EDXRF Analysis Report

Thermo Electron Scientific Instruments Division

INTRODUCTION

Five aqueous metal solution samples were submitted for analysis by the QuanX EDXRF
system. The samples encompassed about 15 elements ranging in concentrations from
2.5 ppm up to 12.5 ppm, as illustrated below:

PROCEDURE

Instrumentation: The samples were analyzed using the QuanX system, which consists
of a 50kV Rhodium target X-ray tube, an eight-position filter wheel, and better-than 170
eV Si(Li) Peltier-cooled detector, coupled to an ADC. Samples were presented to the x-
ray beam using an automated 10-position sample tray with sample-spinning capability.
A PC controls setup, automation and data analysis through the Wintrace software.
Sample Preparation: No sample preparation was performed. A sample of each
solution was transferred into a standard 31-mm plastic cup and sealed by Prolene-
brand x-ray film.
Excitation Conditions: Each sample was analyzed using the following three excitation
conditions to optimize detection limits for the wide range of elements:

The total analysis time per sample was 82 minutes, of which 80 minutes were equally
split between the Mid Zc and High Za conditions.
As with most analytical techniques, the acquisition (measurement) time in EDXRF is the
main determinant of experimental precision, because it directly affects analyte peak size
and the counting statistics.
Peak Integration: Net peak intensities were extracted using the XML peak-fitting
method. The XML routine corrects for peak overlaps using a least-squares algorithm
that fits stored reference spectra of pure analyte elements to a sample spectrum.
Digital filtering of spectra (mathematical treatment) is used to correct for the background
before XML is performed. Together, these methods yield accurate x-ray intensities for
each element.

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Quantitative Analysis: The concentrations reported below were calculated using the
Fundamental Parameters (FP) algorithm. The FP technique greatly facilitated this
analysis with the following features:
Accounts for matrix (inter-element) effects, which are significant for the predominant
elements here, such as Fe, Ni and Cu.
Accounts for effects of components not measured directly by XRF, such as the
oxygen and hydrogen in the water. Since H2O makes up over 95% of these
samples, it has the single greatest matrix effect.
Reduces the number of standards needed to perform accurate quantitative analysis.
Thus, a wide range of unknown compositions can be analyzed with the same
method. As illustrated below, two standards (low and high concentration) would
have been quite sufficient for many of the analytes in this method.
Since the samples themselves were also standards, some other advantages of FP did
not have to be utilized:
Standards can be used that are very different in composition from the samples being
analyzed. For example, pure elements or chemical compounds can be used to
calibrate complex mixtures of elements in unknown oxidation states. Had these
samples been unknowns, commonly available metals-in-oil standards could have
been used to quantify them.
Standard-less analysis of individual elements or even complete samples can be
performed. As a result, elements or materials for which standards may not be
available could still be analyzed with a high degree of accuracy. In this case, Sn
was calibrated by reference to its neighbor, Te.
RESULTS

The analysis results exactly as reported by the software are shown in Appendix A
below. These results can also be exported and viewed in spreadsheet form, as in the
embedded Stillwater.xls spreadsheet in Appendix E.
The spreadsheet also contains the statistical analysis of 10 consecutive measurements
of Sample 3 to determine the experimental precision. For most elements, the precision
was under 10% rsd. The notable exceptions were Ir and Sn, as both were present
below the lower detection limit of the instrument. Se and Te were measured with 4.3%
and 13.4% rsd, respectively. The precision for Te, in particular, might be improved by
using a thicker Cu filter for the acquisition; this decision would be studied as part of final
method optimization.
Appendix C shows overlaid spectra of Sample 1, 3 and 5 under each of the conditions
used for the analysis. In addition, a comparison of the spectra with thick and thin Cu
filters is provided to illustrate the filters effect on peak definition.

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The two figures below show the calibration curves for Se and Te, respectively:

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The Te calibration curve excluded Sample 5 (5 ppm concentration), because it was an
outlier, as illustrated by the following curve that shows all five points together:

The measured peak for Sample 5 was the same size as that measured for Samples 1
and 10, while its concentration was twice as high.
Additional examples of calibration curves for S, Fe, Co, Rh and Pb - are provided in
Appendix B.
CONCLUSION

The analysis results demonstrate the ability of the QuanX system to accurately and
precisely characterize a wide range of trace constituents of aqueous solutions.

