Performance evaluation of rhamnolipid biosurfactant produced by Pseudomonas aeruginosa and its effect on marine oil-spill remediation.

This study aimed to reveal that the effect of biosurfactant on the dispersion and degradation of crude oil. Whole genome analysis showed that Pseudomonas aeruginosa GB-3 contained abundant genes involved in biosurfactant synthesis and metabolic processes and had the potential to degrade oil. The biosurfactant produced by strain GB-3 was screened by various methods. The results showed that the surface tension reduction activity was 28.6 mN·m-1 and emulsification stability was exhibited at different pH, salinity and temperature. The biosurfactant was identified as rhamnolipid by LC-MS and FTIR. The fermentation conditions of strain GB-3 were optimized by response surface methodology, finally the optimal system (carbon source: glucose, nitrogen source: ammonium sulfate, C/N ratio:16:1, pH: 7, temperature: 30-35 °C) was determined. Compared with the initial fermentation, the yield of biosurfactant increased by 4.4 times after optimization. In addition, rhamnolipid biosurfactant as a dispersant could make the dispersion of crude oil reach 38% within seven days, which enhanced the bioavailability of crude oil. As a biostimulant, it could also improve the activity of indigenous microorganism and increase the degradation rate of crude oil by 10-15%. This study suggested that rhamnolipid biosurfactant had application prospect in bioremediation of marine oil-spill.

An immobilized composite microbial material combined with slow release agents enhances oil-contaminated groundwater remediation.

Microbial remediation of oil-contaminated groundwater is often limited by the low temperature and lack of nutrients in the groundwater environment, resulting in low degradation efficiency and a short duration of effectiveness. In order to overcome this problem, an immobilized composite microbial material and two types of slow release agents (SRA) were creatively prepared. Three oil-degrading bacteria, Serratia marcescens X, Serratia sp. BZ-L I1 and Klebsiella pneumoniae M3, were isolated from oil-contaminated groundwater, enriched and compounded, after which the biodegradation rate of the Venezuelan crude oil and diesel in groundwater at 15 °C reached 63 % and 79 %, respectively. The composite microbial agent was immobilized on a mixed material of silver nitrate-modified zeolite and activated carbon with a mass ratio of 1:5, which achieved excellent oil adsorption and water permeability performance. The slow release processes of spherical and tablet SRAs (SSRA, TSRA) all fit well with the Korsmeyer-Peppas kinetic model, and the nitrogen release mechanism of SSRA N2 followed Fick's law of diffusion. The highest oil removal rates by the immobilized microbial material combined with SSRA N2 and oxygen SRA reached 94.9 % (sand column experiment) and 75.1 % (sand tank experiment) during the 45 days of remediation. Moreover, the addition of SRAs promoted the growth of oil-degrading bacteria based on microbial community analysis. This study demonstrates the effectiveness of using immobilized microbial material combined with SRAs to achieve a high efficiency and long-term microbial remediation of oil contaminated shallow groundwater.

Characteristic microbiome and synergistic mechanism by engineering agent MAB-1 to evaluate oil-contaminated soil biodegradation in different layer soil.

Bioremediation is a sustainable and pollution-free technology for crude oil-contaminated soil. However, most studies are limited to the remediation of shallow crude oil-contaminated soil, while ignoring the deeper soil. Here, a high-efficiency composite microbial agent MAB-1 was provided containing Bacillus (naphthalene and pyrene), Acinetobacter (cyclohexane), and Microbacterium (xylene) to be synergism degradation of crude oil components combined with other treatments. According to the crude oil degradation rate, the up-layer (63.64%), middle-layer (50.84%), and underlying-layer (54.21%) crude oil-contaminated soil are suitable for bioaugmentation (BA), biostimulation (BS), and biostimulation+bioventing (BS+BV), respectively. Combined with GC-MS and carbon number distribution analysis, under the optimal biotreatment, the degradation rates of 2-ring and 3-ring PAHs in layers soil were about 70% and 45%, respectively, and the medium and long-chain alkanes were reduced during the remediation. More importantly, the relative abundance of bacteria associated with crude oil degradation increased in each layer after the optimal treatment, such as Microbacterium (2.10-14%), Bacillus (2.56-12.1%), and Acinetobacter (0.95-12.15%) in the up-layer soil; Rhodococcus (1.5-6.9%) in the middle-layer soil; and Pseudomonas (3-5.4%) and Rhodococcus (1.3-13.2%) in the underlying-layer soil. Our evaluation results demonstrated that crude oil removal can be accelerated by adopting appropriate bioremediation approach for different depths of soil, providing a new perspective for the remediation of actual crude oil-contaminated sites.

