Regarding the determination of metallic elements, atomic spectrometry techniques are preferred. Flame atomic absorption spectrometry (FAAS) and electrothermal atomic absorption spectrometry (ETAAS) are the most common ones and they have been used to determine metallic elements (e.g., Ti or Zn in sunscreens or contaminants (e.g., Pb or Cd in lipsticks. Other techniques used are inductively coupled plasma atomic emission spectrometry (ICP-AES), inductively coupled plasma coupled to mass spectrometry (ICP-MS) or atomic fluorescence spectrometry.
Flame Atomic Absorption Spectrometry
Flame atomic absorption spectrometry (FAAS) is a mature analytical method, which is present in almost any analytical laboratory as a working horse for elemental determinations of metals. Innovation, however, is still going on with respect to the introduction of the sample into the atomizer and the increase of the analyte sampling efficiencies and residence times in the atomizer. By the so-called furnace in flame approach for volatile elements or volatile species forming elements especially, the sampling efficiency can be considerably increased as compared to conventional pneumatic nebulization with the possibility to considerably improve the power of detection for a number of elements.
Atomization Processes in the Flame
Once the aerosol reaches the flame the droplets are desolvated to form a mist of salt clotlets which then fuses and evaporates or sublimes. This process is critically dependent on the size and number of the particles, their composition and the flame mixture. As the absolute concentration of analyte in the flame is very small (< 10 -3 atm), the saturated vapour pressure may not be exceded even at temperatures below the melting point. The vaporization is fast; the molecules which make up the vapour decomposing into individual atoms almost instantaneously. In fact the distance which the sample travels through the flame before atomization may be very short, for example less than 1 cm for sodium chloride in an air-acetylene flame. Higher in the flame the sodium concentration will slowly decrease due to cooling of the flame and the composition of the flame has little effect on the atomization process. Other species, however, are more refractory (e.g. the alkaline-earth and rare-earth oxides) and may require a hotter flame and reducing environment to aid dissociation, thus reflecting the importance of flame chemistry (both ground state and excited atoms may be produced by radical reactions in the primary reaction zone of the flame). For many elements the atomization efficiency, defined as the ratio of the number of atoms to the total number of analyte species, atoms, ions and molecules in the flame, is 1, although for other elements (for example the lanthanoids) it is less than 1, even in a nitrous oxide acetylene flame. However, the formation of atoms is not the end of the story since once formed they may be lost through compound formation or ionization. Ionization increases exponentially with temperature and is a particular problem for the elements on the left of the periodic table, i.e. the alkali and the alkaline-earth elements. It is also a problem with Al, Ga, In, Sc, Ti and Tl, in the nitrous oxide-acetylene flame.