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APPENDIX A: RESULTS

EDXRF Analysis Report

Thermo NORAN
Sample List: Stillwater Analyzed: 10/24/01 08:52 AM
Technique: Fundamental Parameters Calibrated: 10/24/01 08:52 AM
Method File: C:\...\Methods for Wintrace 2.0.0\Stillwater hza.MTH Software version: 2.1.0 46

Conditions

Low Za
Voltage 4 kV Current 1.8 mA
Livetime 100 seconds Preset counts 0
Filter No Filter Atmosphere Air
Maximum Energy 10 keV Count rate range Medium
Warmup time 0 seconds

Mid Zc
Voltage 24 kV Current 0.5 mA
Livetime 1000 seconds Preset counts 0
Filter Pd Thick Atmosphere Air
Maximum Energy 20 keV Count rate range Medium
Warmup time 0 seconds

High Za
Voltage 50 kV Current 0.08 mA
Livetime 100 seconds Preset counts 0
Filter Cu Thin Atmosphere Air
Maximum Energy 40 keV Count rate range Medium
Warmup time 0 seconds

Results

Element Concentration Uncertainty Peak cps Background cps

1
S 1.4801 % 8.4141e-003 % 335.54 28.307
Fe 0.24723 % 8.6023e-004 % 88.42 6.2275
Co 253.26 ppm 4.2138 ppm 10.559 20.306
Ni 2.4592 % 1.9045e-003 % 1661.8 -5.4941
Cu 0. % 0. % 0. 74.084
As 0. ppm 0. ppm 0. 5.374
Se 2.1224 ppm 0.29547 ppm 0.5331 4.9749
Ir 0. ppm 0. ppm 0. 4.812
Pt 8.9302 ppm 0.44149 ppm 1.4347 3.5963
Pb 2.7299 ppm 0.34549 ppm 0.63659 5.8544
Ru 2.4965 ppm 0.20728 ppm 1.0516 6.5714
Rh 2.7874 ppm 0.21408 ppm 1.1862 7.1138
Pd 1.5673 ppm 0.22292 ppm 0.71559 9.6434
Sn 3.2784 ppm 0.39191 ppm 1.4517 28.664
Te 2.6592 ppm 0.60803 ppm 1.1413 66.964
H2O 95.785 %

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 3
S 1.2592 % 7.6676e-003 % 295.76 28.576
Fe 0.20124 % 7.7499e-004 % 73.264 6.3437
Co 197.11 ppm 3.7734 ppm 8.5421 18.199
Ni 2.006 % 1.6819e-003 % 1415.8 -6.7732
Cu 2.5044e-002 % 3.4052e-004 % 24.933 89.998
As 11.831 ppm 0.55007 ppm 2.1247 7.6333
Se 12.169 ppm 0.35135 ppm 3.3773 6.1317
Ir 0.57868 ppm 0.40341 ppm 0.1147 6.2783
Pt 8.3901 ppm 0.4483 ppm 1.4857 4.8163
Pb 12.055 ppm 0.5263 ppm 2.1713 6.8147
Ru 12.357 ppm 0.24081 ppm 5.7031 6.6489
Rh 12.383 ppm 0.24588 ppm 5.7635 7.3335
Pd 12.601 ppm 0.25439 ppm 6.2805 9.7965
Sn 2.1376 ppm 0.37021 ppm 1.023 30.365
Te 11.793 ppm 0.59266 ppm 5.4433 69.385
H2O 96.479 %

5
S 0.99117 % 6.6997e-003 % 244.66 28.836
Fe 0.15332 % 6.7763e-004 % 57.564 7.1621
Co 148.78 ppm 3.3187 ppm 6.8059 16.242
Ni 1.5423 % 1.4442e-003 % 1135.5 -4.843
Cu 0.23723 % 5.4435e-004 % 246.5 73.427
As 7.7911 ppm 0.44169 ppm 1.5044 5.7696
Se 4.7955 ppm 0.28564 ppm 1.4317 5.8403
Ir 8.7522 ppm 0.45008 ppm 1.8624 7.3106
Pt 7.6639 ppm 0.40591 ppm 1.4576 4.5024
Pb 4.7785 ppm 0.40142 ppm 1.0635 6.9185
Ru 4.9785 ppm 0.19703 ppm 2.4542 6.9798
Rh 4.9794 ppm 0.19959 ppm 2.4721 7.3469
Pd 4.4631 ppm 0.21028 ppm 2.3693 10.092
Sn 2.9826 ppm 0.35744 ppm 1.5113 31.292
Te 2.7133 ppm 0.55913 ppm 1.321 72.777
H2O 97.056 %

