The document discusses atomic spectroscopy, covering fundamental principles, types of techniques such as atomic absorption spectroscopy (AAS), flame emission spectroscopy (FES), and inductively coupled plasma atomic emission spectrometry (ICP-AES). It details the processes involved in each method, including sample preparation, instrumentation, and applications across fields like clinical analysis, environmental testing, and industry. Various elements detectable by these techniques and calibration concerns related to spectral interferences are also addressed.

1. Atomic Spectroscopy:Basic Principles And InstrumentsVasiliy V. Rosen, M.Sc., ZBM Analytical Laboratorywww.rosen.r8.org2011

2. Atomic SpectroscopyAbsorption Spectroscopy: AAS Emission Spectroscopy: FES, ICP-AES(OES)Mass Spectrometry

3. Atomic SpectroscopyIon EmissionAtom EmissionE – energy difference between two levels;h – Plank’s constant, 6.626068 × 10-34 m2kg/s;c – speed of light, 299 792 458 m/s;λ – wavelenght, nmAfter Boss. C.B. and Freden K.J. Concepts, Instrumentation and Techniques in Inductively Coupled Plasma Optical Emission Spectrometry. 1997

4. Atomic SpectroscopyNebulizer converts the solution into a sprayFlame (or Plasma) causes the solvent to evaporate, leaving dry aerosol particles, then volatilizes the particles, producing atomic, molecular and ionic speciesAfter Skoog D. Fundamentals of Analytical Chemistry, 2004, p. 844

5. Flame Emission Spectroscopy (FES)Propane-butane flame ( 2000 – 3000 º C);

6. Optical filter is used to monitor for the selected emission wavelength produced by the analyte;

7. Suitable for elements with low excitation energy (Na, K, Li, Rb and Ca).Flame Emission Spectroscopy (FES)Optic FilterFlameData DisplayNebulizerFlame Photometer M-410 (Sherwood Scientific, UK)

8. Atomic absorption spectroscopy (AAS)Gases mixture flame (1800 – 4500 º C): air-propane, air-acetylene etc. ;

9. Atomic absorption spectrometry quantifies the absorption of ground state atoms in the gaseous state ;

10. The atoms absorb ultraviolet or visible light and make transitions to higher electronic energy levels . The analyte concentration is determined from the amount of absorption.Atomic absorption spectroscopy (AAS)Elements detectable by AA are highlighted in pink

11. Atomic absorption spectroscopy (AAS)Operation principle of AASLight source – hollow cathode lamp. Each element has its own unique lamp.

12. Atomic cell – flame (gas mixture) or graphite furnance (accepts solutions, slurries, or even solids).

13. Detector – photomultiplier.After G.Ma and G.W. Gonzales, http://www.cee.vt.edu

14. Atomic absorption spectroscopy (AAS)

15. AtomicemissionspectroscopyICP-AESInductively Coupled Plasma -Atomic Emission Spectrometry

16. ICP-AESBasicsAtomic emission spectroscopy measures the intensity of light emitted by atoms or ions of the elements of interest at specific wavelengths;

17. Inductively Coupled Plasma spectrometers use emission spectroscopy to detect and quantify elements in a sample;

18. ICP-AES uses the argon plasma (6000-10000º C) for atomization and excitation of the sample atoms;

19. ICP-AES determines approximately all of the elements except gases and some non-metals (C, N, F, O, H).

20. ICP-aes spectrometer arcos

21. Schematic diagram of the processes in the ICPAfter SpectroGmbh, Germany

22. ICP spectrometerMain SystemsSample Introduction System: to deliver the sample solution to the plasma. Consists of pump, nebulizer and spray chamber.

23. Plasma: to generate the signal. Plasma is forming in the torch from gas argon.

24. Optics: to measure the signal.

25. Computer with appropriate software: for controlling the instrument and measuring process.ICP-AES: Sample introduction systemTorch with PlasmaNebulizer (cross-flow)Spray ChamberTo WasteSample Solution EntranceArgon Supply

26. ICP-AES: PlasmaInductively Coupled Plasma SourceA plasma is a hot, partially ionizedgas. It contains relatively highconcentrations of ions and electrons. Argon ions, once formed in a plasma, are capable of absorbing sufficient power from an external source to maintain the temperature at a level at which further ionization sustains the plasma indefinitely. The plasma temperature is about 10 000 K.After Manning T.J. and Grow W.P., 1997

27. ICP-AES: PlasmaInductively Coupled Plasma Source

28. ICP-AES: Radial (SOP) and axial (EOP)EOP: End-on-PlasmaSOP: Side-on-Plasmamore suitable for hard matrices (concentrated samples);

29. alkali metals (Na, K, Li) calibration is more linear;

30. less spectral interferences;

31. lower sensitivity (Limit-of-Detection is higher);

32. more suitable for light matrices;

33. alkali metals (Na, K, Li) calibration is less linear;

34. more spectral interferences;

35. higher sensitivity (Limit-of-Detection is lower);ICP-AES: Radial (SOP) and axial (EOP)After SpectroGmbh, Germany

36. ICP-AES: opticsAfter SpectroGmbh, Germany

37. ICP-AES: Sample PreparationMicrowave-assisted DigestionHot PlateDigestion BlockMost samples have to be prepared for analysis by ICP. Solid samples are solubilized. Organic matter is "mineralized" i.e. converted to inorganic compounds.

38. ICP-AES: calibration curve

39. ICP-AES: spectral interferencesAu (gold) peak on 242.795 nm

40. ICP-AES: spectral interferencesAu (gold) peak on 242.795 nm is interfered by Mn 242.794 nm Au (gold) peak on 267.595 nm is free of Mn interference!

41. ICP-AES, FEs and AAS: applicationClinical Analysis: metals in biological fluids (blood, urine);

42. Environmental Analysis: trace metals and other elements in waters, soils, plants, composts and sludges;

43. Pharmaceuticals: traces of catalysts used; traces of poison metals (Cd, Pb etc);

44. Industry: trace metal analysis in raw materials; noble metals determination.

45. Forensic science: gunshot powder residue analysis, toxicological examination ( e.g., thallium (Tl) determination)

46. referencesBoss, C.B. and Freden, K.J. Concepts, Instrumentation and Techniques in Inductively Coupled Plasma Optical Emission Spectrometry. 1997

47. Skoog, D. Fundamentals of Analytical Chemistry, 2004

48. Ma, G. and Gonzales, G.B. Flame Atomic Absorption Spectrometry. http://www.cee.vt.edu

49. Manning T.J. and Grow W.P. Inductively Coupled Plasma Atomic Emission Spectrometry. The Chemical Educator, v.1. N 2. 1997.

50. Lecture by Dr. MordechayShoenfeld, “ICP-AES”, Course 71106, Faculty of Agriculture, HUJI. 2010.