Petroleum hydrocarbons, heavy metals and agricultural pesticides have mutagenic, carcinogenic, immunotoxic and teratogenic effects and cause drastic changes in soil physicochemical and microbiological characteristics, thereby representing a serious danger to health and environment. Therefore, soil pollution urgently requires the application of a series of physicochemical and biological techniques and treatments to minimize the extent of damage. Among them, bioremediation has been shown to be an alternative that can offer an economically viable way to restore polluted areas. Due to the difficulty in choosing the best bioremediation technique for each type of pollutant and the paucity of literature on soil bioremediation enhanced by the use of specific additives, we reviewed the main in situ and ex situ methods, their current properties and applications. The first section discusses the characteristics of each class of pollutants in detail, while the second section presents current bioremediation technologies and their main uses, followed by a comparative analysis showing their respective advantages and disadvantages. Finally, we address the application of surfactants and biosurfactants as well as the main trends in the bioremediation of contaminated soils.

Among the innovative technologies utilized for the treatment of contaminated soils, the use of green surfactants appears to be a biocompatible, efficient, and attractive alternative, since the cleaning processes that normally use synthetic surfactants as additives cause other problems due to toxicity and the accumulation of by-products. Three green surfactants, i.e., two biobased (biobased 1 and biobased 2) surfactants produced by chemical synthesis and a microbial surfactant produced from the yeast Starmerella bombicola ATCC 22214, were used as soil remediation agents and compared to a synthetic surfactant (Tween 80). The three surfactants were tested for their ability to emulsify, disperse, and remove different hydrophobic contaminants. The biosurfactant, which was able to reduce the water surface tension to 32.30 mN/m at a critical micelle concentration of 0.65 g/L, was then used to prepare a commercial formulation that showed lower toxicity to the tested environmental bioindicators and lower dispersion capacity than the biobased surfactants. All the green surfactants showed great emulsification capacity, especially against motor oil and petroleum. Therefore, their potential to remove motor oil adsorbed on different types of soils (sandy, silty, and clay soil and beach sand) was investigated either in kinetic (flasks) or static (packed columns) experiments. The commercial biosurfactant formulation showed excellent effectiveness in removing motor oil, especially from contaminated sandy soil (80.0 ± 0.46%) and beach sand (65.0 ± 0.14%) under static conditions, while, in the kinetic experiments, the commercial biosurfactant and the biobased 2 surfactant were able to remove motor oil from all the contaminated soils tested more effectively than the biobased 1 surfactant. Finally, the S. bombicola commercial biosurfactant was evaluated as a soil bioremediation agent. In degradation experiments carried out on motor oil-contaminated soils enriched with sugarcane molasses, oil degradation yield in the sandy soil reached almost 90% after 60 days in the presence of the commercial biosurfactant, while it did not exceed 20% in the presence of only S. bombicola cells. These results promise to contribute to the development of green technologies for the treatment of hydrophobic pollutants with economic gains for the oil industries.

The successful production of a biosurfactant is dependent on the development of processes using low cost raw materials. In the present work, an economically attractive medium composed of corn steep liquor and waste cooking oil was formulated to maximize the production of bioemulsifier by Mucor circinelloides UCP0001. A central rotational composite design was applied to statistical validation of the production. The emulsifying properties, stability under extreme conditions, its toxicity character, and the characterization of the bioemulsifier were determined. The best condition for biomolecule synthesis occurred in the assay 2 containing 4% of corn steep liquor and 3% waste soybean oil and exhibited 100% emulsification index for canola oil and petroleum, as well as excellent emulsifying activity for canola oil and burned engine oil. The nutritional factors studied showed statistical relevance, since all linear, quadratic effects and their interactions were significant. The bioemulsifier showed 2.69 g/L yield and the chemical character of the molecule structure was identified by FT-IR (Fourier Transform Infrared) spectroscopy. The bioemulsifier showed no toxicity to Artemia salina and Chlorella vulgaris. Stable emulsions were obtained under extreme conditions of temperature, pH, and salinity. These findings contribute to understanding of the relationship between production, physical properties, chemical composition, and stability of bioemulsifier for their potential applications in biotechnology, such as bioremediation of hydrocarbon-contaminated soil and water.

Leak of fuels and lubricants occurring during exploration, distribution, refining and storage operations is the major cause of environmental pollution due to petroderivatives dispersion. The quick use of a series of physicochemical and biological techniques is needed to drastically reduce the magnitude of damage provoked by these pollutants. Among them, soil washing proved to be an effective alternative to the remediation of hydrocarbon-polluted sites, mainly if combined with surfactant utilization. However, the direct use of surfactants can lead to problems related to the toxicity and dispersion of the resulting by-products, as the majority of marketed surfactants are produced from oil derivatives. In this context, green surfactants appear as a promising alternative to their synthetic counterpart. In the present study, two green surfactants, i.e., a chemically synthesized biobased surfactant and a Starmerella bombicola biosurfactant, were applied in soil decontamination tests using a concrete mixer-type Mobile Soil Remediation System (MSRS). The system was designed and developed with 3D printing based on bench-scale results. A commercial biosurfactant was formulated based on the microbial surfactant, which was compared with the biobased surfactant in various experimental conditions. A set of factorial designs combined with Response Surface Methodology was used to select the optimal conditions for pollutant removal using the prototype. The following variables were tested: Surfactant type, Surfactant volume, Surfactant dilution, Contaminant concentration, Soil type, Soil mass, Washing duration, Tank tilt angle, Mixing speed, and Type of basket. Under the optimized experimental condition, the commercial biosurfactant allowed to remove 92.4% of the motor oil adsorbed in the sand. These results demonstrate the possibility of using natural surfactants and the development of novel mechanical technologies to degrade hydrocarbons with economic earnings for oil industry.