1. contrAA ® - A Revolution in Spectroscopy Basics and Applications of High-Resolution Continuum Source AAS

2. Methods for element analysis contrAA ® - A Revolution in Spectroscopy2 AAS – a well established method for more than 50 years BUT !!  Simplicity  Less interferences  Robustness  Low purchase cost  Low operation cost  Single element method  Specific HCLs required  Unprofitable for many elements  Limitation in background correction

3. New instrument development needs motivation contrAA ® - A Revolution in Spectroscopy3 AAS goes multielement!

4. LS AAS Cx CuPb Fe Cd Ni Zn Single element method New instrument development needs motivation: We expect fast results 4contrAA ® - A Revolution in Spectroscopy

5. Real multielement Analysis CS AAS Sequential multi element analysis Cu, Pb, Fe, Cd, Ni, Zn… New instrument development needs motivation: We expect fast results 5contrAA ® - A Revolution in Spectroscopy

6. New instrument development needs motivation contrAA ® - A Revolution in Spectroscopy6 In case of a spectral interference, we can see only the result, but not the reason – therefore the optimization of method parameters to avoid the spectral interferences is difficult. Background correction failed, but why??? We need more information!

7. Key components of HR-CS AAS contrAA ® - A Revolution in Spectroscopy7 HR-CS AASLS-AAS Radiation source Xenon – short arc lampHCL, EDL, boosted HCL Atomizer Identical atomizer for flame and graphite technique Monochromator High resolution >1:140000Low resolution Detector CCD array detectorSingle spot detector (PMT) Software ASpectCS ® WinAAS ®

8.  Optical set up CS AAS Furnace Echelle grating Flame Arc lamp High Resolution Monochromator prism CCD detector ISAS Berlin  Low focal length: f  400 mm  High spectral resolution: / Δ > 145 000 8contrAA ® - A Revolution in Spectroscopy

9. Radiation source contrAA ® - A Revolution in Spectroscopy9  LS AAS Hollow cathode lamp (HCL) line radiator Cathode contains the element to be analyzed Xenon short arc lamp continuum radiator Covers whole wave length range 185 – 900 nm Determination of more than 67 elements with one lamp only  HR-CS AAS

10. Radiation source contrAA ® - A Revolution in Spectroscopy10 Different radiation sources in comparison A Xenon-short arc lamp, XBO 301, 300 W, (GLE Berlin), „Hot - Spot“ - Mode B Xenon lamp, L 2479, 300 W, (HAMAMATSU), diffuse mode C D2 - Lamp, MDO 620, 30 W, (HERAEUS) Source: „High-resolution continuum source AAS“ Welz,Becker-Roß,Florek,Heitmann Ag Au Pb Cd Pb Zn As

11. Atomizer in HR-CS AAS contrAA ® - A Revolution in Spectroscopy11 Graphite furnace atomizer Quartz cell atomizer Flame atomizer

12. Double Echelle Monochromator contrAA ® - A Revolution in Spectroscopy12 2 6 5 4 3 1 2 Source: ISAS Berlin 1: entrance slit (fixed) 2: off-axis parabolic mirror 3: prism in Littrow- position 4: intermediate slit (variable) 5: Echelle- grating in Littrow- position 6: CCD – array detector

13. LS AAS Emission scan Mn – Triplet: 279.4817 nm 279.8269 nm 280.1085 nm Monochromator resolution LS AAS vers. HR-CS AAS CS AAS Absorption spectra Resolution factor 100 better than LS AAS !!! 13contrAA ® - A Revolution in Spectroscopy

14. AnalyteWavelength (nm)Disturbing elements Wavelength (nm) -Difference (pm) Se196.03Fe196.06030 As193.70Fe193.67030 Zn213.856Fe213.8593 Cd228.80As Fe 228.810 228.720 10 80 Ni232.003Fe232.03633 Sn224.605Pb Fe 224.690 224.565 85 40 Mn279.48Fe279.47010 Cu324.75Fe324.60015 Al396.15Fe396.11040 High Resolution – spectral interferences 14contrAA ® - A Revolution in Spectroscopy

15. CCD Detector contrAA ® - A Revolution in Spectroscopy15 New detection technology Detector “Pixels” are illuminated and read out simultaneously and independently. 200 Pixels are used analytically 200 independent detectors ! 3 Pixels for AA measurement - and the others???

16. Corrections contrAA ® - A Revolution in Spectroscopy16 Type of interferenceLS-AASHR-CS AAS Lamp intensity driftOptical double beam sequential Reference pixels simultaneous Thermal emissionLamp modulation sequential Reference pixels simultaneous Non specific absorptionBG correction sequential Reference pixels reference spectrum simultaneous

17. Corrections contrAA ® - A Revolution in Spectroscopy17 In HR-CS AAS we have a Third Dimension, i.e. we can see a lot more !  We can see the spectral interference  We can avoid the spectral interference  And we have much better ways to correct for spectral interferences

18. Background correction and resolution contrAA ® - A Revolution in Spectroscopy18 V 318.341 V 318.540 Ni 318.437 Fe 318.490

19. Corrections of discontinuous events contrAA ® - A Revolution in Spectroscopy19  OH, NO, CN are natural constituents of flame gases  NO, PO, SiO, CS etc. might be generated in the presence of high matrix concentration  Neither the D2 nor the Smith-Hieftje system can correct for this background,  the Zeeman system can only correct if the background is not affected by the magnetic field !  In HR-CS AAS we can measure and store a reference spectrum that can be subtracted from the sample spectrum using a least-squares algorithm Diatomic molecules with rotational fine structure

20. A Short Glance on Correction Models “Least Squares Background Correction ” 20contrAA ® - A Revolution in Spectroscopy

21. NO- Structure on Zn- line 213.857 nm Corrections of discontinuous events - Recording of reference spectra blank: 1% HNO 3 1% HNO 3 + 0.05 mg/L Zn 21contrAA ® - A Revolution in Spectroscopy

22. Correction of NO structure at 213.857 nm Zn- line NO structures corrected Zn absorption spectra Corrections of discontinuous events - Recording of reference spectra 22contrAA ® - A Revolution in Spectroscopy

23. 23 Quality is the difference Quality is the difference

24. contrAA ® - A Revolution in Spectroscopy24 Thank you for your attention!