The importance of drying and grinding samples for determining mobile chromium fractions in polluted river sediments.

A possible impact of sample preparation on the chemical fractionation results is generally underestimated in studies of forms of occurrence of heavy metals in river sediments. Our analysis of the recently published results of sequential extraction of chromium has revealed the effect of sample grinding on the result of determination of mobile chromium fractions in river sediments. This observation has been experimentally verified along with the analysation of potential effect of river sediment drying conditions on chromium distribution pattern. The studies were carried out on river sediments polluted with tannery effluents (Cr, 29.2-233 mg/kg). The determined content of chromium bound to carbonates in powdered samples was 2 to 7 times higher than those in raw river sediment samples. It was shown that the main reason was the different kinetic characteristics of chromium leaching in these sediments. Using the shrinking core model, it was found that diffusion through the "ash layer" was the rate-controlling step during the extraction of the carbonate fraction of chromium. It has been additionally confirmed that common air drying of sediment samples does not affect the results of chemical fractionation of chromium.The results of our studies are also vital for the assessment of environmental risk posed by river sediments polluted with heavy metals. In the case of sediment samples used in this study, powdering changed the risk category (RAC) from low risk to high risk. Hence, in order to achieve a realistic assessment of chromium mobility and environmental risk, it is advisable to use raw samples, despite their poorer homogeneity, and thus, lower precision of chemical fractionation results.