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APPLICATION OF OES-AD SOFTWARE PACKAGE FOR DEVELOPING AUTOMATED TECHNIQUES. E.V. Shabanova 1 , I.E. Vasilyeva 1 , and I.L. Vasiliev 2 1 Vinogradov Institute of Geochemistry SB RAS, Favorsky Str., 1a, 664033, Irkutsk, Russia e-mail: shev@igc.irk.ru - PowerPoint PPT Presentation
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APPLICATION OF
OES-AD SOFTWARE PACKAGE FOR
DEVELOPING AUTOMATED TECHNIQUES
E.V. Shabanova1, I.E. Vasilyeva1, and I.L. Vasiliev2
1 Vinogradov Institute of Geochemistry SB RAS, Favorsky Str., 1a, 664033, Irkutsk, Russia e-mail: shev@igc.irk.ru
2 Institute of System Dynamics and Control Theory SB RAS, Lermontov Str., 134, 664033, Irkutsk, Russia
Spectral equipmentSpectral equipment
Multichannel analyzer
Diffraction spectrograph
Arcjet
Vertical direct-current
source
OE spectrum of sample with simple compositionOE spectrum of sample with simple composition(CRM of soil SDPS-1)(CRM of soil SDPS-1)
KNOWLEDGE BASE
Hierarchical tables of
wavelengths of analytical
lines of elements
Search and identification of analytical
lines
Choices of taking into account of
background and AP
calculations
Chemometric selections of
optimal conditions of AP processing and
constructing calibrations
Type of n-dimensional calibration:a) with /without taking into account of spectral interference; б) with /without taking into account of nonspectral influences; в) with /without blank
Forming of training and
test sets
Processing sample spectra
Selection of optimal APs
and calibrations
Comparison of result quality of
learn and test sets
It isn't different
It's d
iffere
nt
Desired condition compliance
No
RETRAINING
Results of determining content
of i-th element
DA
TA
BA
SE
Yes
Requirements to analytical
results (qualitative,
semiquantitative, quantitative)
Table of element
contents of CRMs, theirs
stuff is available in Lab
Measured spectra of CRMs and samples
Scheme of program complex for OEA executingScheme of program complex for OEA executing
OE-Techniques developed by the softwareOE-Techniques developed by the software
OES-AD software package is used to obtain and process spectra when determining: – impurities in quartz and crystalline silicon and
silanes; – Au, Ag and noble metals in nonsoluble
carbonaceous substance from black shales;
– cadmium in crystals of BaF2;
– lanthanum and yttrium in barium fluoride crystals;– boron and tin in granitoids.
Technical approachesTechnical approaches
The primary studies such as:– selection of analytical lines (determination of upper
and low bounds of intensity measuring);
– selection of analytical parameter for each spectral lines (calculation method of intensity);
– selection type of n-dimensional calibration for every analyte or group of analytes.
Table of Ba, La and Y contents in BaFTable of Ba, La and Y contents in BaF22 crystals crystals
RCM Ba content, % La content, % Y content, %
Mixture 1 78.3 - -
Mixture 2 70.5 7.09 -
Mixture 3 62.66 14.18 -
Mixture 4 39.16 35.45 -
Mixture 5 23.5 49.63 -
Mixture 6 15.67 56.72 -
Mixture 7 7.83 63.81 -
Mixture 8 - 70.9 -
La 1 77.23 1 -
La 2 77.97 0.33 -
La 3 78.21 0.11 -
La 4 78.3 0.012 -
Y 1 65.48 - 10
Y 2 71.9 - 5
Y 3 75.12 - 2.5
Y 4 77.04 - 1
Y 5 77.69 - 0.5
Hierarchical tablesHierarchical tables of some elements and analytical linesof some elements and analytical lines
Spectral adjectives of analyte and major element linesSpectral adjectives of analyte and major element lines
Compound / Element
Melting and vaporization temperature
s, С
Wavelength, nm
Detection limit,
%
Line intensity by
Harrison
Excitation
potential, eV
Analytical parameter
BaF2 / Ba 1368; 2250 233.526 II263.478 II264.138 259.6678 I
0.0021–
10
60R305
40
6.017.43
–4.75
Calculation of
intensity as
squares
under the
curve,
the
background
under peak
took into
account
LaF3 / La 1493; 2300 333.749 II324.513 II324.935 II261.034 I289.307 II
0.00010.0010.0010.010.01
800400300106
4.123.993.995.666.94
YF3 / Y 1155; 2230 297.4588 I317.307 II291.905 I276.01 I
0.0010.010.010.03
12201810
4.177.434.244.57
OE spectrum of BaFOE spectrum of BaF22
Some lines of Ba and LaSome lines of Ba and La
Way of calculating their analytical parametersWay of calculating their analytical parameters
Calibration typesCalibration types
Calibration typeCalibration type DescriptionDescription
OLS Ordinary Least Squares (one-dimensional)
to each analytical line with following averaging of results for every element
GLS Ordinary (General) Least Squares (n-dimensional)
to all selected analytical lines
PCR Principal Component Regression
to all selected analytical lines
Information coefficient Q=85%
NW Neural network
to all selected analytical lines
Rank criterion from range of relative bias Rank criterion from range of relative bias
using the Rj-values calculated, the range of relative bias is computed as
All ranges obtained for each calibration were ranked by increase. If some ranges of relative
bias vary by 5 %, then the average of numbers of places, on which they get, is calculated.
