Heterogeneous catalytic processes based on zero-valent iron (ZVI) have been developed to treat soil and wastewater pollutants. However, the agglomeration of ZVI reduces its ability to activate persulfate (PS). In this study, a new Fe-Mn@AC activated material was prepared to activated PS to treat oil-contaminated soil, and using the microscopic characterization of Fe-Mn@AC materials, the electron transfer mode during the Fe-Mn@AC activation of PS was clarified. Firstly, the petroluem degradation rate was optimized. When the PS addition amount was 8%, Fe-Mn@AC addition amount was 3% and the water to soil ratio was 3:1, the petroluem degradation rate in the soil reached to the maximum of 85.69% after 96 h of reaction. Then it was illustrated that sulfate and hydroxyl radicals played major roles in crude oil degradation, while singlet oxygen contributed slightly. Finally, the indigenous microbial community structures remaining after restoring the Fe-Mn@AC/PS systems were analyzed. The proportion of petroleum degrading bacteria in soil increased by 23% after oxidation by Fe-Mn@AC/PS system. Similarly, the germination rate of wheat seeds revealed that soil toxicity was greatly reduced after applying the Fe-Mn@AC/PS system. After the treatment with Fe-Mn@AC/PS system, the germination rate, root length and bud length of wheat seed were increased by 54.05%, 7.98 mm and 6.84 mm, respectively, compared with the polluted soil group. These results showed that the advanced oxidation system of Fe-Mn@AC activates PS and can be used in crude oil-contaminated soil remediation.

Microwave (MW) remediation of organics-contaminated soil technology offers the advantages of high efficiency and minimal damage, representing a new approach of soil thermal remediation. However, soil, being a weak MW-absorbing medium, struggles to convert MW energy into thermal energy, thus failing to attain the necessary temperature for thermal remediation. This paper prepared two new bluecoke (BC)-based modifiers (KHCO3@BC and KHCO3/MnO2@BC) to address temperature problem of MW remediation, as well as enhance soil quality. Their composition, structure and electromagnetic properties were analyzed to investigate their role in assisting with the MW remediation of an artificially crude oil-contaminated soil were investigated. Additionally, the industrial feasibility of MW remediation was addressed for the first time. The results showed that the KHCO3 and MnO2 particles in the two modifiers were covered on the BC surface and exhibited local agglomeration. Their carbon crystalline grain size increased, and the electromagnetic properties were weaker than those of the BC. Following 10 min of MW remediation assisted by KBC or KMnBC, the remediation temperatures exceeded 300 °C, with the removal rates of PHs reaching 76.16% and 88.31%, respectively. The organic matter content, soil potassium and mechanical fraction of the remediated soil were improved, but soil acidification still needed to be further addressed. The industrial application analysis indicated that the technical process and techno-economics of MW remediation of crude oil-contaminated soil were feasible, suggesting significant potential for the large-scale industrial application.

Contamination of soil with crude oil is a serious ecological problem with potential adverse public health effects. This study assessed the germ cell toxicity of simulated leachates from crude oil-contaminated soil before and after bioremediation using the murine sperm abnormality assay, sperm count, and testes histopathology. The levels of Total Testosterone (TT), Follicle Stimulating Hormone (FSH), and Luteinizing Hormone (LH); and activities of catalase (CAT), alkaline phosphatase (ALP), superoxide dismutase (SOD), aspartate aminotransferase (AST), and alanine aminotransferase (ALT) were determined. The physicochemical, Total Petroleum Hydrocarbon (TPH), and heavy metal analyses of the leachates were also carried out. Male mice were exposed to 50, 25, 10, 5, and 1% (v/v; leachate:distilled water) of the leachate samples for five consecutive days, and were sacrificed after 35 days. The result showed a statistically significant (p < 0.05), concentration-dependent increase in abnormal sperm cells in exposed mice, with aberrations such as folded sperm, amorphous head, wrong tail attachment, distal droplet, no hook, and looped tail. Data further showed a concentration-dependent significant reduction in mean sperm count in the exposed mice. Alterations of seminiferous tubules with different lesions and activities of ALT, AST, ALP, FSH, LH, and TT were also recorded. The high level of selected heavy metals (As, Cr, Cd, Cu, and Pb) and TPH was believed to contribute to the observed reproductive toxicity and modulated enzyme activities in the treated mice. It is therefore concluded that the microbial remediation of the crude oil contaminated soil produced a reduction in the levels of heavy metals and TPH in the soil, reduced reproductive toxicity, and modulation of enzyme activities. However, the induced reproductive toxicity by the bioremediated soil is still significant, hence, further work could be done to employ a consortium of bacteria and extend the period of the bioremediation process to ensure complete removal of the contaminants.