In situ generated iron oxide nanosheet on iron foam electrode for enhanced electro-Fenton performance toward pharmaceutical wastewater treatment.

Electro-Fenton (EF) is considered to be an effective technology for the purification of organic wastewater containing antibiotics, but the construction of accessible and efficient heterogeneous EF catalytic materials still faces challenges. In this study, an iron foam-derived electrode (FeOx/if-400) was prepared by a simple method (chemical oxidation combined heat treatment). The fabricated electrode presented great EF degradation efficiency under wide pH range (almost completely removing 50 mg L-1 TNZ within 60 min) and maintained great stability after consecutive operation (>95% removal after six cycles). Also, the FeOx/if-400 electrode showed good purification ability for pharmaceutical wastewater as evaluated by the quadrupole time-of-flight mass spectrometry and the three-dimensional excitation-emission matrix fluorescence spectroscopy. Based on experimental results, characterization analysis, and density functional theory (DFT) calculations, the EF reaction mechanism of FeOx/if-400 electrode and the organics degradation pathways in simulated and real matrices were proposed. Significantly, the biotoxicity assessment of the degradation intermediate products was revealed by ECOSAR software and relative inhibition of E. coli, which fully proved the environmental friendliness of the EF process by the FeOx/if-400 cathode. This work provides a green and effective EF system, showing a promising application potential in the field of organic wastewater treatment containing antibiotic contaminants.

Heterogeneous Fenton treatment of shale gas fracturing flow-back wastewater by spherical Fe/Al2O3 catalyst.

In this work, efficient Fenton strategy have been proposed for degradation of shale gas fracturing flow-back wastewater using the spherical Fe/Al2O3 supported catalyst. Prior to actual fracturing fluid treatment, the typical model wastewaters such as p-nitrophenol and polyacrylamide were employed to evaluate the catalytic properties of prepared catalyst, and then Fenton treatment of the shale gas fracturing flow-back wastewater was performed on the self-assembled catalytic degradation reactor for continuous flow purification. Results showed that under the conditions of 0.25 mol L-1 impregnating concentration, pH 4, 50 g L-1 catalyst and 0.75 mL L-1 30% H2O2, the removal efficiency of p-nitrophenol and polyacrylamide reached 74% and 61%, respectively, while the COD removal of fracturing flow-back fluid was approximately 48% with the residual 88 mg L-1 COD, meeting the emission standards of the integrated wastewater discharge standard (GB 8978-1996, COD < 100 mg L-1). This work offers new alternatives for Fenton treatment of real wastewater by efficient and low-cost supported catalysts.

Marine oil spill remediation by Candelilla wax modified coal fly ash cenospheres.

