to 11/26/2013 03:53:12 PM
Stage (or Beam Deflection) Coordinate Positions:
X Y Z X Y Z
136G 20889.52 -3242.255 .000000000 137G 20893.47 -3242.244 .000000000
138G 20897.50 -3242.259 .000000000 139G 20901.50 -3242.245 .000000000
140G 20905.54 -3242.253 .000000000
On and Off Peak Positions:
ELEM: na ka si ka k ka al ka mg ka fe ka ca ka s ka cl ka ti ka p ka f ka
ONPEAK 46267.0 81466.0 42614.0 32507.0 38401.0 48102.0 38423.0 61432.0 53911.0 68290.0 24051.0 71137.0
OFFSET 95.8477 -11.523 162.785 -41.074 98.1523 13.3867 -23.414 -16.410 139.859 1.39844 -79.539 177.828
HIPEAK ---- ---- 43422.5 ---- ---- ---- ---- 61934.1 54623.5 68781.5 25462.6 72529.0
LOPEAK ---- ---- 41935.1 ---- ---- ---- ---- 60684.5 53300.2 67865.3 23294.2 69800.0
HI-OFF ---- ---- 808.500 ---- ---- ---- ---- 502.102 712.500 491.500 1411.60 1392.00
LO-OFF ---- ---- -678.90 ---- ---- ---- ---- -747.50 -610.80 -424.70 -756.80 -1337.0
Multi-Point Background Positions and Parameters:
ELEM: na ka si ka k ka al ka mg ka fe ka ca ka s ka cl ka ti ka p ka f ka
MULHI: ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
MULHI: ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
MULHI: ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
MULHI: ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
MHIOFF ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
MHIOFF ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
MHIOFF ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
MHIOFF ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
ELEM: na ka si ka k ka al ka mg ka fe ka ca ka s ka cl ka ti ka p ka f ka
MULLO: ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
MULLO: ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
MULLO: ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
MULLO: ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
MLOOFF ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
MLOOFF ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
MLOOFF ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
MLOOFF ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
ELEM: na ka si ka k ka al ka mg ka fe ka ca ka s ka cl ka ti ka p ka f ka
MACQHI ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
MACQLO ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
MUITHI ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
MUITLO ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
MULFIT ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
PHA Parameters:
ELEM: na ka si ka k ka al ka mg ka fe ka ca ka s ka cl ka ti ka p ka f ka
DEAD: 3.00 3.25 3.31 2.90 3.00 2.97 3.25 3.25 3.31 2.97 2.90 3.00
BASE: .56 .50 .56 .56 .56 .56 .56 .50 .56 .56 .56 .56
WINDOW 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00 4.00
MODE: -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1 -1
GAIN: 2321. 960. 1181. 2241. 2321. 600. 700. 960. 992. 700. 1471. 2321.
BIAS: 1300. 1330. 1850. 1293. 1300. 1840. 1330. 1330. 1850. 1840. 1293. 1320.
Last (Current) On and Off Peak Count Times:
ELEM: na ka si ka k ka al ka mg ka fe ka ca ka s ka cl ka ti ka p ka f ka
BGD: MAN MAN OFF MAN MAN MAN MAN OFF OFF OFF OFF OFF
BGDS: MAN MAN LIN MAN MAN MAN MAN LIN LIN LIN EXP LIN
BRAGG: 1 1 1 1 1 1 1 1 1 1 1 1
SPEC: 1 2 3 4 1 5 2 2 3 5 4 1
CRYST: TAP LPET LPET TAP TAP LIF LPET LPET LPET LIF TAP TAP
CRY2D: 25.7450 8.7500 8.7500 25.7450 25.7450 4.0267 8.7500 8.7500 8.7500 4.0267 25.7450 25.7450
CRYK : .002180 .000144 .000144 .002180 .002180 .000058 .000144 .000144 .000144 .000058 .002180 .002180
ORDER: 1 1 1 1 2 1 2 3 2 2 2 3
ONTIM: 30.00 30.00 20.00 40.00 30.00 40.00 20.00 20.00 20.00 20.00 20.00 20.00
HITIM: ---- ---- 10.00 ---- ---- ---- ---- 5.00 5.00 5.00 5.00 10.00
LOTIM: ---- ---- 10.00 ---- ---- ---- ---- 5.00 5.00 5.00 5.00 10.00
Miscellaneous Sample Acquisition/Calculation Parameters:
KILO: 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00 15.00
ENERGY 1.041 1.740 3.313 1.487 1.254 6.400 3.691 2.308 2.622 4.509 2.013 .677
EDGE: 1.073 1.839 3.608 1.560 1.305 7.112 4.039 2.472 2.823 4.967 2.146 .687
Eo/Ec: 13.98 8.16 4.16 9.62 11.49 2.11 3.71 6.07 5.31 3.02 6.99 21.83 <- overvoltage
STDS: 336 162 374 160 162 162 162 730 285 22 285 284
INTE: 0 0 0 0 0 0 0 0 0 0 0 0 <- integrated intensity scan info
INTEIN --- --- --- --- --- --- --- --- --- --- --- ---
INTEMI --- --- --- --- --- --- --- --- --- --- --- ---
Combined Analytical Condition Arrays:
ELEM: na ka si ka k ka al ka mg ka fe ka ca ka s ka cl ka ti ka p ka f ka
TAKE: 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0
KILO: 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0
CURR: 10.0 10.0 10.0 10.0 10.0 10.0 10.0 50.0 50.0 50.0 50.0 50.0
SIZE: 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0
Specified (Fixed) Concentrations:
ELEM: o h
ELWT: .000 .000
Faraday/Aperture Beam Currents:
ELEM: na ka si ka k ka al ka mg ka fe ka ca ka s ka cl ka ti ka p ka f ka
136G 9.994 9.994 9.994 9.994 9.994 9.994 9.994 49.994 49.994 49.994 49.994 49.994
137G 9.988 9.988 9.988 9.988 9.988 9.988 9.988 49.983 49.983 49.983 49.983 49.983
138G 10.011 10.011 10.011 10.011 10.011 10.011 10.011 49.975 49.975 49.975 49.975 49.975
139G 9.999 9.999 9.999 9.999 9.999 9.999 9.999 49.989 49.989 49.989 49.989 49.989
140G 10.005 10.005 10.005 10.005 10.005 10.005 10.005 50.002 50.002 50.002 50.002 50.002
AVER: 9.999 9.999 9.999 9.999 9.999 9.999 9.999 49.989 49.989 49.989 49.989 49.989
SDEV: .009 .009 .009 .009 .009 .009 .009 .011 .011 .011 .011 .011
On-Peak (off-peak corrected) or MAN On-Peak X-ray Counts (cps/1nA) (and Faraday Current):
ELEM: na ka si ka k ka al ka mg ka fe ka ca ka s ka cl ka ti ka p ka f ka
BGD: MAN MAN OFF MAN MAN MAN MAN OFF OFF OFF OFF OFF
SPEC: 1 2 3 4 1 5 2 2 3 5 4 1
CRYST: TAP LPET LPET TAP TAP LIF LPET LPET LPET LIF TAP TAP
CRY2D: 25.7450 8.7500 8.7500 25.7450 25.7450 4.0267 8.7500 8.7500 8.7500 4.0267 25.7450 25.7450
CRYK : .00218 .00014 .00014 .00218 .00218 .00006 .00014 .00014 .00014 .00006 .00218 .00218 <- Bragg crystal refractive index
ORDER: 1 1 1 1 2 1 2 3 2 2 2 3
136G 8.46 148.88 1.53 58.09 56.98 78.59 79.51 -.03 -.05 1.40 -.01 -.01
137G 8.10 149.56 1.88 58.31 58.09 77.35 80.42 .00 -.03 1.40 -.04 -.03
138G 8.18 149.22 1.51 58.47 57.96 78.06 80.08 -.01 .03 1.45 .00 .02
139G 8.06 149.32 1.56 58.14 57.40 78.35 79.83 .00 -.09 1.43 -.05 .00
140G 8.15 149.39 1.80 58.64 57.27 78.28 78.58 .00 .03 1.44 .00 .00
AVER: 8.19 149.27 1.66 58.33 57.54 78.13 79.68 -.01 -.02 1.42 -.02 .00
SDEV: .16 .25 .17 .23 .47 .47 .70 .01 .05 .02 .02 .02
1SIG: .17 .70 .16 .38 .44 .44 .63 .02 .03 .04 .02 .01
SIGR: .96 .36 1.06 .60 1.08 1.07 1.11 .65 1.89 .51 1.07 1.52
SERR: .07 .11 .08 .10 .21 .21 .31 .01 .02 .01 .01 .01
%RSD: 1.94 .17 10.47 .39 .82 .60 .88 -185.47 -231.91 1.57 -97.90-1552.33
Off-Peak (calculated) X-ray Counts (cps/1nA):
ELEM: na ka si ka k ka al ka mg ka fe ka ca ka s ka cl ka ti ka p ka f ka
TYPE: NONE NONE LINEAR NONE NONE NONE NONE LINEAR LINEAR LINEAR EXPONEN LINEAR <- off peak correction type (none= MAN)
COEF1: ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- 2.0000 ----
COEF2: ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
COEF3: ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
136G ---- ---- 3.74 ---- ---- ---- ---- .57 .72 .50 .38 .13 <- these are the interpolated off-peak intensities for each data point
137G ---- ---- 3.57 ---- ---- ---- ---- .50 .71 .48 .40 .14
138G ---- ---- 3.79 ---- ---- ---- ---- .56 .68 .50 .36 .11
139G ---- ---- 3.71 ---- ---- ---- ---- .52 .75 .46 .40 .12
140G ---- ---- 3.60 ---- ---- ---- ---- .52 .67 .48 .38 .12
AVER: ---- ---- 3.68 ---- ---- ---- ---- .53 .71 .48 .38 .12
SDEV: ---- ---- .09 ---- ---- ---- ---- .03 .03 .02 .02 .01
SERR: ---- ---- .04 ---- ---- ---- ---- .01 .01 .01 .01 .00
%RSD: ---- ---- 2.47 ---- ---- ---- ---- 5.82 4.47 3.72 3.95 8.00
Raw On-Peak X-ray Count Times:
ELEM: na ka si ka k ka al ka mg ka fe ka ca ka s ka cl ka ti ka p ka f ka Date and Time
136G 30.00 30.00 20.00 40.00 30.00 40.00 20.00 20.00 20.00 20.00 20.00 20.00 11/26/2013 3:43:20 PM
137G 30.00 30.00 20.00 40.00 30.00 40.00 20.00 20.00 20.00 20.00 20.00 20.00 11/26/2013 3:45:48 PM
138G 30.00 30.00 20.00 40.00 30.00 40.00 20.00 20.00 20.00 20.00 20.00 20.00 11/26/2013 3:48:16 PM
139G 30.00 30.00 20.00 40.00 30.00 40.00 20.00 20.00 20.00 20.00 20.00 20.00 11/26/2013 3:50:44 PM
140G 30.00 30.00 20.00 40.00 30.00 40.00 20.00 20.00 20.00 20.00 20.00 20.00 11/26/2013 3:53:12 PM
AVER: 30.00 30.00 20.00 40.00 30.00 40.00 20.00 20.00 20.00 20.00 20.00 20.00 11/26/2013 3:48:16 PM
Actual Elapsed Acquisition Time (seconds) For On-Peak X-ray Counting:
ELEM: na ka si ka k ka al ka mg ka fe ka ca ka s ka cl ka ti ka p ka f ka
136G 30.00 30.00 20.00 40.00 30.00 40.00 20.00 20.00 20.00 20.00 20.00 20.00
137G 30.00 30.00 20.00 40.00 30.00 40.00 20.00 20.00 20.00 20.00 20.00 20.00
138G 30.00 30.00 20.00 40.00 30.00 40.00 20.00 20.00 20.00 20.00 21.00 20.00
139G 30.00 30.00 20.00 40.00 30.00 40.00 20.00 20.00 20.00 20.00 20.00 20.00
140G 30.00 30.00 20.00 40.00 30.00 40.00 20.00 20.00 20.00 20.00 20.00 20.00
AVER: 30.00 30.00 20.00 40.00 30.00 40.00 20.00 20.00 20.00 20.00 20.20 20.00
Raw On-Peak X-ray Counts (cps/1nA) (and Faraday Current):
ELEM: na ka si ka k ka al ka mg ka fe ka ca ka s ka cl ka ti ka p ka f ka
136G 8.46 148.88 5.27 58.09 56.98 78.59 79.51 .54 .67 1.90 .37 .12 .000
137G 8.10 149.56 5.46 58.31 58.09 77.35 80.42 .50 .68 1.88 .36 .11 .000
138G 8.18 149.22 5.30 58.47 57.96 78.06 80.08 .55 .71 1.95 .36 .13 .000
139G 8.06 149.32 5.26 58.14 57.40 78.35 79.83 .52 .67 1.89 .35 .13 .000
140G 8.15 149.39 5.40 58.64 57.27 78.28 78.58 .52 .70 1.92 .37 .12 .000
AVER: 8.19 149.27 5.34 58.33 57.54 78.13 79.68 .53 .69 1.91 .36 .12
SDEV: .16 .25 .09 .23 .47 .47 .70 .02 .02 .03 .01 .01 <- calculated (measured) standard deviations
1SIG: .17 .70 .16 .38 .44 .44 .63 .02 .03 .04 .02 .01 <- predicted variance (one sigma)
SIGR: .96 .36 .53 .60 1.08 1.07 1.11 .95 .74 .66 .51 .69 sigma ratio (measured SD divided by predicted SD)
SERR: .07 .11 .04 .10 .21 .21 .31 .01 .01 .01 .00 .00 <- standard error (variance of the average)
%RSD: 1.94 .17 1.63 .39 .82 .60 .88 4.13 2.84 1.50 2.65 6.21 <- % relative standard deviation (SD divided by average times 100)
Raw Hi-Peak X-ray Count Times:
ELEM: na ka si ka k ka al ka mg ka fe ka ca ka s ka cl ka ti ka p ka f ka
136G ---- ---- 10.00 ---- ---- ---- ---- 5.00 5.00 5.00 5.00 10.00
137G ---- ---- 10.00 ---- ---- ---- ---- 5.00 5.00 5.00 5.00 10.00
138G ---- ---- 10.00 ---- ---- ---- ---- 5.00 5.00 5.00 5.00 10.00
139G ---- ---- 10.00 ---- ---- ---- ---- 5.00 5.00 5.00 5.00 10.00
140G ---- ---- 10.00 ---- ---- ---- ---- 5.00 5.00 5.00 5.00 10.00
AVER: ---- ---- 10.00 ---- ---- ---- ---- 5.00 5.00 5.00 5.00 10.00
Raw Hi-Peak X-ray Counts (cps/1nA):
ELEM: na ka si ka k ka al ka mg ka fe ka ca ka s ka cl ka ti ka p ka f ka
136G ---- ---- 3.86 ---- ---- ---- ---- .56 .72 .54 .41 .14
137G ---- ---- 3.70 ---- ---- ---- ---- .52 .70 .51 .40 .14
138G ---- ---- 3.84 ---- ---- ---- ---- .55 .72 .52 .33 .11
139G ---- ---- 3.74 ---- ---- ---- ---- .54 .75 .46 .42 .11
140G ---- ---- 3.44 ---- ---- ---- ---- .49 .74 .50 .34 .11
AVER: ---- ---- 3.72 ---- ---- ---- ---- .53 .73 .51 .38 .12
SDEV: ---- ---- .17 ---- ---- ---- ---- .03 .02 .03 .04 .02
1SIG: ---- ---- .19 ---- ---- ---- ---- .05 .05 .04 .04 .02
SIGR: ---- ---- .86 ---- ---- ---- ---- .56 .30 .64 1.09 1.12
SERR: ---- ---- .07 ---- ---- ---- ---- .01 .01 .01 .02 .01
%RSD: ---- ---- 4.48 ---- ---- ---- ---- 4.86 2.22 5.67 11.17 14.48
Raw Lo-Peak X-ray Count Times:
ELEM: na ka si ka k ka al ka mg ka fe ka ca ka s ka cl ka ti ka p ka f ka
136G ---- ---- 10.00 ---- ---- ---- ---- 5.00 5.00 5.00 5.00 10.00
137G ---- ---- 10.00 ---- ---- ---- ---- 5.00 5.00 5.00 5.00 10.00
138G ---- ---- 10.00 ---- ---- ---- ---- 5.00 5.00 5.00 5.00 10.00
139G ---- ---- 10.00 ---- ---- ---- ---- 5.00 5.00 5.00 5.00 10.00
140G ---- ---- 10.00 ---- ---- ---- ---- 5.00 5.00 5.00 5.00 10.00
AVER: ---- ---- 10.00 ---- ---- ---- ---- 5.00 5.00 5.00 5.00 10.00
Raw Lo-Peak X-ray Counts (cps/1nA):
ELEM: na ka si ka k ka al ka mg ka fe ka ca ka s ka cl ka ti ka p ka f ka
136G ---- ---- 3.64 ---- ---- ---- ---- .59 .72 .47 .37 .13
137G ---- ---- 3.47 ---- ---- ---- ---- .47 .72 .45 .40 .13
138G ---- ---- 3.74 ---- ---- ---- ---- .58 .65 .49 .39 .11
139G ---- ---- 3.68 ---- ---- ---- ---- .48 .76 .46 .39 .14
140G ---- ---- 3.74 ---- ---- ---- ---- .56 .62 .45 .40 .13
AVER: ---- ---- 3.65 ---- ---- ---- ---- .53 .69 .46 .39 .13
SDEV: ---- ---- .11 ---- ---- ---- ---- .06 .06 .01 .02 .01
1SIG: ---- ---- .19 ---- ---- ---- ---- .05 .05 .04 .04 .02
SIGR: ---- ---- .58 ---- ---- ---- ---- 1.29 1.08 .34 .38 .56
SERR: ---- ---- .05 ---- ---- ---- ---- .03 .03 .01 .01 .00
%RSD: ---- ---- 3.06 ---- ---- ---- ---- 11.14 8.20 3.18 3.88 6.99
If there is any output that is unclear please post your questions.
