1. 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.rushev@igc.irk.ru 2 Institute of System Dynamics and Control Theory SB RAS, Lermontov Str., 134, 664033, Irkutsk, Russia

2. Spectral equipment Multichannel analyzer Diffraction spectrograph Arcjet Vertical direct- current source

3. OE spectrum of sample with simple composition (CRM of soil SDPS-1)

4. 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 different Desired condition compliance No RETRAINING Results of determining content of i-th element DATABASE 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 executing

5. OE-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 BaF 2 ; –lanthanum and yttrium in barium fluoride crystals; –boron and tin in granitoids.

6. Technical 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.

7. Table of Ba, La and Y contents in BaF 2 crystals RCMBa content, %La content, %Y content, % Mixture 178.3-- Mixture 270.57.09- Mixture 362.6614.18- Mixture 439.1635.45- Mixture 523.549.63- Mixture 615.6756.72- Mixture 77.8363.81- Mixture 8-70.9- La 177.231- La 277.970.33- La 378.210.11- La 478.30.012- Y 165.48-10 Y 271.9-5 Y 375.12-2.5 Y 477.04-1 Y 577.69-0.5

8. Hierarchical tablesof some elements and analytical lines Hierarchical tables of some elements and analytical lines

9. Spectral adjectives of analyte and major element lines Compound / Element Melting and vaporization temperatures, С  Wavelength, nm Detection limit, % Line intensity by Harrison Excitation potential, eV Analytical parameter BaF 2 / Ba 1368; 2250233.526 II 263.478 II 264.138 259.6678 I 0.002 1 – 10 60R 30 5 40 6.01 7.43 – 4.75 Calculation of intensity as squares under the curve, the background under peak took into account LaF 3 / La 1493; 2300333.749 II 324.513 II 324.935 II 261.034 I 289.307 II 0.0001 0.001 0.01 800 400 300 10 6 4.12 3.99 5.66 6.94 YF 3 / Y 1155; 2230297.4588 I 317.307 II 291.905 I 276.01 I 0.001 0.01 0.03 12 20 18 10 4.17 7.43 4.24 4.57

10. OE spectrum of BaF 2

11. Some lines of Ba and La Way of calculating their analytical parameters

12. Calibration types Calibration type Description 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 using the R j -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. The relative bias of analyte determination in the each j-th sample of training set is provided by where C cal. and C cert. are calculated and certificated contents, accordingly. For the entire set of CRMs within the interval

13. Calibrations used for Ba and La determination in BaF 2 crystals Calibration Element line composed of calibration & Its wavelength, nm NWPCRGLSOLS 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 for Ba and Y determination in BaF 2 crystals Calibration Element line composed of calibration & Its wavelength, nm NWNWPCRGLSOLS 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++++

14. Calibration selecting for Ba and La determination by rank criterion Calibration Δ C, %Δ RRank of Δ R Sum of ranks BaLaBaLaBaLa OLS-1 OLS-1 to each analyte line 7.8-78.3 0.01-70.9 3227336 NW NW to all lines of Ba and La1724123 PCR PCR to all lines of Ba and La 0.01-63.8 25358448 GLS GLS to all lines of Ba and La2310213

15. Calibration selecting for Ba and Y determination by rank criterion Calibration Δ C, %Δ RRank of Δ R Sum of ranks BaY Y Y OLS-1 OLS-1 to each analyte line 65.5-77.70.5-10 3293.548 NW NW to all lines of Ba and Y 0.591.52.54 PCR PCR to all lines of Ba and Y 5123.52.56 GLS GLS to all lines of Ba and Y0.411.513

16. Relative bias for determining Ba and Y in training set

17. Relative bias for determining Ba and La in training set

18. Technique of determination of La, Y and Ba in BaF 2 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, s r, are 0.08-0.12; 0.10-0.15;and 0.05-0.07, accordingly