8
S 1.2672 % 7.7444e-003 % 295.33 30.434
Fe 7.498e-002 % 4.9733e-004 % 29.725 9.1462
Co 75.083 ppm 2.5001 ppm 3.7555 11.883
Ni 0.75624 % 1.0262e-003 % 548.4 5.3331
Cu 1.5088 % 1.236e-003 % 1525.1 35.623
As 13.156 ppm 0.56443 ppm 2.2795 7.2846
Se 12.898 ppm 0.36496 ppm 3.4507 6.0833
Ir 3.6955 ppm 0.90705 ppm 0.70818 29.506
Pt 6.8791 ppm 0.47179 ppm 1.1773 5.3417
Pb 13.023 ppm 0.54447 ppm 2.2529 6.6191
Ru 12.72 ppm 0.24889 ppm 5.6492 6.5688
Rh 12.731 ppm 0.25238 ppm 5.7037 7.0813
Pd 12.829 ppm 0.26034 ppm 6.1574 9.4546
Sn 2.0004 ppm 0.37905 ppm 0.92403 29.734
Te 13.113 ppm 0.6065 ppm 5.8518 67.4
H2O 96.375 %

10
S 1.5045 % 8.5574e-003 % 337.23 30.691
Fe 2.3621e-002 % 3.0465e-004 % 11.512 10.533
Co 26.335 ppm 1.7977 ppm 1.5162 9.1958
Ni 0.24646 % 6.0587e-004 % 175.73 10.884
Cu 2.4974 % 1.5958e-003 % 2453. 3.7384
As 0. ppm 0. ppm 0. 5.24
Se 3.0477 ppm 0.30102 ppm 0.74006 4.6029
Ir 0. ppm 0. ppm 0. 47.686
Pt 0. ppm 0. ppm 0. 5.288
Pb -0.44334 ppm -0.1938 ppm 0.17839 5.9026
Ru 2.7988 ppm 0.21176 ppm 1.1351 6.2409
Rh 2.1599 ppm 0.21707 ppm 0.88503 7.026
Pd 2.5496 ppm 0.22572 ppm 1.121 8.728
Sn 2.7106 ppm 0.39855 ppm 1.1575 27.807
Te 2.6847 ppm 0.6191 ppm 1.1126 64.715
H2O 95.724 %

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APPENDIX B: ADDITIONAL CALIBRATION CURVES

Calibration Curves for S (above) and Fe (below).

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Calibration Curves for Co (above) and Rh (below).

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Calibration Curve for Pb (above), showing Sample 10 as an outlier, which was excluded
from the final calibration curve used for the analysis below.

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APPENDIX C: EXAMPLE SPECTRA

Figure C-1 Spectra of Samples 1, 3 and 5 acquired under conditions optimized for S.

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 Figure C-2 Spectra of Samples 1, 3 and 5 acquired under conditions optimized for As, Se and Pb,
but also used for Fe-Cu, and Pt. A magnified version of the same spectrum is shown on the next
page to highlight the trace element peaks.

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 Figure C-3 The same spectrum as in Figure C-2 expanded to show peaks for Se and Pb. Notice the
overlap between the Pb L peak and the (main) As K peak.

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 Figure C-4 Spectrum of Samples 1, 3 and 5 acquired under conditions optimized for Te, but also
showing peaks for Ru, Rh and Pd. Figure C-5 on the next page compares the Te peaks acquired
with a thick and thin Cu filter.

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 Figure C-5 Comparison of Te peaks with Cu Thick filter (above) and Cu Thin filter (below).

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APPENDIX D: EXAMPLE OF PROGRAM LAYOUT

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[Note: Double-click object below to view all values]

Sample S Fe Co Ni Cu As Se Ru R
% % ppm % % ppm ppm ppm pp

1 1.48 0.25 253 2.46 0.00 0.0 2.1 2.5

3 1.26 0.20 197 2.01 0.025 11.8 12.2 12.4
5 0.99 0.15 149 1.54 0.24 7.8 4.8 5.0
8 1.27 0.07 75 0.76 1.51 13.2 12.9 12.7
10 1.50 0.02 26 0.25 2.50 0.0 3.0 2.8

Notes :
1) Pb for Sample 10 came out negative (-0.4 ppm), because a non-zero intercept was used for the calibration
calibration
2) Ir and Sn were present below the lower detection limit of the instrument; Ir overlaps with Pt.
3) As in Samples 1 and 10 was present below the detection limit of the instrument, because of peak overlap w

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