The Debug Mode output for quantitative analysis is more extensive than the raw data output. For example here is the same sample calculated with a matrix correction, but only the first data point for brevity:
MAN fit data and coefficients for na <- The MAN fits for each element are loaded first
Order 2, npts 5
StdAss: 730 162 285 14 22 <- these are the MAN standard assignments for this element
Z-bars: 20.6647 13.2274 14.4794 10.8047 16.3920 <- average Z (Z-bar) for each MAN standard
Counts: 1.13750 1.15515 1.19729 1.18332 1.04192 <- the on-peak counts when the element is not present
AbsCor: 2.62949 2.05361 2.06884 1.75421 2.60603 <- the continuum absorption correction
Counts: 2.99104 2.37223 2.47700 2.07580 2.71528 <- the absorption corrected continuum counts
Coeffs: .168259 .219104 -.00398 <- the polynomial fit coefficients for each standard MAN fit
MAN fit data and coefficients for si
Order 2, npts 5
StdAss: 730 285 25 22 12
Z-bars: 20.6647 14.4794 21.1658 16.3920 10.4267
Counts: 4.22185 3.14173 3.92018 3.30528 1.68767
AbsCor: 1.31229 1.17433 1.47618 1.28689 1.57869
Counts: 5.54028 3.68941 5.78688 4.25354 2.66431
Coeffs: .751678 .132178 .004916
MAN fit data and coefficients for al
Order 2, npts 6
StdAss: 730 285 25 273 14 12
Z-bars: 20.6647 14.4794 21.1658 10.5798 10.8047 10.4267
Counts: 2.11352 2.09359 1.73470 1.42870 1.97240 1.14463
AbsCor: 1.52248 1.31384 1.79283 1.61422 1.20535 1.95626
Counts: 3.21779 2.75064 3.11003 2.30623 2.37744 2.23919
Coeffs: .147184 .264489 -.00576
MAN fit data and coefficients for mg
Order 2, npts 6
StdAss: 374 730 25 336 14 22
Z-bars: 11.9907 20.6647 21.1658 11.0372 10.8047 16.3920
Counts: 1.54308 1.56474 1.28124 1.37161 1.53475 1.39727
AbsCor: 1.44002 1.90232 2.36279 1.54794 1.38991 1.87119
Counts: 2.22206 2.97664 3.02730 2.12316 2.13316 2.61456
Coeffs: 1.12783 .093743 -.00020
MAN fit data and coefficients for fe
Order 2, npts 5
StdAss: 285 273 14 22 12
Z-bars: 14.4794 10.5798 10.8047 16.3920 10.4267
Counts: 2.73536 2.19860 2.30321 2.94939 2.26072
AbsCor: 1.02129 .997516 .998913 1.03724 .996548
Counts: 2.79360 2.19314 2.30071 3.05921 2.25292
Coeffs: .704175 .149354 -.00035
MAN fit data and coefficients for ca
Order 2, npts 4
StdAss: 374 730 14 22
Z-bars: 11.9907 20.6647 10.8047 16.3920
Counts: 2.81666 4.98813 2.59977 4.14098
AbsCor: 1.07150 1.11001 1.04570 1.00488
Counts: 3.01805 5.53687 2.71858 4.16120
Coeffs: 1.06978 .085206 .006333
Sample Line Number: 136
Elements:
na si k al mg fe ca s cl ti p f
Element Standards:
336 162 374 160 162 162 162 730 285 22 285 284 <- primary standard assignments
Element Standard K-Factors:
.0735 .2018 .1132 .0334 .0568 .0950 .1027 .5061 .0601 .5547 .1599 .0256
Element Standard Counts (MAN/Interference corrected):
73.52 202.16 113.18 33.45 56.88 95.38 102.74 101.14 12.07 110.89 31.95 5.07 < MAN standards are background corrected here
Element Standard Percents:
12.552 25.382 12.859 4.906 8.847 11.209 11.057 53.450 6.808 59.939 17.843 9.020
Elements:
na si k al mg fe ca s cl ti p f
MAN Assignments:
730 730 0 730 374 285 374 0 0 0 0 0
162 285 0 285 730 273 730 0 0 0 0 0
285 25 0 25 25 14 14 0 0 0 0 0
14 22 0 273 336 22 22 0 0 0 0 0
22 12 0 14 14 12 0 0 0 0 0 0
0 0 0 12 22 0 0 0 0 0 0 0
BackgroundTypes:
1 1 0 1 1 1 1 0 0 0 0 0 <- background correction types (0=off-peak, 1=MAN, 2=Multi-point)
MAN Fit Orders:
2 2 0 2 2 2 2 0 0 0 0 0 <- polynomial fit order (0 = constant, 1 = linear, 2 = 2nd order polynomial)
MAN Absorption Correction Flags:
-1 -1 0 -1 -1 -1 -1 0 0 0 0 0
MAN Counts:
1.14 4.22 .00 2.11 1.54 2.74 2.82 .00 .00 .00 .00 .00
1.16 3.14 .00 2.09 1.56 2.20 4.99 .00 .00 .00 .00 .00
1.20 3.92 .00 1.73 1.28 2.30 2.60 .00 .00 .00 .00 .00
1.18 3.31 .00 1.43 1.37 2.95 4.14 .00 .00 .00 .00 .00
1.04 1.69 .00 1.97 1.53 2.26 .00 .00 .00 .00 .00 .00
.00 .00 .00 1.14 1.40 .00 .00 .00 .00 .00 .00 .00
MAN Fit Coefficients:
.168259 .751678 .000000 .147184 1.12783 .704175 1.06978 .000000 .000000 .000000 .000000 .000000
.219104 .132178 .000000 .264489 .093743 .149354 .085206 .000000 .000000 .000000 .000000 .000000
-.00398 .004916 .000000 -.00576 -.00020 -.00035 .006333 .000000 .000000 .000000 .000000 .000000
Entering AnalyzeWeightCorrect...
Elements:
na si k al mg fe ca s cl ti p f
Uncorrected Unknown Counts:
8.46 148.88 1.53 58.09 56.98 78.59 79.51 -.03 -.05 1.40 -.01 -.01 <- raw unknown intensities
MAN Background Counts on Unknown (based on unknown Z-bar: 10.8)
2.07 2.75 .00 2.33 2.12 2.28 2.73 .00 .00 .00 .00 .00 <- interpolated MAN for unk at specified z-bar (assumes quartz to begin)
Continuum Absorption Correction Factors on Unknown:
1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 <- first iteration of unknown MAN background (no composition yet)
Absorption Correction Factors on Unknown:
1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 <- matrix correction factors for unk (no composition yet)
Fluorescence Correction Factors on Unknown:
1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000
Atomic Number Correction Factors on Unknown:
1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000
ZAF Correction Factors on Unknown:
1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000 1.0000
Disabled Quant Flag (zeroed intensity if set):
0 0 0 0 0 0 0 0 0 0 0 0
Corrected Unknown Counts:
6.39 146.12 1.53 55.75 54.86 76.31 76.79 -.03 -.05 1.40 -.01 -.01 <- first background corrected intensities (MAN and off-peak)
Convergence Difference Counts:
6.39 146.12 1.53 55.75 54.86 76.31 76.79 .03 .05 1.40 .01 .01 <- matrix iteration residuals
Sum Area-Peak-Factors:
.0000 .0000 .0000 .0000 .0000 .0000 .0000 .0000 .0000 .0000 .0000 .0000
Time Dependent Intensity (TDI) Element Correction Percents:
.00 .00 .00 .00 .00 .00 .00 .00 .00 .00 .00 .00
Time Dependent Intensity (TDI) Element Correction Percent Relative Deviations:
.0 .0 .0 .0 .0 .0 .0 .0 .0 .0 .0 .0
MAN Absorption Correction Percents:
.00 .00 .00 .00 .00 .00 .00 .00 .00 .00 .00 .00
Nominal excess oxygen weight percent: .5606766
Current oxygen weight percent: .5606766
SAMPLE: 136, ITERATIONS: 3, Z-BAR: 12.71593
ELEMENT ABSCOR FLUCOR ZEDCOR ZAFCOR STP-POW BKS-COR F(x)u Ec Eo/Ec MACs <- first matrix correction iteration
Na ka 1.9731 .9943 1.0287 2.0182 1.0188 1.0097 .4266 1.0730 13.9795 3405.27
Si ka 1.3127 .9990 1.0113 1.3262 1.0244 .9873 .6899 1.8390 8.1566 1370.16
K ka 1.0526 .9763 1.0713 1.1009 1.1188 .9575 .9080 3.6080 4.1574 366.982
Al ka 1.4094 .9894 1.0389 1.4488 1.0444 .9948 .6296 1.5600 9.6154 1718.94
Mg ka 1.5401 .9923 1.0059 1.5373 1.0036 1.0023 .5626 1.3050 11.4943 2164.98
Fe ka 1.0027 1.0000 1.1796 1.1828 1.2473 .9457 .9820 7.1120 2.1091 83.5558
Ca ka 1.0336 .9946 1.0502 1.0797 1.1012 .9537 .9316 4.0390 3.7138 273.980
S ka 1.2129 1.0000 1.0234 1.2413 1.0513 .9735 .7677 2.4720 6.0680 984.820
Cl ka 1.1369 1.0000 1.0717 1.2185 1.1078 .9675 .8282 2.8230 5.3135 702.601
Ti ka 1.0253 .9901 1.1574 1.1749 1.2207 .9481 .9480 4.9670 3.0199 216.454
P ka 1.3373 1.0000 1.0478 1.4013 1.0691 .9801 .6867 2.1460 6.9897 1413.60
F ka 3.8664 .9977 1.0159 3.9187 .9932 1.0228 .1938 .6870 21.8341 8188.75
ELEMENT K-RAW K-VALUE ELEMWT% OXIDWT% ATOMIC% FORMULA KILOVOL <- matrix corrected concentrations (see CalcZAF board for more details)
Na ka .08695 .00639 1.290 1.739 1.193 .000 15.00
Si ka .72280 .14587 19.345 41.385 14.640 .000 15.00
K ka .01354 .00153 .169 .203 .092 .000 15.00
Al ka 1.66671 .05572 8.072 15.252 6.359 .000 15.00
Mg ka .96453 .05475 8.417 13.957 7.361 .000 15.00
Fe ka .80005 .07604 8.994 11.570 3.423 .000 15.00
Ca ka .74738 .07673 8.285 11.592 4.394 .000 15.00
S ka -.00034 -.00017 -.021 -.021 -.014 .000 15.00
Cl ka -.00390 -.00023 -.029 -.029 -.017 .000 15.00
Ti ka .01263 .00701 .823 1.373 .365 .000 15.00
P ka -.00040 -.00006 -.009 -.021 -.006 .000 15.00
F ka -.00155 -.00004 -.016 -.016 -.017 .000 15.00
O .561 .561 .745 .000
H .191 1.707 4.028 .000
Mn .116 .150 .045 .000
O 43.217 ----- 57.412 .000
TOTAL: 99.404 99.404 100.000 .000
Entering AnalyzeWeightCorrect...