Biodegradable candelilla wax (CW) was creatively used for hydrophobic modification of coal fly ash cenospheres (FACs), a waste product from thermal power plants, and a new spherical hollow particulate adsorbent with fast oil adsorption rate and easy agglomeration was prepared. CW was confirmed to physically coat FACs and the optimum mass of wax added to 3 g of FACs was 0.05 g. From a series of batch scale experiments, CW-FACs were found to adsorb oil, reaching adsorption efficiency of 80.6% within 10 s, and aggregate into floating clumps which were easily removed from the water's surface. The oil adsorption efficiency was highly dependent on hydrophobicity of the used adsorbent, the adsorption of Venezuela oil onto CW-FACs was found to be a homogenous monolayer, and the capacity and intensity of the adsorption decreased as temperature increased from 10 to 40 °C. The Langmuir isotherm model was the best fit, with the maximum adsorption capacity achieved at 649.38 mg/g. CW-FACs were also found to be highly stable in concentrated acid, alkaline and salt solutions, as well as for spills of different oil products. Furthermore, the retention rate of the oil adsorption capacity of the CW-FACs after 6 cycles of adsorption-extraction was as high as 93.2%. Therefore, CW-FACs can be widely used, easily recycled, and reused for marine oil spill remediation, which is also a good alternative disposal solution for FACs.

Enhanced crude oil degradation by remodeling of crude oil-contaminated soil microbial community structure using sodium alginate/graphene oxide/Bacillus C5 immobilized pellets.

Bioaugmentation (BA) of oil-contaminated soil by immobilized microorganisms is considered to be a promising technology. However, available high-efficiency microbial agents remain very limited. Therefore, we prepared a SA/GO/C5 immobilized gel pellets by embedding the highly efficient crude oil degrading bacteria Bacillus C5 in the SA/GO composite material. The optimum preparation conditions of SA/GO/C5 immobilized gel pellets were: SA 3.0%, GO 25.0 µg/mL, embedding amount of C5 6%, water bath temperature of 50°C, CaCl2 solution concentration 3% and cross-linking time 20 h. BA experiments were carried out on crude oil contaminated soil to explore the removal effect of SA/GO/C5 immobilized pellets. The results showed that the SA/GO/C5 pellets exhibited excellent mechanical strength and specific surface area, which facilitated the attachment and growth of the Bacillus C5. Compared with free bacteria C5, the addition of SA/GO/C5 significantly promoted the removal of crude oil in soil, reaching 64.92% after 30 d, which was 2.1 times the removal rate of C5. The addition of SA/GO/C5 promoted the abundance of soil exogenous Bacillus C5 and indigenous crude oil degrading bacteria Alcanivorax and Marinobacter. In addition, the enrichment of hydrocarbon degradation-related functional abundance was predicted by PICRUSt2 in the SA/GO/C5 treatment group. This study demonstrated that SA/GO/C5 is an effective method for remediating crude oil-contaminated soil, providing a basis and option for immobilized microorganisms bioaugmentation to remediate organic contaminated soil.

A novel dehydrocoenzyme activator combined with a composite microbial agent TY for enhanced bioremediation of crude oil-contaminated soil.

Bioaugmentation (BA) and biostimulation (BS) synergistic remediation is an effective remediation strategy for oil-contaminated soil. In this study, the optimal combination system of composite microbial agent TY (Achromobacter: Pseudomona = 2:1) and dehydrocoenzyme activator (NaNO3 (7.0 g/L), (NH4)2HPO4 (1.0 g/L), riboflavin (6.0 mg/L)) was screened. Under the best combination system, the degradation rate of crude oil in oil-contaminated soil reached 79.44% after 60 d, which was 1.74 times and 1.23 times higher than that of compound microbial agent TY treatment and dehydrogenase activator treatment, respectively. In addition, a highly efficient combination system was found to target the degradation of oil C10-C28 fractions by gas chromatography (GC). The increased abundance of dehydrogenase coenzymes such as flavin nucleotides (FAD and FMN), coenzyme I (NAD+, Co I) and coenzyme II (NADP+, Co II) as well as dioxygenases and monooxygenases promote the degradation of crude oil. Furthermore, the dominant genera at the genus level in soil were analyzed by high-throughput sequencing, which were Nocardioides (46.48%-56.07%), Gordonia (11.40%-14.61%), Intrasporangiaceae (5.05%-10.58%), Pseudomonas (1.39%-1.92%) and Dietzia (0.64%-2.77%). Phylogenetic Investigation of Communities by Reconstruction of Unobserved States (PICRUSt) analysis showed that the abundance of genes associated with crude oil degradation such as ABC transporters (2.89%), fatty acid (1.04%), carbon metabolism (4.5%) and aromatic compound (0.92%) was assigned enhanced after 60 d of remediation. These results indicated that the combination system of the compound bacterium TY and the dehydrocoenzyme activator is a propective option for the bioremediation of oil-contaminated soil.

