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The high geogenic levels of trace metal(loid)s preserved within black shale can be released during natural weathering, causing global concern. Currently, the accumulation, speciation and potential mobilization of two highly toxic metal(loid)s, arsenic (As) and antimony (Sb), from black shale to soils remain unresolved, which hinders the evaluation of their potential risk to surrounding environments. Here, we demonstrate the geochemical enrichment, species transformation, and leaching behavior of As and Sb by applying weathering-induced alteration, sequential extraction and synchrotron-based X-ray absorption near edge spectroscopy (XANES) in the analysis of a range of black shale and weathered samples from two profiles collected from typical Cambrian sedimentary strata of the Pearl River Delta, southern China. The results showed significant accumulation of trace metal(loid)s, including As (43.8–458.0 mg/kg), Sb (7.2–34.5 mg/kg), Cu (8.8–451.0 mg/kg) and Ni (22.2–108.0 mg/kg), in the black shale and weathered products, and high enrichment factors for As (22.0–266.8) and Sb (1.2–6.4) were observed, consistent with the very high degrees of weathering (chemical index of alteration: 83–91). Arsenic in the shale was dominated by arsenate (46–85%), as identified using XANES, and this was resulted from extensive weathering, which facilitated the oxidation of arsenite and arsenopyrite species. Accordingly, significant decreases in sulfide-associated As and Sb were observed in highly weathered products. As a result, As and Sb were primarily in the immobilizable fractions associated with amorphous and well-crystallized Fe/Mn oxides, largely due to the increased formation of secondary Fe (oxyhydr)oxides, including goethite-like minerals, which mainly derived from the oxidative weathering of chlorite-like minerals. Nevertheless, high concentrations of As (<64 μg/L), Sb (14–70 μg/L), and Ni (3–92 μg/L) still leached from black shale samples exposed to synthetic acid rain in the 18-h batch leaching experiment. Our combined characterization results indicated that a small percentage of the high contents of geogenic As and Sb could potentially be released. However, soluble trace metal(loid)s in shale leachate could still endanger surrounding ecosystems, and continual monitoring during long-term natural weathering processes is merited for global black shale regions. • Natural weathering governed the accumulation of trace metal(loid)s in soils derived from black shale • Arsenate dominated in black shale-associated products and soils due to oxidation of reduced As species in oxic environment • In situ-formed secondary Fe-bearing minerals sequestered the pre-released As and Sb from black shale weathering • Low-level but persistent dissolved trace metal(loid)s from black shales still pose ecological risks [ABSTRACT FROM AUTHOR]