Elements:
na si k al mg fe ca s cl ti p f
Uncorrected Unknown Counts:
8.46 148.88 1.53 58.09 56.98 78.59 79.51 -.03 -.05 1.40 -.01 -.01
MAN Background Counts on Unknown (based on unknown Z-bar: 12.71593)
1.17 2.46 .00 1.83 1.49 2.54 3.07 .00 .00 .00 .00 .00 <- next iteration of MAN background (note different z-bar)
Continuum Absorption Correction Factors on Unknown:
1.9731 1.3127 1.0526 1.4094 1.5401 1.0027 1.0336 1.2129 1.1369 1.0253 1.3373 3.8664 <- now we can calculate an actual continuum matrix correction
Absorption Correction Factors on Unknown:
1.9731 1.3127 1.0526 1.4094 1.5401 1.0027 1.0336 1.2129 1.1369 1.0253 1.3373 3.8664
Fluorescence Correction Factors on Unknown:
.9943 .9990 .9763 .9894 .9923 1.0000 .9946 1.0000 1.0000 .9901 1.0000 .9977
Atomic Number Correction Factors on Unknown:
1.0287 1.0113 1.0713 1.0389 1.0059 1.1796 1.0502 1.0234 1.0717 1.1574 1.0478 1.0159
ZAF Correction Factors on Unknown:
2.0182 1.3262 1.1009 1.4488 1.5373 1.1828 1.0797 1.2413 1.2185 1.1749 1.4013 3.9187
Disabled Quant Flag (zeroed intensity if set):
0 0 0 0 0 0 0 0 0 0 0 0
Corrected Unknown Counts:
7.29 146.42 1.53 56.26 55.49 76.05 76.44 -.03 -.05 1.40 -.01 -.01
Convergence Difference Counts:
.90 .29 .00 .50 .63 .26 .35 .00 .00 .00 .00 .00
Sum Area-Peak-Factors:
.0000 .0000 .0000 .0000 .0000 .0000 .0000 .0000 .0000 .0000 .0000 .0000
Time Dependent Intensity (TDI) Element Correction Percents:
.00 .00 .00 .00 .00 .00 .00 .00 .00 .00 .00 .00
Time Dependent Intensity (TDI) Element Correction Percent Relative Deviations:
.0 .0 .0 .0 .0 .0 .0 .0 .0 .0 .0 .0
MAN Absorption Correction Percents:
-49.32 -23.82 .00 -29.05 -35.07 -.27 -3.25 .00 .00 .00 .00 .00
Nominal excess oxygen weight percent: .5606766
Current oxygen weight percent: 43.77725
SAMPLE: 136, ITERATIONS: 3, Z-BAR: 12.69512
ELEMENT ABSCOR FLUCOR ZEDCOR ZAFCOR STP-POW BKS-COR F(x)u Ec Eo/Ec MACs
Na ka 1.9689 .9943 1.0288 2.0141 1.0191 1.0095 .4275 1.0730 13.9795 3414.58
Si ka 1.3137 .9990 1.0114 1.3273 1.0246 .9871 .6893 1.8390 8.1566 1381.19
K ka 1.0526 .9766 1.0714 1.1013 1.1190 .9574 .9080 3.6080 4.1574 369.246
Al ka 1.4105 .9895 1.0390 1.4501 1.0446 .9946 .6291 1.5600 9.6154 1732.03
Mg ka 1.5407 .9923 1.0060 1.5380 1.0038 1.0022 .5624 1.3050 11.4943 2179.22
Fe ka 1.0026 1.0000 1.1798 1.1828 1.2476 .9456 .9820 7.1120 2.1091 83.7876
Ca ka 1.0336 .9947 1.0503 1.0799 1.1015 .9536 .9316 4.0390 3.7138 275.650
S ka 1.2130 1.0000 1.0235 1.2415 1.0515 .9734 .7676 2.4720 6.0680 990.989
Cl ka 1.1370 1.0000 1.0718 1.2187 1.1080 .9674 .8281 2.8230 5.3135 706.981
Ti ka 1.0252 .9902 1.1575 1.1749 1.2210 .9480 .9482 4.9670 3.0199 217.133
P ka 1.3375 1.0000 1.0479 1.4016 1.0693 .9800 .6866 2.1460 6.9897 1422.50
F ka 3.8607 .9977 1.0160 3.9133 .9935 1.0227 .1941 .6870 21.8341 8224.34
ELEMENT K-RAW K-VALUE ELEMWT% OXIDWT% ATOMIC% FORMULA KILOVOL
Na ka .09918 .00729 1.468 1.979 1.349 .000 15.00
Si ka .72426 .14616 19.400 41.503 14.588 .000 15.00
K ka .01354 .00153 .169 .203 .091 .000 15.00
Al ka 1.68172 .05622 8.152 15.403 6.381 .000 15.00
Mg ka .97563 .05538 8.518 14.125 7.401 .000 15.00
Fe ka .79728 .07578 8.963 11.531 3.390 .000 15.00
Ca ka .74402 .07639 8.249 11.542 4.347 .000 15.00
S ka -.00034 -.00017 -.021 -.021 -.014 .000 15.00
Cl ka -.00390 -.00023 -.029 -.029 -.017 .000 15.00
Ti ka .01263 .00701 .823 1.373 .363 .000 15.00
P ka -.00040 -.00006 -.009 -.021 -.006 .000 15.00
F ka -.00155 -.00004 -.016 -.016 -.017 .000 15.00
O .561 .561 .740 .000
H .191 1.707 4.002 .000
Mn .116 .150 .045 .000
O 43.456 ----- 57.360 .000
TOTAL: 99.991 99.991 100.000 .000
Entering AnalyzeWeightCorrect...
Elements:
na si k al mg fe ca s cl ti p f
Uncorrected Unknown Counts:
8.46 148.88 1.53 58.09 56.98 78.59 79.51 -.03 -.05 1.40 -.01 -.01
MAN Background Counts on Unknown (based on unknown Z-bar: 12.69512)
1.17 2.45 .00 1.83 1.48 2.54 3.07 .00 .00 .00 .00 .00
Continuum Absorption Correction Factors on Unknown:
1.9689 1.3137 1.0526 1.4105 1.5407 1.0026 1.0336 1.2130 1.1370 1.0252 1.3375 3.8607
Absorption Correction Factors on Unknown:
1.9689 1.3137 1.0526 1.4105 1.5407 1.0026 1.0336 1.2130 1.1370 1.0252 1.3375 3.8607
Fluorescence Correction Factors on Unknown:
.9943 .9990 .9766 .9895 .9923 1.0000 .9947 1.0000 1.0000 .9902 1.0000 .9977
Atomic Number Correction Factors on Unknown:
1.0288 1.0114 1.0714 1.0390 1.0060 1.1798 1.0503 1.0235 1.0718 1.1575 1.0479 1.0160
ZAF Correction Factors on Unknown:
2.0141 1.3273 1.1013 1.4501 1.5380 1.1828 1.0799 1.2415 1.2187 1.1749 1.4016 3.9133
Disabled Quant Flag (zeroed intensity if set):
0 0 0 0 0 0 0 0 0 0 0 0
Corrected Unknown Counts:
7.29 146.42 1.53 56.26 55.49 76.05 76.45 -.03 -.05 1.40 -.01 -.01
Convergence Difference Counts:
.00 .01 .00 .00 .00 .00 .01 .00 .00 .00 .00 .00
Sum Area-Peak-Factors:
.0000 .0000 .0000 .0000 .0000 .0000 .0000 .0000 .0000 .0000 .0000 .0000
Time Dependent Intensity (TDI) Element Correction Percents:
.00 .00 .00 .00 .00 .00 .00 .00 .00 .00 .00 .00
Time Dependent Intensity (TDI) Element Correction Percent Relative Deviations:
.0 .0 .0 .0 .0 .0 .0 .0 .0 .0 .0 .0
MAN Absorption Correction Percents:
-49.21 -23.88 .00 -29.10 -35.09 -.26 -3.25 .00 .00 .00 .00 .00
Nominal excess oxygen weight percent: .5606766
Current oxygen weight percent: 44.01643
SAMPLE: 136, ITERATIONS: 3, Z-BAR: 12.69514
ELEMENT ABSCOR FLUCOR ZEDCOR ZAFCOR STP-POW BKS-COR F(x)u Ec Eo/Ec MACs
Na ka 1.9690 .9943 1.0288 2.0141 1.0191 1.0095 .4275 1.0730 13.9795 3414.72
Si ka 1.3137 .9990 1.0114 1.3273 1.0246 .9871 .6893 1.8390 8.1566 1381.23
K ka 1.0526 .9766 1.0714 1.1013 1.1190 .9574 .9080 3.6080 4.1574 369.260
Al ka 1.4105 .9895 1.0390 1.4501 1.0446 .9946 .6291 1.5600 9.6154 1732.08
Mg ka 1.5407 .9923 1.0060 1.5380 1.0038 1.0022 .5624 1.3050 11.4943 2179.29
Fe ka 1.0026 1.0000 1.1798 1.1828 1.2476 .9456 .9820 7.1120 2.1091 83.7913
Ca ka 1.0336 .9947 1.0503 1.0799 1.1015 .9536 .9316 4.0390 3.7138 275.660
S ka 1.2130 1.0000 1.0235 1.2415 1.0515 .9734 .7676 2.4720 6.0680 991.026
Cl ka 1.1370 1.0000 1.0718 1.2187 1.1080 .9674 .8281 2.8230 5.3135 707.008
Ti ka 1.0252 .9902 1.1575 1.1749 1.2210 .9480 .9482 4.9670 3.0199 217.143
P ka 1.3375 1.0000 1.0479 1.4016 1.0693 .9800 .6866 2.1460 6.9897 1422.56
F ka 3.8607 .9977 1.0160 3.9133 .9935 1.0227 .1941 .6870 21.8341 8224.67
ELEMENT K-RAW K-VALUE ELEMWT% OXIDWT% ATOMIC% FORMULA KILOVOL
Na ka .09916 .00729 1.468 1.979 1.349 .000 15.00
Si ka .72429 .14617 19.401 41.505 14.588 .000 15.00
K ka .01354 .00153 .169 .203 .091 .000 15.00
Al ka 1.68181 .05622 8.152 15.404 6.381 .000 15.00
Mg ka .97566 .05538 8.518 14.125 7.401 .000 15.00
Fe ka .79731 .07578 8.964 11.532 3.390 .000 15.00
Ca ka .74407 .07639 8.249 11.543 4.347 .000 15.00
S ka -.00034 -.00017 -.021 -.021 -.014 .000 15.00
Cl ka -.00390 -.00023 -.029 -.029 -.017 .000 15.00
Ti ka .01263 .00701 .823 1.373 .363 .000 15.00
P ka -.00040 -.00006 -.009 -.021 -.006 .000 15.00
F ka -.00155 -.00004 -.016 -.016 -.017 .000 15.00
O .561 .561 .740 .000
H .191 1.707 4.002 .000
Mn .116 .150 .045 .000
O 43.457 ----- 57.360 .000
TOTAL: 99.994 99.994 100.000 .000
St 467 Set 2 Hornblende (Arenal) USNM 111356
St 467 Set 2 Hornblende (Arenal) USNM 111356
(Magnification (analytical) = 20000), Beam Mode = Analog Spot
(Magnification (default) = 2524, Magnification (imaging) = 736)
Image Shift (X,Y): -2.00, 3.00
Analysis (wet chemistry) by Gene Jarosewich
Number of Data Lines: 5 Number of 'Good' Data Lines: 1
First/Last Date-Time: 11/26/2013 03:43:20 PM to 11/26/2013 03:53:12 PM
WARNING- Using Exponential Off-Peak correction for p ka
Average Total Oxygen: 44.018 Average Total Weight%: 99.994
Average Calculated Oxygen: 43.457 Average Atomic Number: 12.695
Average Excess Oxygen: .561 Average Atomic Weight: 21.117
Average ZAF Iteration: 3.00 Average Quant Iterate: 3.00
Oxygen Calculated by Cation Stoichiometry and Included in the Matrix Correction
Combined Analytical Condition Arrays:
ELEM: Na Si K Al Mg Fe Ca S Cl Ti P F
TAKE: 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0
KILO: 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0
CURR: 10.0 10.0 10.0 10.0 10.0 10.0 10.0 50.0 50.0 50.0 50.0 50.0
SIZE: 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0
St 467 Set 2 Hornblende (Arenal) USNM 111356, Results in Elemental Weight Percents
ELEM: Na Si K Al Mg Fe Ca S Cl Ti P F O H Mn
TYPE: ANAL ANAL ANAL ANAL ANAL ANAL ANAL ANAL ANAL ANAL ANAL ANAL CALC SPEC SPEC
BGDS: MAN MAN LIN MAN MAN MAN MAN LIN LIN LIN EXP LIN
TIME: 30.00 30.00 20.00 40.00 30.00 40.00 20.00 20.00 20.00 20.00 20.00 20.00
BEAM: 9.99 9.99 9.99 9.99 9.99 9.99 9.99 49.99 49.99 49.99 49.99 49.99 <- note different beam current for different elements
ELEM: Na Si K Al Mg Fe Ca S Cl Ti P F O H Mn SUM
136 1.468 19.401 .169 8.152 8.518 8.964 8.249 -.021 -.029 .823 -.009 -.016 44.018 .191 .116 99.994
AVER: 1.468 19.401 .169 8.152 8.518 8.964 8.249 -.021 -.029 .823 -.009 -.016 44.018 .191 .116 99.994
SDEV: .000 .000 .000 .000 .000 .000 .000 .000 .000 .000 .000 .000 .000 .000 .000 .000
SERR: .000 .000 .000 .000 .000 .000 .000 .000 .000 .000 .000 .000 .000 .000 .000
%RSD: .00 .00 .00 .00 .00 .00 .00 .00 .00 .00 .00 .00 .00 .00 .00
PUBL: 1.417 19.380 .174 8.188 8.587 8.916 8.255 n.a. n.a. .845 n.a. n.a. 44.070 .191 .116 100.139
%VAR: 3.60 .11 -3.02 -.44 -.81 .53 -.07 --- --- -2.59 --- --- -.12 .00 .00
DIFF: .051 .021 -.005 -.036 -.069 .048 -.006 --- --- -.022 --- --- -.052 .000 .000
STDS: 336 162 374 160 162 162 162 730 285 22 285 284 0 0 0
STKF: .0735 .2018 .1132 .0334 .0568 .0950 .1027 .5061 .0601 .5547 .1599 .0256 .0000 .0000 .0000
STCT: 73.52 202.16 113.18 33.45 56.88 95.38 102.74 101.14 12.07 110.89 31.95 5.07 .00 .00 .00
UNKF: .0073 .1462 .0015 .0562 .0554 .0758 .0764 -.0002 -.0002 .0070 -.0001 .0000 .0000 .0000 .0000
UNCT: 7.29 146.42 1.53 56.26 55.49 76.05 76.45 -.03 -.05 1.40 -.01 -.01 .00 .00 .00
UNBG: 1.17 2.45 3.74 1.83 1.48 2.54 3.07 .57 .72 .50 .38 .13 .00 .00 .00
ZCOR: 2.0141 1.3273 1.1013 1.4501 1.5380 1.1828 1.0799 1.2415 1.2187 1.1749 1.4016 3.9133 .0000 .0000 .0000
KRAW: .0992 .7243 .0135 1.6818 .9757 .7973 .7441 -.0003 -.0039 .0126 -.0004 -.0016 .0000 .0000 .0000
PKBG: 7.22 60.70 1.41 31.79 38.40 30.97 25.91 .94 .93 3.80 .97 .94 .00 .00 .00
INT%: ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ---- ----
St 467 Set 2 Hornblende (Arenal) USNM 111356, Results in Oxide Weight Percents
ELEM: Na2O SiO2 K2O Al2O3 MgO FeO CaO S Cl TiO2 P2O5 F O H2O MnO SUM
136 1.979 41.505 .203 15.404 14.125 11.532 11.543 -.021 -.029 1.373 -.021 -.016 .561 1.707 .150 99.994
AVER: 1.979 41.505 .203 15.404 14.125 11.532 11.543 -.021 -.029 1.373 -.021 -.016 .561 1.707 .150 99.994
SDEV: .000 .000 .000 .000 .000 .000 .000 .000 .000 .000 .000 .000 .000 .000 .000 .000
SERR: .000 .000 .000 .000 .000 .000 .000 .000 .000 .000 .000 .000 .000 .000 .000
%RSD: .00 .00 .00 .00 .00 .00 .00 .00 .00 .00 .00 .00 .00 .00 .00
PUBL: 1.910 41.461 .210 15.471 14.240 11.470 11.550 n.a. n.a. 1.410 n.a. n.a. .561 1.707 .150 100.139 <- "published" standard values
%VAR: 3.60 .11 -3.02 -.44 -.81 .53 -.07 --- --- -2.59 --- --- .00 .00 .00 <- % relative accuracy error
DIFF: .069 .044 -.006 -.067 -.115 .061 -.008 --- --- -.037 --- --- .000 .000 .000 <-algebraic difference between average and published
STDS: 336 162 374 160 162 162 162 730 285 22 285 284 0 0 0 <- assigned primary standards
This post is part quant tip and part automation tip for those using interference and/or MAN background corrections with "Quick Standards" from the Automate! window...
