Extractable Cr(VI) Hotspots in the Defor Petrila Tailings Dump, Romania: A Redox-Based Hazard Screening Approach

Chromium-related hazard in mine wastes depends strongly on oxidation state, with hexavalent chromium [Cr(VI)] representing the most mobile and toxicologically relevant chromium form. Abandoned tailings dumps can develop sharp pH and redox gradients that favour either Cr(VI) persistence or attenuation, yet field-based evidence from Eastern European post-mining sites remains limited. This study evaluates the Defor Petrila tailings dump, Jiu Valley, Romania, as a first-tier environmental hazard-screening case study based on repeated monitoring performed during 2022–2024 at twelve permanent sampling points and two local operational control samples. Field pH and redox potential (Eh), moisture, organic matter, acid-extractable Mn and Fe, pseudo-total Cr, and method-defined extractable Cr(VI) were determined. Here, pseudo-total Cr refers to chromium released by microwave-assisted acid digestion and does not represent complete decomposition of the silicate matrix, while extractable Cr(VI) refers to the operationally defined fraction obtained by alkaline extraction. In addition, a conservative redox-based prioritisation score (Rredox) was applied only as an internal ranking layer to identify sectors where Cr(VI) is more likely to persist. The upper dump sector (P1–P4) was alkaline (pH 7.5–8.2), strongly oxidising (+280 to +412 mV), and enriched in Mn and Fe, whereas the lower sector (P9–P12) was wetter, slightly acidic to near-neutral, and reducing (−59 to −10 mV). Extractable Cr(VI) reached 18.7 mg kg−1 at P2 in 2024, while both control samples remained below the quantification limit. Exploratory repeated-site statistics, sector-based comparison, and correlation analysis supported a coherent association between Eh, Mn enrichment, and extractable Cr(VI), but these relationships are interpreted as spatially structured screening evidence rather than proof of a single mineralogical oxidation pathway. No direct exposure, leachability, bioaccessibility, ecotoxicity, airborne dust, water, vegetation, or biomonitoring measurements were included; therefore, the results identify priority zones for confirmatory toxicological and exposure-based assessment, not receptor-specific risk estimates. This study demonstrates that combining chromium speciation with field redox zonation can support conservative monitoring prioritisation at abandoned mine-waste sites where the toxic form of chromium may remain environmentally active.