Geogenic and Anthropogenic Origins of Mercury and Other Potentially Toxic Elements in the Ponce Enriquez Artisanal and Small-Scale Gold Mining District, Southern Ecuador

Artisanal and small-scale gold mining (ASGM) poses significant environmental challenges globally, particularly due to mercury (Hg) use. As an example, in Ecuador, Hg use still persists, despite its official ban in 2015. This study investigated the geogenic and anthro- pogenic contributions of potentially toxic elements (PTEs) in the Ponce Enriquez Mining District (PEMD), a region characterized by hydrothermally altered basaltic bedrock and Au-mineralized quartz veins. To assess local baseline values and identify PTE-bearing minerals, a comprehensive geochemical, mineralogical, and petrographic analysis was conducted on bedrock and mineralized veins. These findings reveal distinct origins for the studied PTEs, which include Hg, As, Cu, Ni, Cr, Co, Sb, Zn, and V. Specifically, Hg concentrations in stream sediments downstream (up to 50 ppm) far exceed natural bedrock levels (0.03–0.707 ppm), unequivocally indicating significant anthropogenic input from gold amalgamation. Furthermore, copper shows elevated concentration primarily linked to gold extraction. Conversely, other elements like As, Ni, Cr, Co, Sb, Zn, and V are primarily exhibited to be naturally abundant in basalts due to the presence of primary mafic minerals and to hydrothermal alterations, with elevated concentrations particularly seen in sulfides like pyrite and arsenopyrite. To distinguish natural geochemical anomalies from mining- related contamination, especially in volcanic terrains, this study utilizes Upper Continental Crust (UCC) normalization and local bedrock baselines. This multi-faceted approach effec- tively helped to differentiate basalt subgroups and assess natural concentrations, thereby avoiding misinterpretations of naturally elevated element concentrations as mining-related pollution. Crucially, this work establishes a robust local geochemical baseline for the PEMD area, providing a critical framework for accurate environmental risk assessments and sustainable mineral resource management, and informing national environmental quality standards and remediation efforts in Ecuador. It underscores the necessity of evaluating local geology, including inherent mineralization, when defining environmental baselines and understanding the fate of PTEs in mining-impacted environments.