Thus, the best calibration has the least rank.
%,100.
..
cert
certcalj C
CCR
The relative bias of analyte determination in the each j-th sample of training set is provided by
where Ccal. and Ccert. are calculated and certificated contents, accordingly.
For the entire set of CRMs within the interval minmax CCC
.minmax RRR
Calibrations used for Ba Calibrations used for Ba and La determination and La determination
in BaFin BaF22 crystals crystals
Calibration
Element line composed of calibration& Its wavelength, nm
NW PCR GLS OLS
Ba II 233.527 + + + +Ba II 263.478 + + + +Ba II 264.138 + + + +Ba I 259.666 + + + +La II 333.749 + + + +La II 324.513 + + + +La II 324.935 + + + +La II 261.034 + + + +La II 289.307 + + + +
Calibrations used Calibrations used for Ba and Y determination for Ba and Y determination
in BaFin BaF22 crystals crystals
Calibration
Element line composed of calibration& Its wavelength, nm
NW PCR GLS OLS
Ba II 233.527 + + + +
Ba II 263.478 + + + +
Ba II 264.138 + + + +
Ba I 259.666 + + + +
Y I 297.459 + + + +
Y II 317.306 + + + +
Y I 291.905 + + + +
Y I 276.01 + + + +
Calibration selecting for Ba and La determination Calibration selecting for Ba and La determination by rank criterionby rank criterion
CalibrationΔ C, % Δ R Rank of Δ R
Sum of ranksBa La Ba La Ba La
OLS-1 OLS-1 to each analyte line
7.8-78.3
0.01-70.932 27 3 3 6
NW NW to all lines of Ba and La
1717 2424 11 22 33
PCR PCR to all lines of Ba and La
0.01-63.8253 58 4 4 8
GLS GLS to all lines of Ba and La
2323 1010 22 11 33
Calibration selecting for Ba and Y determination Calibration selecting for Ba and Y determination by rank criterionby rank criterion
CalibrationΔ C, % Δ R Rank of Δ R
Sum of ranksBa Y Ba Y Ba Y
OLS-1 OLS-1 to each analyte line
65.5-77.7 0.5-10
3 29 3.5 4 8
NW NW to all lines of Ba and Y
0.5 9 1.5 2.5 4
PCR PCR to all lines of Ba and Y
5 12 3.5 2.5 6
GLS GLS to all lines of Ba and Y
0.40.4 11 1.51.5 11 33
Relative bias Relative bias for determining Ba and Y in training setfor determining Ba and Y in training set
Y5 Y4 Y3 Y2 Y1
-4
-2
0
2
4
6
GLS NW
Re
lativ
e b
ias
of
Ba
, %
Train sample
0
10
20
30
40
50
60
70
80
C (Ba), % C (Y), %
Con
tent
, % m
ass.
Y5 Y4 Y3 Y2 Y1
-4
-2
0
2
4
6
GLS NW
Re
lativ
e b
ias
of
Y, %
Train sample
0
10
20
30
40
50
60
70
80
C (Y), % C (Ba), %
Con
tent
, % m
ass.
Relative bias Relative bias for determining Ba and La in training setfor determining Ba and La in training set
La4 La3 La2 La1 M1 M2 M3 M4 M5 M6 M7-30
-20
-10
0
10
20
30 GLS NW
Re
lativ
e b
ias
of
Ba
, %
Train sample
0
10
20
30
40
50
60
70
80
90
100 C (Ba), % C (La), %
Con
tent
, % m
ass.
La4 La3 La2 La1 M1 M2 M3 M4 M5 M6 M7 M8-30
-20
-10
0
10
20
30 GLS NW
Re
lativ
e b
ias
of
La
, %
Train sample
0
10
20
30
40
50
60
70
80
90
100 C (La), % C (Ba), %
Con
tent
, % m
ass.
Technique of determination of La, Y and Ba in BaFTechnique of determination of La, Y and Ba in BaF22
• The spectral equipment: diffraction spectrograph DFS-
458, arcjet "Vesuvius", and multichannel analyzer MAES
• 5 mg of sample and 5 mg of buffer (graphite powder) is
completely evaporated with the direct current is 15 A
• La content area is 0.01-63 %
while Ba content changes 8-78 %
• Y content area is 0.5-10 %
while Ba content changes 66-78 %
• Reproducibility of La, Y and Ba measurements, sr , are
0.08-0.12; 0.10-0.15;and 0.05-0.07, accordingly
Recommended