Assessment of Potentially Toxic Elements in Technosols by Tailings Derived from Pb–Zn–Ag Mining Activities at San Quintín (Ciudad Real, Spain): Some Insights into the Importance of Integral Studies to Evaluate Metal Contamination Pollution Hazards

Abstract

This work presents an integral methodological approach to assess the environmental potential hazards posed by metals and metalloids hosted by spolic technosols derived from old tailings from a mining operation for galena (PbS, with high Ag contents)-sphalerite (ZnS, with a varied cohort of trace elements contents) in central Spain. We studied the total and soluble concentrations and spatial distribution of Pb, Zn, Cd, As, and Fe and the mineralogy of these soils, as well as an ecotoxicological evaluation by means of bioassays. The indices assessing soil contamination such as pollution load index (PI) and natural mobility index (NMI) have been calculated. Furthermore, the phytotoxic effect of the soil samples has been determined and a chronic sediment toxicity test using the benthic ostracod Heterocypris incongruens was applied. The geochemical study of 33 spolic technosols samples indicates large to extremely large metal and metalloid total contents: up to 48,600 mg kg−1 Pb, 34,000 mg kg−1 Zn, 500 mg kg−1 Cd, and 1000 mg kg−1 As. Given that sphalerite is usually the most important host mineral for cadmium in hydrothermal mineral deposits, there is a high correlation (R = 0.75) between this element and Zn. On the other hand, despite being two metallogenically intertwined elements in ore deposits, Pb and Zn show a less significant relationship, which can be attributed both to heterogeneities in the mineralogical composition of the veins, and to the complex history of the mineral concentration process: In the older process, the interest was only for Pb, meanwhile in the late period, the interest was focused in Zn. The Phytotoxkit® bioassay showed that soils with high PTEs presented very high toxicity, particularly the inhibition germination is related to Pb, As, and Cd content and root inhibition with Pb content. Both indexes were correlated with pH and electrical conductivity; samples with lower pH and higher soluble salt content are those with higher seed germination inhibition and root growth inhibition. On the other hand, the Ostracodtoxkit® bioassay showed very high sensitivity, with 100% mortality. The applied bioassays confirmed the soil toxicity and it is highly recommended to complement the results from environmental chemistry with results from bioassays, in order to provide a more complete and relevant information on the bioavailability of contaminants and to characterize the risk of contaminated areas.