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Chapter 9:  Atomic Absorption & Atomic Fluorescence Spectrometry
  • Sample Atomization
  • Atomic Absorption (AA)
  • Atomic Fluorescence (AF)


  • Both AA and AF require a light source
  • Like Molecular Absorption & Fluorescence, in AA high intensity is NOT required, in AF high intensity results in greater sensitivity
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AA Slot Burner and Flame
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There are many possible variations  for the hydride generation apparatus
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"Interferences in AA can be"
  • Interferences in AA can be
  • Spectral – atomic spectral lines overlap or are too close to resolve – these are rare & generally well known or characterized
  • Matrix – scattering of radiation during atomization (smoke), enhancement by matrix elements, structured background – handled by background correction
  • Chemical – reactions that take place to alter the analyte (like Ca atoms reacting with PO4 to form a new species) – change conditions
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"Background Correction in AA"
  • Background Correction in AA
  • Two-Line correction (not very common)
  • Continuous source correction (very common)
  • Zeeman background correction (common for graphite furnace instruments)
  • Smith-Hieftje correction (relatively new ‘83)
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Normal or idealized situation for the absorption of source radiation in AA
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Normally assume baseline is flat not structured.  In the absence of peak would have flat baseline Peak height easily measured
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The AA source (HCL or EDL) tells us the absorbance at the λ of interest
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The Zeeman effect splits the absorption peak in a magnetic field & shifts absorption to higher & lower wavelength.  The new absorption peaks interact differently with polarized light allowing analyte & background absorbance to be measured
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Another type of matrix interference not alleviated by background correction involves variable amounts of analyte  ionization in flames or plasmas
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One other factor (other than temp.) that influences degree of ionization is the presence of another easily ionized species. Here K enhances the Sr AA signal by suppressing Sr ionization
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"Atomic Fluorescence – use an..."
  • Atomic Fluorescence – use an intense light source to excite AF of elements in a flame or plasma.
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Chapter 10:  Emission Spectroscopy Using Plasmas, Arcs or Sparks
  • Inductively Coupled Plasma (ICP)
  • Direct Current Plasma (DCP)
  • Arcs and Sparks


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Inductively Coupled Plasma (ICP)
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ICP Torch with sample introduction system (nebulizer and spray chamber)
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An alternate means of getting sample into ICP
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ICP Temps.

The viewing area for each element is typically reported as mm above the load coil
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