The "quick standards" option in the Automate! window is really cool in that it tells the app to not acquire any elements in each standard that aren't assigned for use for the primary, interference or MAN assignments, unless the standard is not used in any assignments at all, in which case it acquires all elements currently being analyzed in the run on that standard, seen here:
(https://smf.probesoftware.com/oldpics/i62.tinypic.com/20htro6.jpg)
This allows for quick acquisition of standard intensities. There are several options for this feature that can be found in the Acquisition Options dialog from the Acquire! windows as seen here:
(https://smf.probesoftware.com/oldpics/i61.tinypic.com/2uz8pvl.jpg)
However, a caveat: The "quick standard" option is best utilized *after* your first standardization! Why? Because unless the interferences and/or MAN background *assignments* are already complete, the "quick" standardization will skip the acquisition of those elements for the interference and/or MAN calibrations. Note in the above image, the (initial) standardization option is checked but not the quick stds option...
Once the standards are acquired *without* the quick stds option, since all elements are acquired on all standards, we can go through the standards looking for unsuspected interferences (can we measure zero with sufficient accuracy in the presence of element "X"?), and specify these spectral interferences from the Standard Assignments button in Analyze!. Also, the MAN background calibration curves can also be examined and any outliers due to interferences or contamination can be eliminated. See these two links for more details:
http://smf.probesoftware.com/index.php?topic=69.msg257#msg257
http://smf.probesoftware.com/index.php?topic=4.msg499#msg499
Now that all interferences and MAN assignments are complete, *now* we can utilize the "quick stds" option to quickly acquire only the elements we actually need for the primary standard, interferences and MAN calibration curves as seen here:
(https://smf.probesoftware.com/oldpics/i60.tinypic.com/sxbpxd.jpg)
Here's another useful "hidden feature" that some of you might find useful.
When the Digitize window is open from the Automate! window as seen here, and the Standard option is selected:
(https://smf.probesoftware.com/oldpics/i61.tinypic.com/2hh1zpc.jpg)
we can select a standard.
From this window, if a BMP image exists in the StandardPOSFileDirectory as defined in the [standards] section of the probewin.ini file with the first 4 characters of the filename containing the standard number, the application will automatically open the image up for the user. It could be a SE image of the standard grains with annotations or perhaps an EDS spectrum of the standard or whatever... as seen here:
(https://smf.probesoftware.com/oldpics/i59.tinypic.com/15yjbj5.jpg)
I recently found this short note I made some time ago on using the Halogen Correction feature in Probe for EPMA. Please let me know if you have any questions. Bottom line: if you have significant weight percent levels of halogens and you are trying to calculate oxygen by stoichiometry (I'm lookin' at you- geologists!), you need this correction...
Oxygen From Halogens (F, Cl, Br and I) Correction
Introduction
A new feature to accurately calculate stoichiometric oxygen when halogens replace some of the oxygen is now available. This option will allow the program to calculate the equivalent oxygen from the measured or specified halogen concentrations (F, Cl, Br and I) and subtract that amount from the amount of calculated stoichiometric oxygen during the matrix ZAF iteration. Without this correction not only will the total be over estimated, but the matrix correction will be incorrectly calculated for the other elements in the sample. The largest error will be an overcorrection of F in samples containing significant F replacement of stoichiometric oxygen such as fluorine bearing phlogopites and apatites.
Calculation Details
During the calculation, since it requires two halogen atoms to replace one oxygen atom, one-half (by atom) of the halogens present are converted to equivalent oxygen and that amount is subtracted during the compositional iteration procedure. The adjustment is iterated along with the modified matrix correction factors, due to the change in overall composition. This option is applicable for ZAF/pr(z), Bence-Albee and calibration curve matrix correction calculations. This option applies only to samples where oxygen is calculated by stoichiometry and have measured or specified F, Cl, Br or I.
If this option is NOT used for samples where oxygen is calculated by stoichiometry and halogens are present, the software will simply report the oxygen equivalent of the halogens without subtracting the calculated amount. In this case, the user may then manually subtract the oxygen equivalent from the stoichiometric calculated oxygen, however, since the matrix correction is not adjusted for the change in oxygen concentration, the calculation of the other elements (especially F, due to it's large correction factor in the presence of oxygen) will be slightly in error.
Finally it should be noted that to be internally consistent in the matrix calculations, all oxide standard compositions used in halogen analyses should reflect the same adjustment for equivalent oxygen in the standard database as is used for the unknown (or standard) analysis in Probe for Windows.
Example
For example, the following standard composition is entered with the assumption that all cations have a full complement of stoichiometric oxygen:
St 112 biotite #3
TakeOff = 40 KiloVolts = 15
Oxide and Elemental Composition
Average Total Oxygen: 40.474 Average Total Weight%: 101.488
Average Calculated Oxygen: 40.474 Average Atomic Number: 13.413
Average Excess Oxygen: .000 Average Atomic Weight: 21.358
Oxygen Equiv. from Halogen: 1.697
ELEM: SiO2 Al2O3 FeO MgO CaO Na2O K2O TiO2
XRAY: ka ka ka ka ka ka ka ka
OXWT: 38.622 10.721 18.131 14.011 .020 .690 9.210 2.290
ELWT: 18.053 5.674 14.093 8.449 .014 .512 7.646 1.373
KFAC: .1368 .0382 .1205 .0528 .0001 .0024 .0689 .0119
ZCOR: 1.3201 1.4841 1.1692 1.6008 1.0860 2.1594 1.1093 1.1506
ATWT: 13.527 4.426 5.311 7.316 .007 .469 4.115 .603
ELEM: MnO BaO Rb2O Cl F H2O O
XRAY: ka la la ka ka ka
OXWT: .950 .111 .030 .020 4.020 2.663 .000
ELWT: .736 .099 .027 .020 4.020 .298 40.474
KFAC: .0062 .0008 .0002 .0002 .0112 .0030 .1826
ZCOR: 1.1891 1.3161 1.4008 1.2064 3.6053 .0000 2.2167
ATWT: .282 .015 .007 .012 4.453 6.222 53.236
Note that the total for the above composition is actually greater than 100% due to the fact that in reality the fluorine and chlorine actually replace some of the cation oxygen in this mineral. Note also, the oxygen equivalent from all halogens (F, Cl, Br and I) is reported, but not subtracted from the stoichiometric oxygen (oxygen from cations).
Calculations using this standard composition and an adjustment for equivalent oxygen from halogens in the matrix correction procedure will be slightly in error due to the fact that the standard k-factor calculation will not reflect the proper reduction of stoichiometric oxygen due to the presence of halogens.
Since the default mode of this analysis option (unchecked) is to only display the equivalent oxygen and not actually utilize it in the matrix corrections, then results calculated using typical standard compositions will at least be internally consistent.
However, if it is desired to use this analysis option by reducing the calculated stoichiometric oxygen in the matrix correction then for internally consistent results, the user should make an adjustment (reduction) in the amount of stoichiometric oxygen in the standard composition. This is easily done by noting the actual amount of stoichiometric oxygen (adjusted) in the Standard Composition dialog (see menu Standard | Modify) and entering that value for the concentration of oxygen as seen here:
St 112 biotite #3
TakeOff = 40 KiloVolts = 15
Oxide and Elemental Composition
Average Total Oxygen: 38.777 Average Total Weight%: 99.791
Average Calculated Oxygen: 40.474 Average Atomic Number: 13.505
Average Excess Oxygen: -1.697 Average Atomic Weight: 21.480
Oxygen Equiv. from Halogen: 1.697
ELEM: SiO2 Al2O3 FeO MgO CaO Na2O K2O TiO2
XRAY: ka ka ka ka ka ka ka ka
OXWT: 38.622 10.721 18.131 14.011 .020 .690 9.210 2.290
ELWT: 18.053 5.674 14.093 8.449 .014 .512 7.646 1.373
KFAC: .1367 .0382 .1207 .0529 .0001 .0024 .0689 .0119
ZCOR: 1.3208 1.4841 1.1681 1.5982 1.0858 2.1546 1.1091 1.1499
ATWT: 13.836 4.527 5.432 7.483 .008 .479 4.209 .617
ELEM: MnO BaO Rb2O Cl F H2O O
XRAY: ka la la ka ka ka
OXWT: .950 .111 .030 .020 4.020 2.663 -1.697 <-- this is correct! (think about it)
ELWT: .736 .099 .027 .020 4.020 .298 38.777
KFAC: .0062 .0008 .0002 .0002 .0113 .0030 .1731
ZCOR: 1.1881 1.3153 1.4016 1.2073 3.5626 .0000 2.2398
ATWT: .288 .016 .007 .012 4.555 6.364 52.168
Magnitude of the Effect
Note that the matrix correction for F ka changes from 3.6053 in the first example where the excess oxygen has not be subtracted, to 3.5626 in the second example where the oxygen was subtracted during the ZAF calculation. This is a change of about 1.1% in the calculated concentration for an unknown of similar composition, but will be significantly larger in samples with higher concentrations of F.
Note that if excess oxygen from Fe is also present and reported, then that concentration needs to be added to the actual oxygen concentration after subtraction of the oxygen equivalent from the halogens.
Hi,
I thought I share this little trick I just realized and maybe others would find it useful (as it is rooted in old Jeol software routines of mine).
At times I would like to run varying number of points on each standard but still do an automated calibration in PFE. For example the first point on albite is almost always a throwaway (from the peaking) or some standards are difficult to polish and require more points but I don't want to spend the time and run the same number of points on well-behaving standards.
In the automation dialog, I can only define a single number for standard points to acquire which in most cases is the most efficient. If not enough locations are digitized, the program will increment as needed (which is great if you have the type of vast, nicely polished standard and not small crappy ones).
So how can I have my cake and eat it too (automated acquisition with variable number of points).
I force PFE to only run digitized positions (in the "Acquisitions options" dialog in "Acquire!" and set positions as needed on my standards
Then I enter the maximum number in the Automate! dialog.
That way I can have, for example, 15 points on my BN standard and only 5 on my forsterite all in one automated run.
If you want to have Probe for EPMA play a little tune whenever your automation finishes (a feature John Fournelle asked for many moons ago!), you simply need to edit the [general] section in your Probewin.ini file for the following keyword:
UseWavFileAfterAutomationString="blowthiswhistle.wav"
Basically, this parameter specifies a .WAV audio file to be played after an automation has been completed. If the .WAV file is located in the Probe for EPMA application folder or a folder in the system path then the filename only can be specified. If the file is located in another folder, the complete path must be designated.
Attached below are a number of "cute" WAV files that play a little tune after the PFE automation is complete.
Not sure if this really qualifies as a "trick" but I think it is worth examining a particularly nasty binary system and that is Si Ka in Hf.
I was running some trace zircon analyses and normally I don't measure Si (or Zr) because for trace analysis I usually just specify the ZrSiO4 formula by difference in the Calculation Options dialog for a complete matrix correction. But this time I did and when I analyzed my Hf standard for Si, I got some strange analyses.
I should say that this isn't the first time I've seen this as shown by the post from a couple of years ago:
http://smf.probesoftware.com/index.php?topic=158.msg815#msg815
but this time I will follow up further on the quant question. By the way, I should also note that if I analyze the Hf in the Hf standard (HfSiO4 from John Hanchar) using pure Hf metal (using the Hf La line, so very energetic), I get almost exactly the expected Hf content in HfSiO4, so I'm pretty sure it's HfSiO4 (not sure if it could be anything else given only Hf, Si and O).
