Geochemical Regulation of Heavy Metal Speciation in Subtropical Peatlands: A Case Study in Dajiuhu Peatland

Heavy metals in peatland pose significant ecological risks due to their persistence, bioaccumulation, and dynamic mobilization under fluctuating environmental conditions. Understanding heavy metal dynamics in subtropical peatlands is critical for addressing global gaps in wetland metal cycling, as these ecosystems face intensified organic decomposition and climatic fluctuations that amplify mobilization risks—contrasting starkly with stable northern counterparts. This study investigates the geochemistry of heavy metals (Cr, Cu, Cd, and Pb) of Dajiuhu peatland in central China, using sequential extraction, gradient diffusion (DGT), and random forest modeling. The mean concentrations of Cr, Cu, Cd, and Pb in peat samples were 24.6 ± 13.7 mg/kg, 14.9 ± 2.51 mg/kg, 1.15 ± 0.62 mg/kg, and 54.9 ± 16.16 mg/kg. Principal component analysis identified three sources: plant-derived litter, bedrock weathering, and atmospheric deposition. Metal speciation revealed the predominance of residual fractions (Cr: 64%, Cu: 61%, Pb: 65%, Cd: 35%), with Cd exhibiting higher mobility (exchangeable: 20%, reducible: 25%). DGT measurements further confirmed distinct migration behaviors, as Cd stored in peat actively diffuses into the surrounding environment, while Pb present in the environment becomes immobilized within the peat matrix. Environmental factors regulate heavy metal speciation through distinct mechanisms. The exchangeable fractions of Cu and Cr are primarily controlled by the C/N ratio, whereas their oxidizable forms are significantly associated with Al content and pH levels. The exchangeable fractions of Pb and Cd are largely influenced by oxidation-reduction potential (ORP) and Ca concentrations, and their reduced forms are closely linked to total sulfur (TS) content. Furthermore, the reducible fractions of Cr and Cd are not only regulated by ORP but also modulated by TS. Our study highlights that the mobility of heavy metals in subtropical peatlands is likely to increase substantially as a result of environmental changes.