Determination of metal-humic complexes, free metal ions and total concentrations in natural waters

Abstract

A comparison of two systems for the quantitation of metal-humic complexes and free metal ions, consisting of the separation by coupled ion exchange columns followed by detection by inductively coupled plasma mass spectrometry or cold vapour atomic fluorescence spectrometry, is presented. The systems evaluated comprised the serially coupled anion and cation exchangers, Sephadex A-25/Chelex 100 and Dowex 1X8/Chelamine Metalfix. Separation and preconcentration of the species studied were accomplished with both systems, elution being carried out using 2 M HNO ₃ . Total concentrations, metal-humic complex fractions and free metal ion fractions of Al, Ba, Cd, Co, Cu, Fe, Hg, Mn, Pb, Sr, U and Zn in nine natural waters were determined. Statistical evaluation of the data from the two cation exchange materials, including results for additional elements, showed better precision (for Al, Ba, Cr, Cu and Mo) and higher recoveries (Al, Ba, Cd, Fe, Sr and Zn) for Chelex 100 than Chelamine Metalfix for free metal ions. On the other hand, Chelamine Metalfix recovered a significantly greater amount of Ni. The amounts of metal-humic complexes were compared with modelled distributions of these species, and one advantage of the preferred Sephadex A-25/Chelex 100 system is that the elements studied are all correctly classified with respect to their binding strengths to humic substances, which is not the case with the Dowex 1X8/Chelamine Metalfix pair. With the preferred system, metal-humic complexes can be reliably determined, as indicated by the results of equilibrium speciation modelling. However, comparison with the total concentrations showed statistically significant, non-quantitative recoveries of Al, Cu, Hg, Mn, U and Zn from some samples. Thus a combination of speciation and total concentration measurements is required to obtain a complete representation of the distribution of trace elements in natural waters.