Chromium speciation in tannery effluent—I. An assessment of techniques and the role of organic Cr(III) complexes

Three methods of chromium speciation were assessed in relation to possible interferences from Cr(III)-organic complexes. They were, namely: 1,5-diphenyl-carbazide (DPC) spectrophotometry, organic extraction with methyl isobutyl ketone (MIBK) and co-precipitation with iron and bismuth salts. Initially, a number of organic ligands, i.e. proteins, amino acids and organic acids were reacted with Cr(III) and only those complexes with solubility levels above that of ionic Cr(III) were assessed further. The spectrophotometric method was found to suffer minor interferences which were attributable to a non-specific turbidity effect. In comparison, two methods of MIBK extraction were found to suffer severe interferences with Cr(III)-protein complexes. Also, co-precipitation with iron salts resulted in high levels of contamination by Cr(III)-organic complexes in the ionic chromium fractions. Due to the poor solubility of bismuth salts, this method was discarded. The results demonstrate that chromium speciation in the presence of organic complexes can lead to erroneous results. However, with recognition of the presence of such complexes, corrections can be made. Since the co-precipitation behaviour of organic Cr(III) appears to be relatively specific, a scheme is described for the speciation of Cr(III) in tannery contaminated waterways. In addition, it is recommeded that a separate determination of Cr(VI) is conducted using a modification of the DPC method.