Reconstruction of microbiome and functionality accelerated crude oil biodegradation of 2,4-DCP-oil-contaminated soil systems using composite microbial agent B-Cl.

Biodegradation is one of the safest and most economical methods for the elimination of toxic chlorophenols and crude oil from the environment. In this study, aerobic degradation of the aforementioned compounds by composite microbial agent B-Cl, which consisted of Bacillus B1 and B2 in a 3:2 ratio, was analyzed. The biodegradation mechanism of B-Cl was assessed based on whole genome sequencing, Fourier transform infrared spectroscopy and gas chromatographic analyses. B-Cl was most effective at reducing Cl- concentrations (65.17%) and crude oil biodegradation (59.18%) at 7 d, which was when the content of alkanes ≤ C30 showed the greatest decrease. Furthermore, adding B-Cl solution to soil significantly decreased the 2,4-DCP and oil content to below the detection limit and by 80.68%, respectively, and reconstructed of the soil microbial into a system containing more CPs-degrading (exaA, frmA, L-2-HAD, dehH, ALDH, catABE), aromatic compounds-degrading (pcaGH, catAE, benA-xylX, paaHF) and alkane- and fatty acid-degrading (alkB, atoB, fadANJ) microorganisms. Moreover, the presence of 2,4-DCP was the main hinder of the observed effects. This study demonstrates the importance of adding B-Cl solution to determine the interplay of CPs with microbes and accelerating oil degradation, which can be used for in-situ bioremediation of CPs and oil-contaminated soil.

A novel chitosan-biochar immobilized microorganism strategy to enhance bioremediation of crude oil in soil.

The chitosan-biochar composite is a clean and environmentally friendly immobilized microorganisms carrier. In this study, the chitosan-biochar composite as a carrier to immobilize a compound microbial agent contained Pseudomonas aeruginosa and Bacillus licheniformis, and investigated its role in the remediation of oil-contaminated soil. When using 1% (v/v) acetic acid, 3% (m/v) chitosan solution, 0.1% biochar, 4% (v/v) NaOH solution, freeze-drying 6 h, the optimal chitosan-biochar composite material could be obtained. The specific surfacearea of the material increased to 1.725 m2/g and the average pore size also increased from 130.2260 nm to 165.2980 nm after the addition of biochar through the analysis of specific surface area and pore size, which enlarged the contact area of microorganisms and crude oil with the material. SEM showed that the bacterial successfully adhered to the surface and internal of the material. Using FTIR, the results showed that the synthesis of composite carrier material was the covalent combination of -NH2 on chitosan and -COOH on biochar, forming a new chemical bond -NH-CO-. After 60 days of remediation of oil-contaminated soil, the removal rate of crude oil by chitosan-biochar composite immobilized microorganism method was 45.82%, which was 21.26% higher than that of natural remediation. Simultaneously, several oil-degrading bacteria increased at genus level, including Nocardioides (26.79%-33.09%), Bacillus (3.01%-4.10%), Dietzia (1.84%-5.56%), Pseudomonas (0-0.78%), among which Pseudomonas belongs to exogenous bacteria. The results indicated that the chitosan-biochar composite material has high application value in removing crude oil, and further provides a new strategy for bioremediation of oil-contaminated soil.

Heterogeneous electro-Fenton catalysis with self-supporting CFP@MnO2-Fe3O4/C cathode for shale gas fracturing flowback wastewater.

