Removing petroleum hydrocarbons (PHCs) from polluted soil is challenging due to their low bioavailability and degradability. In this study, an experiment was carried out to treat soil polluted with petroleum hydrocarbon using a hybrid electro-Fenton (with BDD anode electrode) and biological processes stimulated with long-chain rhamnolipids (biosurfactants). Electro-Fenton treatment was applied as a pretreatment before the biological process to enhance PHC biodegradability, which would benefit the subsequent biological process. The effects of initial pH, hydroxide concentration, soil organic matter composition, PHCs intermediates during the electro-Fenton process, and total numbers of bacteria in the biological process were analyzed to determine the optimum conditions. The results showed that the optimized electrolysis time for the electro-Fenton was 12 h. The change induced during pretreatment at a specified time was found suitable for the biological process stage and led to 93.6% PHC degradation in combination with the electro-Fenton-and-biological process after 72 h. The combined system's performance was almost 40% higher than individual electro-Fenton and biological treatments. GC-MS analysis confirms the formation of 9-octadecen-1-ol (Z), 2-heptadecene, 1-nonadecene, 1-heneicosene, and pentacosane as fragmentation during the PHCs degradation process. Thus, the electro-Fenton process as pretreatment combined with a biological process stimulated with rhamnolipids (biosurfactants) could be effectively applied to remediate soil polluted with PHCs. However, the system needs further research and investigation to optimize electrolysis time and biosurfactant dose to advance this approach in the soil remediation process. © 2023 Elsevier Ltd

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