Supramolecular bioamphiphile facilitated bioemulsification and concomitant treatment of recalcitrant hydrocarbons in petroleum refining industry oily waste

Bioremediation of real-time petroleum refining industry oily waste (PRIOW) is a major challenge due to the poor emulsification potential and oil sludge disintegration efficiency of conventional bioamphiphile molecules. The present study was focused on the design of a covalently engineered supramolecular bioamphiphile complex (SUBC) rich in hydrophobic amino acids for proficient emulsification of hydrocarbons followed by the concomitant degradation of total petroleum hydrocarbons (TPH) in PRIOW using the hydrocarbonoclastic microbial bio-formulation system. The synthesis of SUBC was carried out by pH regulated microbial biosynthesis process and the yield was obtained to be 450.8 mg/g of petroleum oil sludge. The FT-IR and XPS analyses of SUBC revealed the anchoring of hydrophilic moieties of monomeric bioamphiphilic molecules, resulting in the formation of SUBC via covalent interaction. The SUBC was found to be lipoprotein in nature. The maximum loading capacity of SUBC onto surface modified rice hull (SMRH) was achieved to be 45.25 mg/g SMRH at the optimized conditions using RSM-CCD design. The SUBC anchored SMRH was confirmed using SEM, FT-IR, XRD and TGA analyses. The adsorption isotherm models of SUBC onto SMRH were performed. The integrated approach of SUBC-SMRH and hydrocarbonoclastic microbial bio-formulation system, emulsified oil from PRIOW by 92.86 ± 2.26% within 24 h and degraded TPH by 89.25 ± 1.75% within 4 days at the optimum dosage ratio of SUBC-SMRH (0.25 g): PRIOW (1 g): mass of microbial-assisted biocarrier material (0.05 g). The TPH degradation was confirmed by SARA fractional analysis, FT-IR, ¹H NMR and GC-MS analyses. The study suggested that the application of covalently engineered SUBC has resulted in the accelerated degradation of real-time PRIOW in a very short duration without any secondary sludge generation. Thus, the SUBC integrated approach can be considered to effectively manage the hydrocarbon contaminants from petroleum refining industries under optimal conditions.