Sequential extractions on mine tailings samples after and before bioassays: implications on the speciation of metals during microbial re-colonization

Mine tailings may be remediated using metal tolerant microorganisms as they may solve the limiting conditions for healthy development of plants (i.e., low organic mater content and poor physical conditions). The aim of this study was to investigate the consequences of microbial colonization on the chemical speciation of trace metals. Surface samples from the Valenciana mine tailings (Guanajuato, Mexico) were used for long-term bioassays (BA), which consisted in the promotion of microorganisms, development on tailings material under stable laboratory conditions (humidity, temperature, and light exposure). A five-step sequential extraction method (exchangeable, carbonate/specifically adsorbed, Fe–Mn oxides, organic matter (OM)/sulfide, and residual fractions) was performed before and after BA. Extraction solutions and leachates were analyzed by inductively coupled plasma-mass spectrometry. OM content, cationic exchange capacity, and pH values were also assessed before and after BA. The results indicate that trace elements are generally present in nonresidual fractions, mainly in the Fe–Mn oxides fraction. The concentration of total Zn, As, Se, Pb, and exchangeable Cu and Pb is above the recommendable limits for soils. Despite the high bioavailability of the former elements, biofilms successfully colonized the tailing samples during the BA. Cyanobacteria and green algae, heterotrophic fungi, aerobic bacteria, and anaerobic bacteria composed the developed biofilms. Chemical controls of trace elements could be attributed to absorption onto inorganic complexes (carbonates, metal oxides), while biofilm occurrence seems to enhance complexation and immobilization of Cr, Ni, Cu, Zn, As, and Pb. The biofilm developed does not increase the bioavailable forms and the leaching of the trace elements, but significantly improves the OM contents (natural fertilization). The results suggest that biofilms are useful during the first steps of the mine tailings remediation.