Assessment of Potential Environmental Risks Posed by Soils of a Deactivated Coal Mining Area in Northern Portugal—Impact of Arsenic and Antimony

Active and abandoned mining sites are significant sources of heavy metals and metalloid pollution, leading to serious environmental issues. This study assessed the environmental risks posed by potentially toxic elements (PTEs), specifically arsenic (As) and antimony (Sb), in the Technosols (mining residues) of the former Pejão coal mine complex in Northern Portugal, a site impacted by forest wildfires in October 2017 that triggered underground combustion within the waste heaps. Our methodology involved determining the “pseudo-total” concentrations of As and Sb in the collected heap samples using microwave digestion with aqua regia (ISO 12914), followed by analysis using hydride generation-atomic absorption spectroscopy (HG-AAS). The concentrations of As an Sb ranging from 31.0 to 68.6 mg kg−1 and 4.8 to 8.3 mg kg−1, respectively, were found to be above the European background values reported in project FOREGS (11.6 mg kg−1 for As and 1.04 mg kg−1 for Sb) and Portuguese Environment Agency (APA) reference values for agricultural soils (11 mg kg−1 for As and 7.5 mg kg−1 for Sb), indicating significant enrichment of these PTEs. Based on average Igeo values, As contamination overall was classified as “unpolluted to moderately polluted” while Sb contamination was classified as “moderately polluted” in the waste pile samples and “unpolluted to moderately polluted” in the downhill soil samples. However, total PTE content alone is insufficient for a comprehensive environmental risk assessment. Therefore, further studies on As and Sb fractionation and speciation were conducted using the Shiowatana sequential extraction procedure (SEP). The results showed that As and Sb levels in the more mobile fractions were not significant. This suggests that the enrichment in the burned (BCW) and unburned (UCW) coal waste areas of the mine is likely due to the stockpiling of lithic fragments, primarily coals hosting arsenian pyrites and stibnite which largely traps these elements within its crystalline structure. The observed enrichment in downhill soils (DS) is attributed to mechanical weathering, rock fragment erosion, and transport processes. Given the strong association of these elements with solid phases, the risk of leaching into surface waters and aquifers is considered low. This work underscores the importance of a holistic approach to environmental risk assessment at former mining sites, contributing to the development of sustainable remediation strategies for long-term environmental protection.