Sulfur-containing iron carbon nanocomposites activate persulfate for combined chemical oxidation and microbial remediation of petroleum-polluted soil.

In this study, sulfur-containing iron carbon nanocomposites (S@Fe-CN) were synthesized by calcining iron-loaded biomass and utilized to activate persulfate (PS) for the combined chemical oxidation and microbial remediation of petroleum-polluted soil. The highest removal efficiency of total petroleum hydrocarbons (TPHs) was achieved at 0.2% of activator, 1% of PS and 1:1 soil-water ratio. The EPR and quenching experiments demonstrated that the degradation of TPHs was caused by the combination of 1O2,·OH, SO4·-, and O2·-. In the S@Fe-CN activated PS (S@Fe-CN/PS) system, the degradation of TPHs underwent two phases: chemical oxidation (days 0 to 3) and microbial degradation (days 3 to 28), with kinetic constants consistent with the pseudo-first-order kinetics of chemical and microbial remediation, respectively. In the S@Fe-CN/PS system, soil enzyme activities decreased and then increased, indicating that microbial activities were restored after chemical oxidation under the protection of the activators. The microbial community analysis showed that the S@Fe-CN/PS group affected the abundance and structure of microorganisms, with the relative abundance of TPH-degrading bacteria increased after 28 days. Moreover, S@Fe-CN/PS enhanced the microbial interactions and mitigated microbial competition, thereby improving the ability of indigenous microorganisms to degrade TPHs.

New insight into desorption behavior and mechanism of oil from aged oil-contaminated soil in microemulsion.

The intractable nature of oil-contaminated soil (OS) constitutes the chief limiting factor for its remediation. Herein, the aging effect (i.e., oil-soil interactions and pore-scale effect) was investigated by analyzing the properties of aged OS and further demonstrated by investigating the desorption behavior of the oil from the OS. XPS was performed to detect the chemical environment of N, O, and Al, indicating the coordination adsorption of carbonyl groups (oil) on the soil surface. Alterations in the functional groups of the OS were detected using FT-IR, indicating that the oil-soil interactions were enhanced via wind-thermal aging. SEM and BET were used to analyze the structural morphology and pore-scale of the OS. The analysis revealed that aging promoted the development of the pore-scale effect in the OS. Moreover, the desorption behavior of oil molecules from the aged OS was investigated via desorption thermodynamics and kinetics. The desorption mechanism of the OS was elucidated via intraparticle diffusion kinetics. The desorption process of oil molecules underwent three stages: film diffusion, intraparticle diffusion, and surface desorption. Owing to the aging effect, the latter two stages constituted the major steps for controlling oil desorption. This mechanism provided theoretical guidance to apply microemulsion elution for remedying industrial OS.

In situ synthesis of Fe-N co-doped carbonaceous nanocomposites using biogas residue as an effective persulfate activator for remediation of aged petroleum contaminated soils.

Persulfate (PS)-based chemical oxidation is an effective method for the remediation of petroleum-contaminated soils, but higher concentrations of PS (3-40%) may lead to soil acidification (pH decreased by 1.8-6.2 units) and affect the microbial communities. In this study, Fe/N co-doped carbonaceous nanocomposites (Fe-N @ CN) that can efficiently activate PS were developed from biogas residue for the remediation of petroleum-contaminated soil. The as-obtained Fe-N@CN displayed that the Fe-based nanoparticles were encapsulated in graphitic nanosheets, with Fe3C and FeN0.0760 as the main bonding modes. The removal efficiency of total petroleum hydrocarbons (TPHs) reached 73.14% in 3 days with a PS dose of 2% and catalyst dose of 0.4%, and increased by 15.8% on adding 30 mmol/kg of ß-cyclodextrin. The free-radical quenching experiment and electron paramagnetic resonance revealed that SO4·-,·OH, O2·-, and 1O2 were involved in the removal of TPHs. Because of the low PS dosage, the remediation process had no significant effect on the soil pH. During the remediation process, soil catalase activity was enhanced and then recovered, whereas the soil bacterial community, reflected by the operational taxonomic unit values, decreased and then recovered. TPH-degrading bacteria were produced in the Fe-N@CN/PS/soil system after chemical oxidation, further contributing to soil remediation.

A study on the reaction mechanism of microwave pyrolysis of oily sludge by products analysis and ReaxFF MD simulation.

The products distributions of oily sludge (OS) pyrolysis was fully explored by combining the pyrolysis experiments and molecular simulation, to help to deeply understand this complicated reaction process. The results of products analysis indicated that the main reactions include chain-breaking reactions, dehydrogenation reactions, aromatization reactions, alkylation reactions, and dehydrogenation condensation reactions. Microwave pyrolysis of model OS comprised of n-dodecane and OS sediment were conducted to further explore the specific reaction during the pyrolysis process, and the results showed that the pyrolysis of saturated alkanes begins at 350℃, and dehydrogenation condensation begins at 500℃. Specifically, saturated alkanes first dehydrogenated to form large molecules of α-alkene, then α-alkenes broke chains to form smaller molecules of alkanes. Furthermore, the pyrolysis process of n-dodecane was simulated by Reactive force field molecular dynamics (ReaxFF MD), and the molecular pyrolysis products distribution obtained by simulation was in good agreement with the experimental result.