Self-supporting electrodes have triggered great interests in improving electro-Fenton (EF) system for degradation of refractory organic pollutants. In this work, a novel self-supporting carbon fiber paper (CFP) electrode modified by transition metals, e.g. Fe and Mn, was fabricated and employed as a heterogeneous EF cathode. The prepared electrode exhibited excellent degradation for a number of typical organic pollutants along with superior stability. Remarkably, a high removal efficiency was achieved in the EF treatment of shale gas fracturing flowback wastewater. Results indicated that 65.2% TOC and 74.8% COD were eliminated after 4 h degradation. The residual COD value of the real wastewater was 80 mg L-1, meeting the emission requirement of the integrated wastewater discharge standard (COD＜100 mg L-1) with a low specific energy consumption of 6.9kWhkg-1COD-1. This work demonstrates a competing alternative for efficient decontamination of real wastewater using an electro-Fenton strategy with a low-cost electrode.

Synthesis and application of Cu-BTC@ZSM-5 composites as effective adsorbents for removal of toluene gas under moist ambience: kinetics, thermodynamics, and mechanism studies.

Metal organic frameworks (MOFs) are excellent adsorbents that provide abundant specific surface area, adjustable pore structure, and rich active sites. The purpose of this study was to prepare composites with hydrophobic and high microporous specific surface area and to adsorb toluene gas in moist ambience. An ethanol activation-assisted hydrothermal method was proposed to synthesize copper-benzene-1,3,5-tricarboxylic acid (Cu-BTC) metal-organic framework, Cu-BTC, and ZSM-5 molecular sieve composites (Cu-BTC@ZSM-5). The dynamic adsorption process of toluene on different adsorbents was investigated, and the results showed that the toluene adsorption capacity of Cu-BTC@ZSM-5 (158.6 mg/g) was 2.53 times higher than Cu-BTC (62.7 mg/g), when the ZSM-5 content is 5% and the humidity is 30%RH. Compared with other factors, the humidity inhibited the adsorption of toluene on Cu-BTC@ZSM-5. Langmuir model and the pseudo-second kinetics model can better describe the adsorption behavior of Cu-BTC@ZSM-5. The thermodynamic results showed the adsorption process was a spontaneous exothermic process at low temperature and mainly physical adsorption. The relative regenerability can still up to 80.4% after six cycles. The adsorption mechanisms of Cu-BTC@ZSM-5 were pore-filling adsorption, π-π interaction, cation-π bonding, and hydrophobic interactions. This study will help to design a systematic route to evaluate the adsorption performance of Cu-BTC@ZSM-5 for toluene.

Biodesulfurization of diesel oil in oil-water two phase reaction system by Gordonia sp. SC-10.

OBJECTIVES: Different sulfur contents of diesel oils were used for biodesulfurization to study the desulfurization capacity of Gordonia sp. SC-10 in oil-water two-phase reaction system. RESULTS: Gordonia sp. SC-10 showed great properties in desulfurizing diesel oil with different sulfur contents. This bacterium could decrease sulfur contents in different diesel oils from 194.7 ± 3.7 to 30.4 ± 0.5 mg/l and from 3035.3 ± 23.8 to 1792.8 ± 48.9 mg/l, respectively. Furthermore, this bacterium could desulfurize broad range of organosulfur compounds and had strong desulfurization activity against alkylated DBTs. For low-sulfur diesel oil, sulfur could be removed from 10.2 ± 0.1 to 5.0 ± 0.1 mg/l. CONCLUSIONS: The newly isolated bacteria Gordonia sp. SC-10 showed a good performance in desulfurizing diesel oils, and it might be a useful desulfurizing biocatalyst to enable the industrialized application of biodesulfurization process.

Graphene oxide wrapped copper-benzene-1,3,5-tricarboxylate metal organic framework as efficient absorbent for gaseous toluene under ambient conditions.

