APPLICATION OF OES-AD SOFTWARE PACKAGE FOR DEVELOPING AUTOMATED TECHNIQUES

1. 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

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

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

4. Scheme of program complex for OEA executing KNOWLEDGE BASE 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 Choices of taking into account of background and AP calculations Chemometric selections of optimal conditions of AP processing and constructing calibrations Hierarchical tables of wavelengths of analytical lines of elements Search and identification of analytical lines It's different DATABASE Comparison of result quality of learn and test sets Table of element contents of CRMs,theirs stuff is available in Lab Forming of training and test sets Selection of optimal APs and calibrations Measured spectra of CRMs and samples It isn't different RETRAINING Desiredconditioncompliance Requirements to analytical results (qualitative, semiquantitative, quantitative) No Yes Results of determining content of i-thelement Processing sample spectra

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 BaF2; • 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 BaF2 crystals

8. Hierarchical tablesof some elements and analytical lines

9. Spectral adjectives of analyte and major element lines

10. OE spectrum of BaF2

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

12. 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 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. Calibration types Rank criterion from range of relative bias

13. Calibrations used for Ba and Y determination in BaF2 crystals Calibrations used for Ba and La determination in BaF2 crystals

14. Calibration selecting for Ba and La determination by rank criterion

15. Calibration selecting for Ba and Y determination by rank criterion

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 BaF2 • 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