Effect of additives on cadmium chemical vapor generation and reliable quantification of generation efficiency

Chemical vapor generation (CVG) of cadmium was optimized based on response from atomic absorption spectrometry (AAS) with a heated quartz tube atomizer (QTA). Effect of several modifiers on analytical performance was studied. These additives were: inorganic salts of Cr³⁺, Ti⁴⁺ and Co²⁺ and their on-line synthesized complexes with KCN and thiourea, respectively. The use of these additives resulted in sensitivity enhancement, better repeatability and correspondingly in improvement of overall CVG efficiency. The latter was quantified by two independent approaches: a) by means of ^115mCd radioactive indicator, b) from comparison of sensitivities obtained with conventional solution nebulization and with CVG, both coupled simultaneously to inductively coupled plasma mass spectrometry. Both approaches provided comparable results. The highest efficiency, between 60 and 70%, was reached in the presence of Cr³⁺/KCN and Ti⁴⁺/KCN while 19% was achieved in Co²⁺/ascorbic acid/thiourea environment. Highly irreproducible results with low CVG efficiency ranging from 2.5 to 15% were reached in the absence of any additives. The generated cadmium species were identified to be mostly free atoms regardless of the additives presence or their absence. Cr³⁺/KCN environment was selected as the most robust for CVG of Cd reaching sensitivity of 6.6 s ng^-1 Cd and limit of detection of 60 pg mL^-1 Cd (9 pg Cd absolute) with detection by QTA-AAS.