The ultrasonic-assisted hydrothermal and ethanol activation method was proposed to synthesize copper-benzene-1,3,5-tricarboxylate (Cu-BTC) metal organic framework and Cu-BTC/graphene oxide (GO) composites (Cu-BTC@GO). The dynamic adsorption behavior of toluene on two adsorbents was studied and compared with that of GO and reduced graphene oxide (RGO). The Cu-BTC@GO exhibited high adsorption capacity (183 mg/g) for toluene, which is nearly three times as much as that of Cu-BTC (62.7 mg/g) with the GO mass fraction of 20%. Furthermore, the adsorption of toluene on Cu-BTC@GO composites was positively correlated with the initial concentration of toluene and the adsorbent dosage, and negatively correlated with the temperature. The adsorption data of toluene on Cu-BTC@GO composites were well in accordance with pseudo-first kinetics model. Langmuir model had a better fit than Freundlich model. The adsorption thermodynamic results showed that the adsorption process was mainly physical adsorption and the adsorption process was spontaneous at low temperature. After five adsorption-desorption cycles, the adsorption efficiency can still reach 82.1%.This study will help to draw a promising roadmap to describe the adsorption performance of Cu-BTC@GO composites for toluene.

Thermophilic biodesulfurization and its application in oil desulfurization.

To reduce the harm caused to the environment by fuel combustion and meet the increasingly stringent emission standards, the sulfur content of fuels should be reduced. Dibenzothiophene, benzothiophene, and their derivatives are sulfur-containing components of fuels that are difficult to desulfurize and can therefore cause great environmental damage. Biodesulfurization is a desulfurization method that has the advantage of being able to remove dibenzothiophene and its derivatives removed easily under conditions that are relatively mild when compared with hydrodesulfurization. This paper introduces the advantages of thermophilic biodesulfurization compared with mesophilic biodesulfurization; analyzes the desulfurization mechanism, including the desulfurization pathways and enzymic systems of desulfurization bacteria; and discusses the application of biodesulfurization in oil desulfurization. The main problems existing in biodesulfurization and possible solutions are also analyzed in this paper. Biological desulfurization is a promising method for desulfurization; accordingly, more studies investigating biodesulfurization of actual oil are needed to enable the industrialized application of biodesulfurization.

Laboratory investigation of oil-suspended particulate matter aggregation under different mixing conditions.

Oil-suspended particulate matter aggregation (OSA) has been recognized by the oil spill remediation community to effectively enhance the cleansing of spilled oil in the marine environment. While studies have investigated the application of mineral fines as an effective method to facilitate oil dispersion, decision-makers still lack information on the role of mixing energy in OSA formation and its significance to oil dispersion in real spills. This work studied the effect of level and duration of mixing energy on OSA formation using the standard reference material 1,941 b and Arabian light crude oil. The results showed that dispersed small oil droplets increased with an increase of both the level and duration of mixing energy to form multi-droplet OSAs. The sizes of the dispersed droplets varied between 5 and 10 µm under different conditions studied. The maximum oil trapping efficiency increased from 23% to 33%, the oil to sediment ratio increased from 0.30 to 0.43 g oil/g sediment, and the required shaking time decreased from 2.3 to 1.1h as the shaking rate increased from 2.0 to 2.3 Hz. Based on the size measurement results, a breakage effect on the formed OSAs and sediment flocs was confirmed under high mixing energy level.

Investigation of the kinetics of oil-suspended particulate matter aggregation.

The process of oil-suspended particulate matter aggregation (OSA) has been recognized by the oil spill remediation community to enhance the natural cleansing of oiled shorelines. A laboratory study was conducted to investigate the kinetics of OSA formation under various mixing intensities using the standard reference material 1941b and Arabian heavy crude oil. The results showed that formation of OSAs increased exponentially with mixing time and reached a maximum within 5h. The maximum oil trapping efficiency increased from 24% to 47%, and the required shaking time decreased from 4.5 to 1.2h as the sediment concentration and mixing energy increased. The maximum oil-to-sediment ratio reached 0.24-0.68 g oil/g sediment within 5h. Most of the formed OSAs were solid OSAs and single droplet OSAs with low mixing energies, and multi-droplet OSAs with high mixing energies. The sizes of the dispersed oil droplets and OSAs were also investigated.