Element fractionation by sequential extraction in a soil with high carbonate content

Abstract

The influence of carbonate and other buffering substances in soils on the results of a 3-step sequential extraction procedure (BCR) used for metal fractionation was investigated. Deviating from the original extraction scheme, where the extracts are analysed only for a limited number of metals, almost all elements in the soils were quantified by X-ray fluorescence spectroscopy, in the initial samples as well as in the residues of all extraction steps. Additionally, the mineral contents were determined by X-ray diffractometry. Using this methodology, it was possible to correlate changes in soil composition caused by the extraction procedure with the release of elements. Furthermore, the pH values of all extracts were monitored, and certain extraction steps were repeated until no significant pH-rise occurred. A soil with high dolomite content (27%) and a carbonate free soil were extracted. Applying the original BCR-sequence to the calcareous soil, carbonate was found in the residues of the first two steps and extract pH-values rose by around two units in the first and second step, caused mainly by carbonate dissolution. This led to wrong assignment of the carbonate elements Ca, Mg, Sr, Ba, and also to decreased desorption and increased re-adsorption of ions in those steps. After repetition of the acetic acid step until extract pH remained low, the carbonate was completely destroyed and the distributions of the elements Ca, Mg, Sr, Ba as well as those of Co, Ni, Cu, Zn and Pb were found to be quite different to those determined in the original extraction. Furthermore, it could be shown that the effectiveness of the reduction process in step two was reduced by increasing pH: Fe oxides were not significantly attacked by the repeated acetic acid treatments, but a 10-fold amount of Fe was mobilized by hydroxylamine hydrochloride after complete carbonate destruction. On the other hand, only small amounts of Fe were released anyway. Even repeated reduction steps did not destroy the amorphous Fe oxides completely, showing that 0.1 mol L −1 hydroxylamine hydrochloride was not strong enough to attack these oxides effectively. The extraction sequences were carried out not only on the soil samples, but also on their coarse and fine fractions (> or <2 μm). The fine fraction of the calcareous soil contained only 10% dolomite, but was enriched in organic matter and clay minerals, which also resulted in increased extract pH-values during the sequential extraction. Hence, the effects on ion release in the fine fraction were similar to those of the whole soil. Since the destruction of the organic matter was incomplete after regular oxidation, the H 2O 2-treatment of the fine fraction had to be repeated. The addition of the extractable amounts of the two fractions showed good agreement to the results obtained for extraction of the whole soils. Likewise the pH-values of the carbonate-free soil extracts did not increase significantly, therefore it was concluded that repetitions of extraction steps for this soil were not necessary. Extract-pHs should always be controlled so that extraction conditions are comparable; to be able to use the BCR extraction scheme or similar ones for carbonate- and organic-rich samples this is mandatory. Single extraction steps should be repeated if pH rises too much; additionally the oxidizing step should be performed more than twice for samples rich in organic substances, depending upon the violence of the reaction with H 2O 2. If these precautions are neglected the validity of the extraction data is likely to be questionable.