Crude oil contaminated lands are recognised to have significant contributions to airborne volatile organic compounds (VOCs) with adverse effects on human health and tropospheric ozone. Soil capping systems for controlling harmful emissions are critical engineering solutions where advanced soil remediation techniques are neither available nor feasible. Studies on the adsorption of single VOC species in biochar have shown promising results as a potential capping material; however, current understanding of mixed gas system and multi-component adsorption of VOCs on biochar which would represent more realistic in situ conditions is very limited. We present, for the first time, the results of a study on competitive adsorption of mixed VOCs, including aromatic and non-aromatic VOCs commonly emitted from crude oil contaminated sites on two types of biochar pyrolysed at 500°C from wheat straw and bagasse as feedstock. The kinetics of sorption of multicomponent VOCs including acetone, hexane, toluene and p-xylene in biochar are studied based on the results of an extensive experimental investigation using a bespoke laboratory setup. Both biochar types used in this study presented a high sorption capacity for VOC compounds when tested individually (51-110 mg/g). For the multicomponent mixture, the competition for occupying sorption sites on biochar surface resulted in a lower absolute sorption capacity for each species, however, the overall sorption capacity of biochar remained more or less similar to that observed in the single gas experiments (50-109 mg/g). The chemical interactions via hydrogen bonds, electrostatic attraction, and pore-filling were found to be the main mechanisms of adsorption of VOC in the biochar studied. The efficiency of biochar regeneration was assessed through five cycles of adsorption-desorption tests and was found to be between 88% and 96%. The incomplete desorption observed confirm the formation of likely permanent bonds and heel build-ups during the sorption process.

This study aims at exploring the mechanism of fast-stimulating bioremediation of macro crude oil using matching Fenton pre-oxidation. The 80-day biodegradation experiment for soil S1 and S2, containing macro crude oil: C19-C29 and C17-C29 respectively, was conducted after Fenton pre-oxidation with three concentrations of H2O2 (225 mM, 450 mM, and 900 mM). Experimental results indicated that the bioremediation efficiency of macro crude oil was up to 57.1% (8853 mg/kg, S1) and 64.4% (11,719 mg/kg, S2) for 80-day fast-stimulating bioremediation using matching Fenton pre-oxidation (450 mM H2O2), which was 1.8-2.6 times that (S1: 22.2-37.1%; S2: 36.1-39.6%) for slow-stimulating bioremediation using un-matching Fenton pre-oxidation. Furthermore, the high-throughput analysis revealed that genera Sedimentibacter, Caenispirillum, and Brevundimonas became the dominant bacteria after matching Fenton pre-oxidation. Meanwhile, the highest logarithmic growth rate of indigenous hydrocarbon degraders (IHD) was obtained (S1: 64% and S2: 60%) for fast-stimulating bioremediation. And the consumption of NH4+-N was up to 90% and 94% in S1 and S2 within 60 days for fast-stimulating bioremediation, approximately 1.4 and 2.2 times that (S1: 65% and 62%; S2: 47% and 41%) for slow-stimulating remediation. The results showed that the macro crude oil became the main carbon source for IHD for the fast-stimulating bioremediation, resulting in the rapid growth of IHD. Thus, this study provides a fast and efficient remediation technology for bioremediation of macro crude oil-contaminated soils.

Choline-based deep eutectic solvents (DESs) have many outstanding features as they are easy to prepare, inexpensive, low-toxic, low volatile, and biodegradable, which make them increasingly attractive in industrial chemistry and green chemistry. In this paper, the abilities of three different kinds of DESs for crude oil removal from contaminated soils were compared and it was found the DES formed by phenylpropionic acid and choline chloride (mole ratio = 2:1) had the best performance. The effects of extraction time, temperature and the solvent-soil ratio on phenylpropionic acid/choline chloride DES performance were evaluated. The rational extraction conditions were recommended as follows: mass ratio of DES to soil was 10:1 and 60 min extraction time at 80°C. The extraction (desorption) process could be described by Freundlich desorption isotherm mode. In addition, the phenylpropionic acid/choline chloride DES could be recycled and the oil removal efficiency was about 90% after 10 cycles. This finding suggested that choline-based DES extraction was a promising technology for crude oil removal from contaminated soil.