Anyway, here is the analysis of HfSiO4 using HfSiO4 as the Hf standard and ZrSiO4 as the Si standard:
ELEM: Zr Hf Si O
TYPE: ANAL ANAL ANAL SPEC
BGDS: LIN EXP LIN
TIME: 60.00 60.00 60.00 ---
BEAM: 29.89 29.89 29.89 ---
ELEM: Zr Hf Si O SUM
1533 .021 66.797 15.337 23.653 105.809
1534 -.014 66.405 14.935 23.653 104.979
1535 .028 66.587 15.288 23.653 105.556
AVER: .012 66.596 15.187 23.653 105.448
SDEV: .023 .196 .219 .000 .426
SERR: .013 .113 .127 .000
%RSD: 196.68 .29 1.44 .00
PUBL: n.a. 65.967 10.380 23.653 100.000
%VAR: --- (.95) 46.31 .00
DIFF: --- (.63) 4.807 .000
STDS: 257 19 257 ---
STKF: .4109 .5749 .1274 ---
STCT: 4215.7 14642.2 792.6 ---
UNKF: .0001 .5750 .0555 ---
UNCT: .6 14643.7 345.3 ---
UNBG: 9.4 245.2 3.4 ---
ZCOR: 2.0927 1.1582 2.7362 ---
KRAW: .0001 1.0001 .4357 ---
PKBG: 1.07 60.76 102.80 ---
I think we can all agree that a 46% relative error on a 10% value isn't very good! So then I ran all 10 matrix corrections in PFE and they all fail pretty miserably:
Summary of All Calculated (averaged) Matrix Corrections:
St 19 Set 6 HfSiO4 (Hafnon)
LINEMU Henke (LBL, 1985) < 10KeV / CITZMU > 10KeV
Elemental Weight Percents:
ELEM: Zr Hf Si O TOTAL
1 .012 66.596 15.187 23.653 105.448 Armstrong/Love Scott (default)
2 .010 66.525 13.361 23.653 103.549 Conventional Philibert/Duncumb-Reed
3 .010 66.337 13.382 23.653 103.383 Heinrich/Duncumb-Reed
4 .011 66.464 13.954 23.653 104.083 Love-Scott I
5 .011 66.477 14.110 23.653 104.251 Love-Scott II
6 .010 66.482 13.564 23.653 103.709 Packwood Phi(pz) (EPQ-91)
7 .011 66.193 15.002 23.653 104.861 Bastin (original) Phi(pz)
8 .011 66.595 14.639 23.653 104.898 Bastin PROZA Phi(pz) (EPQ-91)
9 .011 66.492 13.905 23.653 104.061 Pouchou and Pichoir-Full (Original)
10 .010 66.446 13.630 23.653 103.740 Pouchou and Pichoir-Simplified (XPP)
AVER: .011 66.461 14.073 23.653 104.198
SDEV: .000 .120 .659 .000 .672
SERR: .000 .038 .208 .000
MIN: .010 66.193 13.361 23.653 103.383
MAX: .012 66.596 15.187 23.653 105.448
The Si concentrations range from 13.3 wt% to 15.1 wt%, but all are pretty far from the expected 10.38 wt% Si. So what is going on?
Well obviously there is an enormous atomic number correction for this system, and that is the main reason why there is so much variation in the different matrix corrections for Si Ka. Remember, all these matrix corrections are using the same MAC for Si Ka in Hf.
But there is also a very large absorption correction, as seen from a formula calculation in CalcZAF:
ELEMENT ABSCOR FLUCOR ZEDCOR ZAFCOR STP-POW BKS-COR F(x)u Ec Eo/Ec MACs
Hf la .9854 .9999 1.2376 1.2194 1.3252 .9339 .9760 9.5610 1.5689 122.199
Si ka 2.3552 1.0000 .8271 1.9481 .6972 1.1864 .3845 1.8390 8.1566 3875.50
O ka 3.7987 .9998 .7433 2.8232 .6220 1.1950 .1845 .5317 28.2114 7904.62
ELEMENT K-RAW K-VALUE ELEMWT% OXIDWT% ATOMIC% FORMULA KILOVOL
Hf la .00000 .54099 65.967 ----- 16.667 .500 15.00
Si ka .00000 .05328 10.380 ----- 16.667 .500 15.00
O ka .00000 .08378 23.653 ----- 66.667 2.000 15.00
TOTAL: 100.000 ----- 100.000 3.000
and in fact if we examine the different available MACs for Si Ka in Hf we can see there is a large range:
MAC value for Si Ka in Hf = 5449.15 (LINEMU Henke (LBL, 1985) < 10KeV / CITZMU > 10KeV)
MAC value for Si Ka in Hf = 5151.30 (CITZMU Heinrich (1966) and Henke and Ebisu (1974))
MAC value for Si Ka in Hf = 5635.09 (MCMASTER McMaster (LLL, 1969) (modified by Rivers))
MAC value for Si Ka in Hf = 5037.41 (MAC30 Heinrich (Fit to Goldstein tables, 1987))
MAC value for Si Ka in Hf = 5152.54 (MACJTA Armstrong (FRAME equations, 1992))
MAC value for Si Ka in Hf = 4926.87 (FFAST Chantler (NIST v 2.1, 2005))
MAC value for Si Ka in Hf = 5061.00 (USERMAC User Defined MAC Table)
in fact, the Henke value is the 2nd highest available. What if we utilize the FFAST value?
Summary of All Calculated (averaged) Matrix Corrections:
St 19 Set 6 HfSiO4 (Hafnon)
FFAST Chantler (NIST v 2.1, 2005)
Elemental Weight Percents:
ELEM: Zr Hf Si O TOTAL
1 .011 66.523 14.493 23.653 104.680 Armstrong/Love Scott (default)
2 .010 66.431 12.831 23.653 102.925 Conventional Philibert/Duncumb-Reed
3 .010 66.282 12.858 23.653 102.803 Heinrich/Duncumb-Reed
4 .010 66.387 13.326 23.653 103.377 Love-Scott I
5 .010 66.399 13.447 23.653 103.509 Love-Scott II
6 .010 66.388 12.922 23.653 102.972 Packwood Phi(pz) (EPQ-91)
7 .011 66.173 14.335 23.653 104.172 Bastin (original) Phi(pz)
8 .011 66.514 13.990 23.653 104.168 Bastin PROZA Phi(pz) (EPQ-91)
9 .010 66.417 13.321 23.653 103.402 Pouchou and Pichoir-Full (Original)
10 .010 66.372 13.049 23.653 103.084 Pouchou and Pichoir-Simplified (XPP)
AVER: .010 66.389 13.457 23.653 103.509
SDEV: .000 .102 .612 .000 .631
SERR: .000 .032 .193 .000
MIN: .010 66.173 12.831 23.653 102.803
MAX: .011 66.523 14.493 23.653 104.680
Better, but still pretty high compared to the expected 10.38 wt%. What if we try the fast Monte Carlo method?
ELEM: Zr Hf Si O SUM
1533 .019 66.368 12.375 23.653 102.415
1534 -.013 65.993 12.043 23.653 101.677
1535 .024 66.161 12.336 23.653 102.175
AVER: .010 66.174 12.251 23.653 102.089
SDEV: .020 .188 .181 .000 .377
SERR: .012 .109 .105 .000
%RSD: 196.62 .28 1.48 .00
PUBL: n.a. 65.967 10.380 23.653 100.000
%VAR: --- (.31) 18.03 .00
DIFF: --- (.21) 1.871 .000
STDS: 257 19 257 ---
STBE: 1.2931 1.1413 1.2894 ---
STCT: 4215.7 14642.2 792.6 ---
UNBE: 1.9602 1.1448 2.3660 ---
UNCT: .6 14643.7 345.3 ---
UNBG: 9.4 245.2 3.4 ---
KRAW: .0001 1.0001 .4357 ---
PKBG: 1.07 60.76 102.80 ---
So, it's better than the best matrix correction with the FFAST MAC but still off by some 18% relative.
So now let's pull out the "big gun", which is an empirical MAC I measured for Si Ka in Hf some years ago (3.4770e+03) using Pouchou's XMAC app and a number of measurements at multiple keVs, and see what we get:
ELEM: Zr Hf Si O SUM
1533 .020 66.308 11.493 23.653 101.474
1534 -.014 65.925 11.185 23.653 100.750
1535 .026 66.101 11.457 23.653 101.237
AVER: .011 66.111 11.378 23.653 101.154
SDEV: .022 .191 .169 .000 .369
SERR: .012 .111 .097 .000
%RSD: 196.65 .29 1.48 .00
PUBL: n.a. 65.967 10.380 23.653 100.000
%VAR: --- (.22) 9.62 .00
DIFF: --- (.14) .998 .000
STDS: 257 19 257 ---
STKF: .4045 .5730 .1304 ---
STCT: 4215.7 14642.2 792.6 ---
UNKF: .0001 .5730 .0568 ---
UNCT: .6 14643.7 345.3 ---
UNBG: 9.4 245.2 3.4 ---
ZCOR: 2.0110 1.1537 2.0020 ---
KRAW: .0001 1.0001 .4357 ---
PKBG: 1.07 60.76 102.80 ---
So we're still off by some 9.6% relative, but that's a heck of a lot better than an error of 46% relative!
And the beat goes on... :D
Someone asked about the possibility of an interference of Si Ka by the Hf Ll IV line and that does show as an interference as seen here:
(https://smf.probesoftware.com/gallery/1_28_10_16_10_59_34.png)
However, when I analyzed Si in Hf metal I get essentially zero Si, so that is apparently not an issue:
ELEM: Zr Hf Si SUM
1539 3.090 98.388 -.008 101.470
1540 3.065 98.300 .024 101.389
1541 3.092 98.362 .008 101.462
AVER: 3.082 98.350 .008 101.440
SDEV: .015 .045 .016 .045
SERR: .009 .026 .009
%RSD: .49 .05 197.86
PUBL: 3.000 97.000 n.a. 100.000
%VAR: 2.74 1.39 ---
DIFF: .082 1.350 ---
STDS: 257 19 257
Note that the Hf concentration is calculated from extrapolation from HfSiO4 (KRAW = 1.709).
Quote from: Probeman on October 27, 2016, 04:37:14 PM
So, it's better than the best matrix correction with the FFAST MAC but still off by some 18% relative.
So now let's pull out the "big gun", which is an empirical MAC I measured for Si Ka in Hf some years ago (3.4770e+03) using Pouchou's XMAC app and a number of measurements at multiple keVs, and see what we get:
ELEM: Zr Hf Si O SUM
1533 .020 66.308 11.493 23.653 101.474
1534 -.014 65.925 11.185 23.653 100.750
1535 .026 66.101 11.457 23.653 101.237
AVER: .011 66.111 11.378 23.653 101.154
SDEV: .022 .191 .169 .000 .369
SERR: .012 .111 .097 .000
%RSD: 196.65 .29 1.48 .00
PUBL: n.a. 65.967 10.380 23.653 100.000
%VAR: --- (.22) 9.62 .00
DIFF: --- (.14) .998 .000
STDS: 257 19 257 ---
STKF: .4045 .5730 .1304 ---
STCT: 4215.7 14642.2 792.6 ---
UNKF: .0001 .5730 .0568 ---
UNCT: .6 14643.7 345.3 ---
UNBG: 9.4 245.2 3.4 ---
ZCOR: 2.0110 1.1537 2.0020 ---
KRAW: .0001 1.0001 .4357 ---
PKBG: 1.07 60.76 102.80 ---
So we're still off by some 9.6% relative, but that's a heck of a lot better than an error of 46% relative!
And the beat goes on... :D
OK, so I decided this morning to recalculate all the matrix corrections using my empirically measured MAC from a number of years ago (as in the above output), but when I went to recalculate the value, I am now getting a slightly different number and I can't figure out why:
ELEM: Zr Hf Si O SUM
1533 .021 66.261 11.165 23.653 101.100
1534 -.014 65.880 10.866 23.653 100.384
1535 .028 66.053 11.131 23.653 100.865
AVER: .012 66.065 11.054 23.653 100.783
SDEV: .023 .191 .164 .000 .365
SERR: .013 .110 .095 .000
%RSD: 196.68 .29 1.48 .00
PUBL: n.a. 65.967 10.380 23.653 100.000
%VAR: --- (.15) 6.49 .00
DIFF: --- (.10) .674 .000
STDS: 257 19 257 ---
STKF: .4109 .5749 .1274 ---
STCT: 4215.7 14642.2 792.6 ---
UNKF: .0001 .5750 .0555 ---
UNCT: .6 14643.7 345.3 ---
UNBG: 9.4 245.2 3.4 ---
ZCOR: 2.0885 1.1489 1.9915 ---
KRAW: .0001 1.0001 .4357 ---
PKBG: 1.07 60.76 102.80 ---
The std counts, unk counts and peak to bgd values are the same as before, so I know it's the same sample, but until I get back home (where I did the previous calculations), I probably won't be able to tell what was configured differently for the matrix correction. Don't you just love analytical mysteries? ;D
As chance would have it, the default "Armstrong" correction gives the worst result! Anyway here are all 10 matrix corrections in PFE, run this time with the empirical MAC for Si Ka in Hf:
Summary of All Calculated (averaged) Matrix Corrections:
St 19 Set 6 HfSiO4 (Hafnon)
Elemental Weight Percents:
ELEM: Zr Hf Si O TOTAL
1 .012 66.065 11.054 23.653 100.783 Armstrong/Love Scott (default)
2 .010 65.906 10.005 23.653 99.574 Conventional Philibert/Duncumb-Reed
3 .010 65.932 10.055 23.653 99.651 Heinrich/Duncumb-Reed
4 .011 65.948 10.209 23.653 99.821 Love-Scott I
5 .011 65.954 10.255 23.653 99.873 Love-Scott II
6 .010 65.887 9.869 23.653 99.420 Packwood Phi(pz) (EPQ-91)
7 .011 66.002 10.961 23.653 100.628 Bastin (original) Phi(pz)
8 .011 66.017 10.659 23.653 100.340 Bastin PROZA Phi(pz) (EPQ-91)
9 .011 65.964 10.293 23.653 99.920 Pouchou and Pichoir-Full (Original)
10 .010 65.933 10.086 23.653 99.682 Pouchou and Pichoir-Simplified (XPP)
AVER: .011 65.961 10.345 23.653 99.969
SDEV: .000 .054 .409 .000 .461
SERR: .000 .017 .129 .000
MIN: .010 65.887 9.869 23.653 99.420
MAX: .012 66.065 11.054 23.653 100.783
So the "published" value (based on stoichiometry) for Si in HfSiO4 is 10.38 wt%, and the average of all 10 matrix corrections is 10.345 +/- 0.409 wt.%, so within the accuracy variance.
So I investigated further the previously mentioned issue where I got different relative errors on the Si Ka in HfSiO4 when using the empirically measured MAC for Si ka in Hf and found the reason. Unfortunately I do understand the physics of the reason. I even ran this by Paul Carpenter earlier this week, but he was stumped as well. Maybe some of you can enlighten us on what exactly is going on here, because it sure seems unintuitive. But that's physics for you!
Ok, I made a new short run of ZrSiO4 as the Si standard and HfSiO4 as the Hf standard (oxygen by specification), so let's start by comparing the analysis of Si Ka in HfSiO4 using Hf La and 20 keV beam (just to make things difficult). Here is the analysis of HfSiO4 using the default Henke MACs (without the empirically measured MAC for Si Ka in Hf):
ELEM: Zr Hf Si O SUM
101 .016 66.589 15.174 23.653 105.431
102 .038 66.616 15.214 23.653 105.522
103 .049 66.556 15.096 23.653 105.354
AVER: .034 66.587 15.161 23.653 105.436
SDEV: .017 .030 .060 .000 .084
SERR: .010 .017 .035 .000
%RSD: 49.46 .04 .40 .00
PUBL: n.a. 65.967 10.380 23.653 100.000
%VAR: --- (.94) 46.06 .00
DIFF: --- (.62) 4.781 .000
STDS: 257 19 257 ---
STKF: .4109 .5749 .1274 ---
STCT: 4248.7 14759.3 787.7 ---
UNKF: .0002 .5749 .0554 ---
UNCT: 1.7 14759.3 342.6 ---
UNBG: 9.1 243.1 3.8 ---
ZCOR: 2.0923 1.1581 2.7362 ---
KRAW: .0004 1.0000 .4350 ---
PKBG: 1.19 61.73 91.83 ---
Yes, nasty. And remember, the default Armstrong phi-rho-z gave the *worst* correction of all 10 matrix corrections in PFE, but don't worry about that for now.
And here for the record are the Henke MACs that were utilized:
Current Mass Absorption Coefficients From:
LINEMU Henke (LBL, 1985) < 10KeV / CITZMU > 10KeV
Z-LINE X-RAY Z-ABSOR MAC
Zr la Zr 7.7749e+02
Zr la Hf 3.6888e+03
Zr la Si 2.6349e+03
Zr la Co 1.6648e+03
Zr la O 6.6065e+02
Hf la Zr 1.3762e+02
Hf la Hf 1.7099e+02
Hf la Si 6.3939e+01
Hf la Co 3.3125e+02
Hf la O 1.1692e+01
Si ka Zr 1.1459e+03
Si ka Hf 5.4492e+03
Si ka Si 3.5048e+02
Si ka Co 2.5192e+03
Si ka O 1.0337e+03
The ones in red are the MACs that matter for measuring Si Ka in HfSiO4. Now the same thing but using the FFAST MACs from NIST:
ELEM: Zr Hf Si O SUM
101 .015 66.515 14.480 23.653 104.664
102 .036 66.543 14.519 23.653 104.752
103 .046 66.483 14.406 23.653 104.589
AVER: .033 66.514 14.469 23.653 104.668
SDEV: .016 .030 .058 .000 .082
SERR: .009 .017 .033 .000
%RSD: 49.46 .04 .40 .00
PUBL: n.a. 65.967 10.380 23.653 100.000
%VAR: --- (.83) 39.39 .00
DIFF: --- (.55) 4.088 .000
STDS: 257 19 257 ---
STKF: .4045 .5730 .1304 ---
STCT: 4248.7 14759.3 787.7 ---
UNKF: .0002 .5730 .0567 ---
UNCT: 1.7 14759.3 342.6 ---
UNBG: 9.1 243.1 3.8 ---
ZCOR: 2.0185 1.1608 2.5500 ---
KRAW: .0004 1.0000 .4350 ---
PKBG: 1.19 61.73 91.83 ---
Better, but still pretty bad. And here are the FFAST MACs:
Current Mass Absorption Coefficients From:
FFAST Chantler (NIST v 2.1, 2005)
Z-LINE X-RAY Z-ABSOR MAC
Zr la Zr 6.9520e+02
Zr la Hf 3.3049e+03
Zr la Si 2.6600e+03
Zr la Co 1.5860e+03
Zr la O 6.2295e+02
Hf la Zr 1.3390e+02
Hf la Hf 1.5115e+02
Hf la Si 6.4790e+01
Hf la Co 3.3857e+02
Hf la O 1.1053e+01
Si ka Zr 1.0291e+03
Si ka Hf 4.9269e+03
Si ka Si 3.2280e+02
Si ka Co 2.4047e+03
Si ka O 9.6997e+02
So far so good as this makes sense to me because the FFAST MACs for Si ka in Hf (and O) are both lower than the Henke MACs, so we expect the Si concentration to be lower, correct?
Now, let try the same thing, but this time we'll use the empirically measured MAC for Si Ka in Hf, and the other MACs from the Henke or FFAST look up tables.
So here is the analysis using Henke MACs:
ELEM: Zr Hf Si O SUM
101 .016 66.057 11.044 23.653 100.770
102 .038 66.083 11.075 23.653 100.850
103 .049 66.027 10.986 23.653 100.715
AVER: .034 66.056 11.035 23.653 100.778
SDEV: .017 .028 .045 .000 .068
SERR: .010 .016 .026 .000
%RSD: 49.46 .04 .41 .00
PUBL: n.a. 65.967 10.380 23.653 100.000
%VAR: --- (.14) 6.31 .00
DIFF: --- (.09) .655 .000
STDS: 257 19 257 ---
STKF: .4109 .5749 .1274 ---
STCT: 4248.7 14759.3 787.7 ---
UNKF: .0002 .5749 .0554 ---
UNCT: 1.7 14759.3 342.6 ---
UNBG: 9.1 243.1 3.8 ---
ZCOR: 2.0881 1.1489 1.9915 ---
KRAW: .0004 1.0000 .4350 ---
PKBG: 1.19 61.73 91.83 ---
So that is when we see the ~6% relative accuracy error. And here are the MACs utilized:
Current Mass Absorption Coefficients From:
LINEMU Henke (LBL, 1985) < 10KeV / CITZMU > 10KeV
Z-LINE X-RAY Z-ABSOR MAC
Zr la Zr 7.7749e+02
Zr la Hf 3.6888e+03
Zr la Si 2.6349e+03
Zr la Co 1.6648e+03
Zr la O 6.6065e+02
Hf la Zr 1.3762e+02
Hf la Hf 1.7099e+02
Hf la Si 6.3939e+01
Hf la Co 3.3125e+02
Hf la O 1.1692e+01
Si ka Zr 1.1459e+03
Si ka Hf 3.4770e+03 *
Si ka Si 3.5048e+02
Si ka Co 2.5192e+03
Si ka O 1.0337e+03
* indicates empirical MAC
Empirical Mass Absorption Coefficients From:
C:\ProgramData\Probe Software\Probe for EPMA\EMPMAC.DAT
Z-LINE X-RAY Z-ABSOR MAC
Si ka Hf 3.4770e+03 Donovan (2011)
Now, the same thing but this time we use the FFAST MACs:
ELEM: Zr Hf Si O SUM
101 .015 66.104 11.368 23.653 101.140
102 .036 66.130 11.400 23.653 101.220
103 .046 66.073 11.309 23.653 101.081
AVER: .032 66.103 11.359 23.653 101.147
SDEV: .016 .029 .046 .000 .069
SERR: .009 .017 .027 .000
%RSD: 49.46 .04 .41 .00
PUBL: n.a. 65.967 10.380 23.653 100.000
%VAR: --- (.21) 9.43 .00
DIFF: --- (.14) .979 .000
STDS: 257 19 257 ---
STKF: .4045 .5730 .1304 ---
STCT: 4248.7 14759.3 787.7 ---
UNKF: .0002 .5730 .0567 ---
UNCT: 1.7 14759.3 342.6 ---
UNBG: 9.1 243.1 3.8 ---
ZCOR: 2.0107 1.1536 2.0019 ---
KRAW: .0004 1.0000 .4350 ---
PKBG: 1.19 61.73 91.83 ---
Ok, so there's the ~9% relative error I was seeing. And here are the MACs utilized:
Current Mass Absorption Coefficients From:
FFAST Chantler (NIST v 2.1, 2005)
Z-LINE X-RAY Z-ABSOR MAC
Zr la Zr 6.9520e+02
Zr la Hf 3.3049e+03
Zr la Si 2.6600e+03
Zr la Co 1.5860e+03
Zr la O 6.2295e+02
Hf la Zr 1.3390e+02
Hf la Hf 1.5115e+02
Hf la Si 6.4790e+01
Hf la Co 3.3857e+02
Hf la O 1.1053e+01
Si ka Zr 1.0291e+03
Si ka Hf 3.4770e+03 *
Si ka Si 3.2280e+02
Si ka Co 2.4047e+03
Si ka O 9.6997e+02
* indicates empirical MAC
Empirical Mass Absorption Coefficients From:
C:\ProgramData\Probe Software\Probe for EPMA\EMPMAC.DAT
Z-LINE X-RAY Z-ABSOR MAC
Si ka Hf 3.4770e+03 Donovan (2011)
Ok, so here is the question I have: why is the concentration so much different when the only difference is the Si Ka in oxygen MAC, and even more weird, why is the Si concentration *higher* in the FFAST calculation, when the Si Ka in O FFAST MAC is *lower* than the Henke MAC value!
:o
In summary here are the results for all 10 analytical expressions using the Henke MACs (and the empirically measured MAC for Si ka in Hf):
Summary of All Calculated (averaged) Matrix Corrections:
St 19 Set 1 HfSiO4 (Hafnon)
LINEMU Henke (LBL, 1985) < 10KeV / CITZMU > 10KeV
Elemental Weight Percents:
ELEM: Zr Hf Si O TOTAL
1 .034 66.056 11.035 23.653 100.778 Armstrong/Love Scott (default)
2 .030 65.896 9.987 23.653 99.566 Conventional Philibert/Duncumb-Reed
3 .031 65.923 10.038 23.653 99.645 Heinrich/Duncumb-Reed
4 .031 65.939 10.192 23.653 99.816 Love-Scott I
5 .032 65.946 10.237 23.653 99.868 Love-Scott II
6 .030 65.878 9.852 23.653 99.414 Packwood Phi(pz) (EPQ-91)
7 .034 65.993 10.943 23.653 100.622 Bastin (original) Phi(pz)
8 .033 66.008 10.640 23.653 100.334 Bastin PROZA Phi(pz) (EPQ-91)
9 .031 65.955 10.275 23.653 99.914 Pouchou and Pichoir-Full (Original)
10 .031 65.924 10.069 23.653 99.676 Pouchou and Pichoir-Simplified (XPP)
AVER: .032 65.952 10.327 23.653 99.963
SDEV: .001 .054 .408 .000 .461
SERR: .000 .017 .129 .000
MIN: .030 65.878 9.852 23.653 99.414
MAX: .034 66.056 11.035 23.653 100.778
And here are the results for all 10 analytical expressions using the FFAST MACs (and the empirically measured MAC for Si ka in Hf):
Summary of All Calculated (averaged) Matrix Corrections:
St 19 Set 1 HfSiO4 (Hafnon)
FFAST Chantler (NIST v 2.1, 2005)
Elemental Weight Percents:
ELEM: Zr Hf Si O TOTAL
1 .032 66.103 11.359 23.653 101.147 Armstrong/Love Scott (default)
2 .028 65.953 10.284 23.653 99.919 Conventional Philibert/Duncumb-Reed
3 .029 65.960 10.333 23.653 99.976 Heinrich/Duncumb-Reed
4 .030 65.982 10.488 23.653 100.153 Love-Scott I
5 .030 65.988 10.538 23.653 100.210 Love-Scott II
6 .029 65.922 10.126 23.653 99.731 Packwood Phi(pz) (EPQ-91)
7 .032 66.012 11.270 23.653 100.967 Bastin (original) Phi(pz)
8 .031 66.059 10.968 23.653 100.711 Bastin PROZA Phi(pz) (EPQ-91)
9 .030 66.002 10.578 23.653 100.263 Pouchou and Pichoir-Full (Original)
10 .029 65.969 10.363 23.653 100.014 Pouchou and Pichoir-Simplified (XPP)
AVER: .030 65.995 10.631 23.653 100.309
SDEV: .001 .053 .424 .000 .473
SERR: .000 .017 .134 .000
MIN: .028 65.922 10.126 23.653 99.731
MAX: .032 66.103 11.359 23.653 101.147
Please note that the correct value for Si in HfSiO4 should be close to 10.38 wt.%...
By the way, I did have a thought (dangerous I know), that perhaps it's the standard k-factor calculation for Si ka in the Si standard which is ZrSiO4. Note that the value for Si Ka in Zr is quite large for both, as seen here:
Henke:
Si ka Zr 1.1459e+03
FFAST:
Si ka Zr 1.0291e+03
and in fact are some 10 or 11% different. But more interesting is that the FFAST value is lower, which in the standard, could push the calculated analysis for Si in the unknown (the HfSiO4) in the opposite direction... so maybe that's the answer?
I've attached the MDB file below is anyone wants to play with it. If you don't have PFE and just CalcZAF, I've also attached a CalcZAF input file...
I think I've mentioned this previously, but I thought I should point out that any data type that is displayed in the PFE Analyze! window, can also be exported directly to Excel by first opening a link to Excel using the Output | Open Link To Excel menu, then by clicking the >>Excel button in Analyze! as seen here:
(https://smf.probesoftware.com/gallery/395_22_01_17_11_16_46.png)
john
There are often several different ways to design one's analytical approach to a specific sample. For example, trace element characterization can be approached using various methods contained in Probe for EPMA and it is up to the analyst to decide which approach they deem the best for a particular situation.
For instance, often when I want to measure trace elements in a beam sensitive glass or apatite, my students will often design a "combined condition" analytical setup where the major elements are measured at a low beam current, often using the TDI (time dependent intensity) correction, followed by the trace elements measured at a higher beam current for better sensitivity. An example of this approach is seen here:
(https://smf.probesoftware.com/gallery/395_04_03_17_9_46_29.png)
Note that both the 30 nA and the 100 nA conditions are contained in the single sample for acquisition and analysis, hence the term "combined condition" sample. There are other approaches...
Recently a student of Paul Carpenter's wanted to measure trace elements in olivine, so Paul set them up with an analytical method using two separate analytical setups, the first for the major elements at 25 nA, and a second analytical setup at 100 nA (note that Al is acquired on two spectrometers for better sensitivity) as seen here for the 25 nA setup:
(https://smf.probesoftware.com/gallery/395_04_03_17_9_28_35.png)
and here for the 100 nA setup:
(https://smf.probesoftware.com/gallery/395_04_03_17_9_28_50.png)
Look closely and you will note that both samples have the same elements! However, the first analytical setup has all the trace elements disabled for acquisition (and quant), and the second analytical setup has all the major elements disabled for acquisition (and quant). Please note that the disable acquisition and disable quant checkboxes are found in the Elements/Cations dialog for each element.