Crude oil contamination adversely affects soil water repellency. In this study the effect of biochar on this soil characteristic has been investigated in the laboratory. Soil sample was collected from a field located near Pars Oil Company, at the top depth of 0-15 cm below surface. After air-drying and passing through a 2-mm sieve, the soil was artificially contaminated with four levels of crude oil (1:0, 1:25, 1:16.6, and 1:12.5 ratios). Biochars used in this research were generated from beechwood and maize residues at three different pyrolysis temperatures (350 °C, 550 °C, and 750 °C). Chemical functionality of all biochar samples was determined using Fourier-transform infrared spectrometry. Sufficient amounts of beechwood and maize biochars, passed through a 0.053-mm and 2-mm sieves, were mixed into crude oil-contaminated soil at the rate of 0, 0.5, 1, and 2% of total dry soil weight. The mixed samples were then laboratory incubated for 90 days at 24 °C and 10% soil moisture. Water repellency was measured using water drop penetration time (WDPT). The experimental results showed that functional groups on the biochars\' surfaces produced at the studied temperatures were distinct. Beechwood and fine size of biochar showed more ability in reducing the hydrophobicity. The produced biochars, at higher temperature, had more potential to alleviate water repellency due to the strong interactions between functional groups of biochars and crude oil. The highest amount of biochar used (2%) significantly alleviated water repellency.

To obtain a mild Fenton pre-oxidation method, which could promote the efficient degradation of total petroleum hydrocarbons (TPH) in subsequent bioremediation, the differences in the characteristics of the hydroxyl radical (·OH), nutrient consumption, activity of indigenous bacteria (CO2), and TPH removal were investigated during subsequent bioremediation after different Fenton pre-oxidation treatments. The results showed that high biodegradation of TPH was observed after mild Fenton pre-oxidation (·OH existence time:73 h; H2O2 concentration:225 mmol·L-1), because of the high activity of residual bacteria. Moreover, the same TPH removal with the addition of bacteria could be achieved without adding bacteria (the TPH removal rate 38%) because the activity of the residual bacteria was strong after mild Fenton pre-oxidation. Under the condition of no additional bacteria source, mild Fenton pre-oxidation TPH removal (approximately 38%) was higher than that after ordinary Fenton pre-oxidation (15.32%-33.15%). Further analysis of the removal efficiency of each chain of hydrocarbons revealed that the mild pre-oxidation group could reduce the inhibition of the chain hydrocarbon components (C17-C21) in the subsequent bioremediation stage. Comparing the activity of the indigenous bacteria in each group, revealed that mild pre-oxidation could appropriately stimulate the growth and increase the activity of indigenous microorganisms, all of which are beneficial to the removal of TPH.

This study investigated the changes in the indigenous microbial community structure with hemoglobin (Hb) application to determine the role of Hb in Hb-based remediation of crude oil-contaminated soil. The phylogenetic diversity of the bacterial community showed that the Hb addition selected surfactants-producing species, thereby, promoting TPH degradation. The significant increase in the CO2 generation, which can be related to the increase in the bacterial abundance inferred from the 16S rRNA gene copy number, supports the enhanced TPH degradation with Hb application. The similar residual TPH concentrations in the presence of only hydrogen peroxide (H2O2) and both Hb and H2O2 suggested that the role of Hb as a catalyst was not as significant as the role of Hb as a nutrient. Also, in the presence of H2O2, a greater recovery of the microbial community structure was observed with the double Hb injection than the single Hb injection. Overall, this study shows that the Hb-based remediation strategies via microbial metabolism can be successfully applied to remediate the crude-oil contaminated Kuwaiti soil.

Fenton pre-oxidation and a subsequent bioremediation phase of 80 days were used to investigate the importance of matching concentration of residual indigenous bacteria and nutrient levels on subsequent bioremediation of crude oil. Experiments were performed using either high (>107.7 ± 0.2 CFU/g soil) or low (<105.9 ± 0.1 CFU/g soil) concentrations of bacteria and three different nutrient levels: enough (C/N > 9.8), moderate (C/N:5-9.8), and lacking nutrient level (C/N < 5) conditions. Weak Fenton pre-oxidation (225 mM H2O2 and 2.9 mM Fe2+) resulted in highly matching between nutrient level and the population of residual indigenous bacteria. Up to 53% of total petroleum hydrocarbon (TPH) and 58% of main hydrocarbon (C15C25, during the first 10 days) were removed from the soil. Under matching conditions, the activity of indigenous bacteria and nutrient mobilization were enhanced, promoting the bioremediation of crude oil. In addition, the biodegradation of long chain molecules (C26C30) required a high level of NH4+-N.