So, what Paul does is have the student assign *both* analytical setups to each digitized stage coordinate in the Automate! window using the Multiple Setups button. That way the program acquires each analytical setup (with the different beam currents and different elements disabled for acquisition) one after the other. Once that is done, the user can go to the Analyze! window and combine the elements for the two setups using either of the two buttons highlighted here:
(https://smf.probesoftware.com/gallery/395_04_03_17_9_29_03.png)
The upper button doesn't permanently combine the data into a new sample, the lower button does permanently combine them. The results for the "combine selected samples" method is shown here:
(https://smf.probesoftware.com/gallery/395_04_03_17_9_29_21.png)
Finally, we can turn on the "aggregate" mode under the Analysis Options dialog and "aggregate" the two aluminum channels for better trace element sensitivity as seen here:
(https://smf.probesoftware.com/gallery/395_04_03_17_10_02_13.png)
Here's something I ran across today...
I'm running some diffusion profiles in some metallurgical samples and I noticed that my totals were somewhat high around 101.5 wt.% or so. These are PbS and PbTe samples at 15 keV, so first I checked for interferences, and they are all corrected for properly (one really needs a good Pb standard that doesn't contain S for an interference correction of S Ka on Pb Ma, so I use alamosite or PbSiO3). Then I checked the focus on the unknowns and the standards and that was good too. No significant intensity drift either. So why the high totals as seen here?
(https://smf.probesoftware.com/gallery/395_07_03_17_4_03_30.png)
Then it occurred to me, the standards are carbon coated, but the unknown is not (the customer doesn't want us to carbon coat their samples, so we've been using Cu tape to ground them to the sample holder). Could that make this much of a difference for Pb Ma and Te La?
So first I went to the Calculation Options dialog in the Analyze! window and unchecked the Use Unknown Conductive Coating as seen here:
(https://smf.probesoftware.com/gallery/395_07_03_17_4_55_21.png)
Now, if you re-calculate the analysis, one gets the same results, and why is that? It's because the coatings corrections are not actually utilized in the software unless one specifically turns them on in the Analytical | Analysis Options dialog as seen here:
(https://smf.probesoftware.com/gallery/395_07_03_17_5_06_26.png)
Now we re-calculate our results and dang if that didn't take care of the high totals:
(https://smf.probesoftware.com/gallery/395_07_03_17_5_06_40.png)
This is more of a tip than a trick, but I mention it because we recently improved the Report button output to better handle the presence of elements quantified using the EDS WDS integration feature in Probe for EPMA. The WDS and EDS integration in Probe for EPMA can utilize SDD EDS systems from Thermo (NSS and Pathfinder), Bruker (Esprit) and most recently JEOL (OEM) EDS detectors.
The Report button is located in the Analyze! window as seen here and can be applied to any unknown or standard sample in your run:
(https://smf.probesoftware.com/gallery/1_14_06_19_9_04_27.png)
This feature can be utilized to export both a text description and a tab delimited spreadsheet format of the current analytical conditions and parameters. The text output consists of (almost!) English sentences as seen here that can be edited for including in your own reports and manuscripts:
Probe for EPMA Xtreme Edition for Electron Probe Micro Analysis
Database File: C:\UserData\Eastman\06-2019\Fe, V, C, O_06-03-2019.MDB
Database File Type: PROBE
DataFile Version Number: 12.6.2
Program Version Number: 12.6.3
Database File User Name: Chris Eastman
Database File Description: C and O by WDS, V, Fe, etc. by EDS
Database Created: 6/3/2019 11:01:40 AM
Last Updated: 6/3/2019 11:01:40 AM
Last Modified: 6/13/2019 1:12:23 PM
Current Date and Time: 6/13/2019 1:13:24 PM
Nominal Beam: 54.2881 (nA)
Faraday/Absorbed Averages: 1
Correction Method and Mass Absorption Coefficient File:
ZAF or Phi-Rho-Z Calculations
LINEMU Henke (LBL, 1985) < 10KeV / CITZMU > 10KeV
Current ZAF or Phi-Rho-Z Selection:
Armstrong/Love Scott (default)
Correction Selections:
Phi(pz) Absorption of Armstrong/Packwood-Brown 1981 MAS
Stopping Power of Philibert and Tixier
Backscatter Coefficient of Love-Scott
Backscatter of Love-Scott
Mean Ionization of Berger-Seltzer
Phi(pz) Equation of Love-Scott
Reed/JTA w/ M-Line Correction and JTA Intensity Mod.
Fluorescence by Beta Lines NOT Included
Un 2 Fe, V, C, O trav1
TakeOff = 40.0 KiloVolt = 15.0 Beam Current = 30.0 Beam Size = 0
(Magnification (analytical) = 40000), Beam Mode = Analog Spot
(Magnification (default) = 2245, Magnification (imaging) = 2857)
Image Shift (X,Y): .00, .00
Compositional analyses were acquired on an electron microprobe (Cameca SX100/SXFive (TCP/IP Socket)) equipped with 5 tunable wavelength dispersive spectrometers.
EDS spectra were acquired and processed using a Thermo NSS or PF EDS system.
Operating conditions were 40 degrees takeoff angle, and a beam energy of 15 keV.
The beam current was 30 nA, and the beam diameter was 0 microns.
Elements were acquired using analyzing crystals EDS for Fe ka, Nb la, V ka, PC1 for O ka, and PC2 for C ka.
The standards were Carbon (graphite) for C ka, Vanadium metal for V ka, Iron metal for Fe ka, Niobium metal for Nb la, and Al2O3 (elemental) (#13) for O ka.
Iron metal
From Johnson-Matthey, Vacuum remelted, Batch BM1664
Optical emission: Al < 1ppm, Ca < 1 ppm,
Cr 2 ppm, Co 20 ppm, Cu 3 ppm, Ni 3 ppm
Si 60 ppm, Sn 10 ppm, Ag < 1 ppm
Oxygen 310 ppm, Nitrogen 10 ppm
Vanadium metal
From Aesar, #143594, Lot #19778
99.95%, 1.0 mm wire
Carbon (graphite)
1. single crystal (synthetic) from Union Carbide
Grade 2YA, serial #8403, contains ~2.4% oxygen (from H2O?)
Al2O3 (elemental) (#13)
Specimen from Baikowski Int'l, North Carolina
'crackle' from seed crystal, 99.99%
Si ~330 PPM by EPMA (JJD), 05-30-2012
Niobium metal
Aesar, 99.99%, 0.25mm sheet
Lot #10258
Possible 0.19 wt% Ta (?)
The counting time was 30 seconds for C ka, O ka, and 45 seconds for Nb la, V ka, Fe ka.
The intensity data was corrected for Time Dependent Intensity (TDI) loss (or gain) using a self calibrated correction for C ka, O ka.
The off peak counting time was 10 seconds for C ka, O ka.
Off Peak correction method was Exponential for C ka, O ka.
Unknown and standard intensities were corrected for deadtime.
Interference corrections were applied to C for interference by Nb, and to O for interference by V, Nb,
See J.J. Donovan, D.A. Snyder and M.L. Rivers, An Improved Interference Correction for Trace Element Analysis in Microbeam Analysis, 2: 23-28, 1993
Results are the average of 10 points and detection limits ranged from .037 weight percent for C ka to .177 weight percent for O ka.
Analytical sensitivity (at the 99% confidence level) ranged from 2.222 percent relative for C ka to 10.142 percent relative for O ka.
The quantitative blank correction was utilized.
The exponential or polynomial background fit was utilized.
See John J. Donovan, Heather A. Lowers and Brian G. Rusk, Improved electron probe microanalysis of trace elements in quartz, American Mineralogist, 96, 274282, 2011
The matrix correction method was ZAF or Phi-Rho-Z Calculations and the mass absorption coefficients dataset was LINEMU Henke (LBL, 1985) < 10KeV / CITZMU > 10KeV.
The ZAF or Phi-Rho-Z algorithm utilized was Armstrong/Love Scott (default).
Note the integration of EDS and WDS elements including the ability to apply spectral interference corrections between elements by WDS and EDS.
And here is the tab delimited report format suitable for import to Excel as seen here:
(https://smf.probesoftware.com/gallery/1_14_06_19_8_58_47.png)
Just FYI. Available for download now.
Edit by John: In case anyone is wondering why we decided to run O and C by WDS and Fe, V and Nb by EDS, it's a long story, but basically the sample is so magnetic (and re-magnetizes in the instrument), that the Bragg defocus between the standards and unknowns was killing us. So we ran Fe, V and Nb by EDS to avoid the Bragg defocus issue, and ran O and C by WDS because the EDS just can't handle these elements at trace levels. Also because the WDS peaks for O and C are so broad that the Bragg defocus is much less of an issue. The remaining problem now is trying to figure out where the darn beam is/was. Tough problem.
Here's another tip for those working with unusual compositions and wanting to classify those compositions and their modal abundances.
Normally for modal calculations of common silicates and oxides one can utilize the DHZ.MDB standard composition database because it contains most common rock forming minerals. But when working with unusual compositions, one should consider creating their own "custom" standard database (custom.mdb) for modal calculations.
One way to do this (other than simply entering the compositions by hand into the custom.mdb file), is when you are in the Analyze! window and have an analysis displayed, to simply right click the analyzed sample and click the Export Selected Samples To Custom.MDB menu.
(https://smf.probesoftware.com/gallery/1_06_12_19_9_53_22.png)
The Probe for EPMA software will then export the average composition of each sample to the custom.mdb standard database, which can then be used on your quantitative WDS maps for modal identification in the CalcImage software as described here:
https://smf.probesoftware.com/index.php?topic=1071.msg7095#msg7095
Hi all,
A useful approach that I've been using to assess the quality of standard analyses (unknowns too) within the Analyze! window is to use the String Selection field to search for and highlight all instances of a particular standard across multiple standard sets (where * can be used as a wildcard), and then output all these analyses with "Combine Data Lines from Selected Samples". This results in a easy to view output of all standards run for that entire session, so that the intensity reproducibility and/or drift with time can be seen. It is then easy to Disable anomalous measurements from within the data display.
I follow suite with particular sets of unknowns of interest, and "Combine Analysis Lines from Selected Samples" to easily view the output data + assess totals.
(https://smf.probesoftware.com/gallery/1344_05_02_20_4_20_35.png)
Best,
Allan Lerner
Just to add to Alan's point above, the latest version of Probe for EPMA now allows one to combine data lines from 2 or more samples (up to 500 lines total) now including the EDS spectra elements as well:
(https://smf.probesoftware.com/gallery/1_10_11_21_8_36_47.png)
In the above example, the elements Mg, K and Fe were acquired by EDS for quantification. This is seen in the following screenshot with the same samples combined and just displaying the intensities:
(https://smf.probesoftware.com/gallery/1_10_11_21_8_37_06.png)
Thanks to Scott Boroughs for calling attention to a bug when including the quant EDS elements that is now fixed.
Hi everyone,
could you explain how I can use options "standard X increment, ..." only for some standards of my "Run", not for all standards which will measure.
Thank you.
Digitize the standard positions exactly as you want them in the Automate! window, then in Acquisition Options check the checkbox "Use Only Digitized Standard Positions".
See also:
https://smf.probesoftware.com/index.php?topic=8.msg4011#msg4011
The option "acquire standard samples (again)" work at this way, but the points positions on the second, third, ... run will be the same - am I right?
Or checkbox "re-standard Y increment" will work?
Easy enough to test it, but yes, re-standard increment in Y still applies for standards.
Thank you!
Here's an interesting "trick".
Some of you may already utilize the Load Image button from the Imaging button (Acquire!) or the Digitize Image button (Digitize!) windows to load an image acquired using another software (e.g., JEOL, Cameca, Thermo, Bruker, etc. applications) into Probe for EPMA, for documentation or digitizing stage positions as described here:
https://smf.probesoftware.com/index.php?topic=42.msg9193#msg9193
The idea being that if the instrument is still at the same stage position and the same magnification (FOV) as when the loaded image was acquired, then the loaded image will be properly calibrated for the stage coordinates.
But it should be noted that one can load even images not acquired using a scanned beam, for example, an optical image from the light optics camera as seen here:
(https://smf.probesoftware.com/gallery/1_09_02_22_8_48_58.png)
The only important thing to remember is to utilize the stage position from when the optical image was captured in the PeakSight software, and especially to set the electron optics FOV to a value that corresponds to the optical FOV.
On SX100/SXFive Cameca instruments the light optics FOV is variable, but since we use the 500 um FOV as the default optical zoom, that corresponds to about 800x magnification for the electron optics. Other optical FOVs can also be used to capture and load light optics images, just be sure to set the magnification of the instrument to the light optics FOV for proper stage calibration of the loaded images.
Here's a few tips for utilizing previously acquired standard intensities from other runs.
So normally we would create a new run, then maybe load the sample setup from a previous run that had similar elements/conditions using the Acquire! window New Sample/Setup button as seen here:
(https://smf.probesoftware.com/gallery/395_12_04_22_11_50_35.png)
This will load not only the selected sample setup, but also all run (globals) specified in that run, and optionally all the standard intensities required for that specified sample setup.
This is a great way to get going quickly with a new run and of course the imported sample setup can be further modified and/or re-standardiazed.
The other more manual method to load standard intensities requires some preparation. Some of you may already utilize the Save Element Setup feature in Probe for EPMA to save specific element setups to the public SETUP.MDB file, so that these element setups can be recalled later by any user.
What you may not have noticed is that if the sample is a standard it will also save the standard intensity for that element. But to streamline this method, one can simply utilize the Save Setups as seen here from the Analyze! window:
(https://smf.probesoftware.com/gallery/1_20_08_25_7_56_17.png)
This button will automatically search the sample and automatically output all element setups associated with that sample including the standard (and interference and MAN) standard intensities to the (several) element setup databases. One click is all it takes! 8)
Once you have saved a number of element setups, you can import them into new runs using the button shown below. Personally when using this Load Element Setup dialog, I usually just load the element setups (without the standard intensities) and then re-acquire the standards, just to be sure to get up to date standard intensities.
But if desired, one can also load individual standard intensities using the button shown below.
(https://smf.probesoftware.com/gallery/395_12_04_22_11_44_12.png)
For this "tips and tricks" feature you will need the latest version of Probe for EPMA (as usual update from the Help | Update Probe for EPMA menu).
Sometimes a user will analyze for oxygen, but then later on would like to try simply calculating oxygen by stoichiometry.
However, if one goes into the Calculation Options dialog and clicks on the Calculate With Stoichiometric Oxygen option, they will get this warning:
(https://smf.probesoftware.com/gallery/1_07_06_22_8_32_05.png)
To remedy this, just go to the Elements Cations dialog and first, disable the analyzed oxygen for quantification by clicking on the analyzed oxygen row, then checking the Disable Quant checkbox.
Next click on on an empty row in the Elements/Cations dialog and enter oxygen with no x-ray line (no x-ray line indicates an unanalyzed element).
Now, go back to the Calculations Options dialog and now you will be able to click the Calculate With Stoichiometric Oxygen option. After clicking the Analyze button you will now see output similar to this:
(https://smf.probesoftware.com/gallery/1_07_06_22_8_32_30.png)
This is very much a beginner question, but I think it might help those who are just starting to use the Probe for EPMA software, because Probe for EPMA is designed completely differently than the JEOL and Cameca EPMA software.
The main point is that Probe for EPMA is intentionally designed from a "sample centric" perspective, while other EPMA software seems to be more designed from an "instrument centric" perspective. Basically when one looks at the Probe for EPMA software it appears to show a sample or samples. A sample being a collection of intensity or position data. The JEOL or Cameca software, on the other hand, appears (to me at least) to show the instrument more. Which makes sense to me because the JEOL and Cameca softwares were designed by instrument engineers, while Probe for EPMA was designed by scientists.
Basically, Probe for EPMA has two primary types of samples, each of which can contain zero to N data points. First, intensity samples (standards, unknowns and wavescans visible from the Acquire! and Analyze! windows), and second, position samples (standards, unknowns and wavescans visible from the Automate!, Digitize and Positions windows) that contain stage positions (and optionally sample conditions, setups, etc). Here is a more detailed description:
The samples in Acquire! and Analyze! windows are intensity samples (with or without intensity data). The samples in the Automate! window are position samples (with or without position data). Once intensity samples have been created and intensity data acquired (in Acquire! manually or in Automate! automatically), these intensity samples can be viewed in the Analyze! window.
You can add position data for automated acquisition from the Automate! window using the Digitize button. When you add (stage) position data to samples in the Automate! they can then be automated and then the intensity data samples will appear in the Analyze! window for quantification.
The Acquire! window only works with the "current" or last intensity sample created (usually an unknown sample). And the "current" sample can only be modified if it contains no intensity data (except changes for some background models, matrix corrections, software dead time, etc., etc.). So just create a new "current" sample if you want to change any acquisition conditions.
Remember, you cannot change sample conditions if the sample already contains intensity data (that would be unscientific!), but you can view the sample conditions from the Analyze! window using the Data, Elements/Cations and Conditions buttons.
Quote from: John Donovan on January 18, 2023, 09:21:54 AM
Basically, Probe for EPMA has two primary types of samples, each of which can contain zero to N data points. First, intensity samples (standards, unknowns and wavescans visible from the Acquire! and Analyze! windows), and second, position samples (standards, unknowns and wavescans visible from the Automate!, Digitize and Positions windows) that contain stage positions (and optionally sample conditions, setups, etc).
Sometimes the shortest explanation is the best explanation!
This is what one of our installers wrote to me on how they explain it:
- Acquire is where you tell it what to do.
- Automate is where you tell it where to do it.
- Analyze is where you look at what it did.
8)
My version on Owen,
-Acquire is where you create setup (with option of insitu acquistion, and record of all positions)
-Automate is where you automate
-Analyze is where you review standards and unknown results
How to quickly add a custom list of standards to a run
If you have a longer and disjointed list of standards that need to be frequently added to a run, here is a good trick.
1. In the Automate! window, first select all the standards that need to be added. Then, export this selection to a position list.
(https://smf.probesoftware.com/gallery/17_09_06_23_5_20_06.png)
2. Go to your "Standard Assignments" and "Add/Remove" standards and load in this .pos file.
(https://smf.probesoftware.com/gallery/17_09_06_23_5_20_27.png)
3. Admire that it only took you two mouse clicks to get all your standards into your run. This can be very useful for situations where a file setup load is not desired but I want users (or myself) give easy access to a curated list of standards.
(https://smf.probesoftware.com/gallery/17_09_06_23_5_54_26.png)
Duplicate positions as unknowns or wavescans
Maybe not so much a trick, just a well hidden function. PFE distinguishes three different position "types": standard, unknown and wavescans. Did you know that you can use one set of positions (like standards) to a create a different type (like wavescans). It not only copies over the X,Y,Z positions but also the comment name.
For this you need to get to the Positions window, which is accessible either through the "Digitize positions" dialog (in Automate!)
(https://smf.probesoftware.com/gallery/17_14_06_23_5_27_39.png)
or through the Move window (in Acquire!). You can find the Move window in Acquire!
(https://smf.probesoftware.com/gallery/17_09_06_23_5_20_57.png)
In the positions dialog, you can duplicate any position as either "unknown" or "wavescan" position.
(https://smf.probesoftware.com/gallery/17_09_06_23_5_21_24.png)
How do I use/abuse this function?
1) Standard evaluation: When I have a new standard block, I can easily set up wavescans for all standards after recording the standard locations. And they all have the proper comment name.
2) Changing the order of blocks of unknown positions. For example, I decide I want to run all positions in sample three first and not last, I just duplicate the positions in the order I would like to run them and delete the old one (or just not select them)
3) Create perfectly parallel traverses by setting up the first traverse, duplicate it as many times as needed and then use the update function in Acquire! to shift them around.
I am sure there are many other. By the way, this dialog is also where you can also shift positions by an increment.
Shift positions with Update
In case not everyone is aware of this trick (and it plays well with the Duplicate tip from my last post): The Update function in the Acquire window shifts all positions in same unknown based on the current stage position. So, usually the first position gets updated with the current stage position and all following positions get shifted by the same relative shift in X/Y/Z. This is great to update standard positions for example.
Not everyone may know that this can be applied to any position in your unknown.
(https://smf.probesoftware.com/gallery/17_15_06_23_3_47_34.png)
If I have a traverse going across a large grain and I want to make sure that I hit the core of the grain exactly, I will select the halfway position in my traverse, go to my desired location at the grain center and hit update. So, you can really select any point as the reference for your "Update" and the possibilities are endless if you want to quickly shift sets of positions (traverses, grids) around.
And to add further to Anette's post above, if you want to only update a single position, simply select the position and use the mouse right click to select the update single position menu as shown here:
(https://smf.probesoftware.com/gallery/1_15_06_23_9_46_59.png)
And another addendum, regarding the order of unknown or wavescan positions in the position list: You can reorder them using the little arrows although only one by one. For larger batches, I use the duplicate function as described in my earlier post.
(https://smf.probesoftware.com/gallery/17_21_06_23_11_16_49.png)
Using varying numbers of standard positions during an automated standard acquisition run
PFE allows to easily change the absolute number of standard positions run during a standard intensity acquisition through the "Standard Points to Acquire" field in Automate!. But what if I want to vary them within my standard run?
A trick is to set the checkmark for "Use Only Digitized Standard Positions" in the Acquisition Options dialog. Then add/delete positions for each standard to match what your desired positions count is and set the value for "Standard Points to Acquire" to the highest value. So if you set that value to 15 and one standard has 15 positions but all the other ones have 7, then this is exactly what will run.
(https://smf.probesoftware.com/gallery/17_14_06_23_3_10_16.png)
Quote from: Probeman on April 12, 2022, 12:56:55 PM...The other more manual method to load standard intensities requires some preparation. Some of you may already utilize the Save Element Setup feature in Probe for EPMA to save specific element setups to the public SETUP.MDB file, so that these element setups can be recalled later by any user.
What you may not have noticed is that if the sample is a standard it will also save the standard intensity for that element. But to streamline this method, one can simply utilize the Save Setups as seen here from the Analyze! window:
(https://smf.probesoftware.com/gallery/1_20_08_25_7_56_17.png)
This button will automatically search the sample and automatically output all element setups associated with that sample including the standard (and interference and MAN) standard intensities to the (several) element setup databases. One click is all it takes! 8)
Once you have saved a number of element setups, you can import them into new runs using the button shown below. Personally when using this Load Element Setup dialog, I usually just load the element setups (without the standard intensities) and then re-acquire the standards, just to be sure to get up to date standard intensities.
But if desired, one can also load individual standard intensities using the button shown below.
(https://smf.probesoftware.com/gallery/395_12_04_22_11_44_12.png)
I should add that this button is only available from the Elements/Cations dialog from the Analyze! window as shown here:(https://smf.probesoftware.com/gallery/395_30_11_23_8_25_07.png)
Now normally I just use the Load File Setup button to load a sample setup from an old run (usually without the standard intensities and then re-run the standards to get appropriate intensities), but once in a great while, I'll want to try a specific standard intensity from an old run (that was saved to the element setup database) and then this feature can be useful.
For example, maybe the filament died and I just needed to quickly acquire another standard or two for some trace elements:
https://smf.probesoftware.com/index.php?topic=610.msg11752#msg11752
Remember, for trace elements, the primary standard intensity is the *least* important parameter!
I was collecting some data last weekend on our JEOL 8530F simultaneously using WDS and our JEOL EDS in PfE. I wasn't really using the EDS, but I always collect the data just in case I might need it later on.
On reviewing the weekend run, I noticed that one of the WD spectrometers decided to start misbehaving part way through the analysis. Unfortunately, this was a major element and was consequently throwing the totals all over the place.
"No problem" thought I, "I'll just switch to using the EDS instead". Unfortunately, that particular element had a horrendous interference from another major element and whilst I could use the EDS data, I'd rather just do that particular element by difference.
I duly disabled the problematic element in the Elements/Cations option in the Analyze! window, and went to add this element back in (so that I could specify the element by difference). When the Element/Cation Properties window first loaded, the radio buttons for Analyzed vs Specified were greyed out (i.e. unselectable), with Specified selected by default. The WDS option was also selected but greyed out, with EDS selectable but unselected:
(https://smf.probesoftware.com/gallery/796_18_03_24_8_52_50.jpeg)
As soon as I either typed an element in to the Element box, or selected an element from the drop down, the radio buttons jumped from Specified to Analyzed and from WDS to EDS, and I couldn't revert back as all the options were unselectable!:
(https://smf.probesoftware.com/gallery/796_18_03_24_8_53_24.jpeg)
As I didn't want to analyze this element by EDS (or WDS), but I wanted to specify this element by difference, what I had to do was scroll down to the bottom of the X-Ray Line list and select the blank space:
(https://smf.probesoftware.com/gallery/796_14_03_24_3_58_49.png)
This then jumped the radio button selection back to Specified and allowed me to select this element from the Element By Difference (as elemental) drop down menu in the Calculation Options window from the Analyze! window. Hurrah!
It also turns out there's an even easier way to do this! Instead of going through the rigmarole of adding the element to the list of elements in the Element/Cations window, I could simply have disabled the troublesome element and added it back in via the Formula By Difference (e.g. Li2B4O7) text entry box in the Calculation Options window in Analyze!:
(https://smf.probesoftware.com/gallery/796_18_03_24_8_53_56.jpeg)
We recently had a customer report that they were getting an error in the matrix correction, specifically in the fluorescence correction: ZAFFlu2 - Overflow. But when they sent us the PFE MDB file, we could not reproduce the error.
We then wondered if they might have inadvertently somehow corrupted the default x-ray line data files used in the matrix corrections. These are the XLINE.DAT, XLINE2.DAT, XEDGE.DAT and XFLUOR.DAT and XFLUOR2.DAT data files. We do not overwrite these file normally when the software is updated because we do allow these files to be edited by the user (power users?), so we suggested that they try copying these original files (attached below) over their current files.
That seems to have fixed the issue. None of us have any idea how these x-ray emission files could have become corrupted. But they are attached below in case anyone runs into a similar issue and wants to update their default emission files.
Sometimes we get requests for features that are already implemented, but "undiscovered"!
Someone recently asked "Is there a way to have the analysis output automatically after an acquisition?" and the answer is "yes", and here is where to find it:
(https://smf.probesoftware.com/gallery/1_22_02_25_2_10_04.png)
Note the the software will ask you the first time:
(https://smf.probesoftware.com/gallery/1_22_02_25_2_10_35.png)
so you'll want to make sure that your primary standards (and MAN/interference stds, etc.) are already acquired and assigned(!) before you activate this feature. Otherwise you'll get this error:
(https://smf.probesoftware.com/gallery/1_22_02_25_2_10_49.png)
and your automation will halt.
Note also that this feature works for manual single point acquisitions from the Acquire! window and automated acquisitions from the Automate! window. Also note that if you have a link to an Excel spreadsheet opened, by using the this menu:
(https://smf.probesoftware.com/gallery/1_22_02_25_2_10_19.png)
your results will also be sent to Excel after each analysis. See the other automatic output options in the Acquisition Options dialog from the Acquire! window.
A colleague asked how to change the standard assignments from the Analyze! window for multiple samples...
Start by selecting the samples that you want to change the standard assignments for:
(https://smf.probesoftware.com/gallery/1_21_08_25_4_58_30.png)
Then click the Standard Assignments button and confirm the samples that you want to edit. The selected sample indicates the basis for the elements to modify (in case different samples have different elements):
(https://smf.probesoftware.com/gallery/1_21_08_25_4_58_48.png)
Then click the element you want to modify the standard assignments for.
Note that you can also utilize the text selection control to quickly select all samples, for example that contain the string "garnet", etc.:
https://smf.probesoftware.com/index.php?topic=42.msg8602#msg8602
This is a small thing but sometimes we need to add unanalyzed elements to our samples in order to calculate the complete matrix effects accurately:
https://smf.probesoftware.com/index.php?topic=92.0
For example, adding ZrSiO4 by difference when analyzing only traces in zircons, or carbon by stoichiometry when analyzing Ca, Mg, etc in carbonates.
Usually we can quickly change or add an element as an unanalyzed element by clicking the "Specified" option in the Elements/Cations dialog. But depending on whether the sample already contains data (you must make a new sample to add an analyzed (WDS) element), or you also have elements by EDS (where you can add an analyzed element even when the sample already contains data), these controls may or may not be enabled.
This is indicated by the tool tip help as seen here:
(https://smf.probesoftware.com/gallery/1_17_09_25_9_53_31.png)
To add an unanalyzed element when EDS data is present (and these controls are disabled), you simply need to select the last x-ray selection, which is a blank as seen here:
(https://smf.probesoftware.com/gallery/1_17_09_25_9_53_48.png)
Alternatively, one can also simply delete the x-ray line leaving it blank. That action tells the software that the element is not by EDS (or WDS), but is instead unanalyzed (or specified).