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.

Catalytic flash pyrolysis of Scenedesmus sp. post-extraction residue using low-cost HZSM-5 catalyst with the perspective to produce renewable aromatic hydrocarbons.

Recovering renewable chemicals from de-fatted microalgal residue derived from lipid extraction within the algal-derived biofuel sector is crucial, given the rising significance of microalgal-derived biodiesel as a potential substitute for petroleum-based liquid fuels. As a circular economy strategy, effective valorization of de-fatted biomass significantly improves the energetic and economic facets of establishing a sustainable algal-derived biofuel industry. In this scenario, this study investigates flash catalytic pyrolysis as a sustainable pathway for valorizing Scenedesmus sp. post-extraction residue (SPR), potentially yielding a bio-oil enriched with upgraded characteristics, especially renewable aromatic hydrocarbons. In the scope of this study, volatile products from catalytic and non-catalytic flash pyrolysis were characterized using a micro-furnace type temperature programmable pyrolyzer coupled with gas chromatographic separation and mass spectrometry detection (Py-GC/MS). Flash pyrolysis of SPR resulted in volatile products with elevated oxygen and nitrogen compounds with concentrations of 46.4% and 26.4%, respectively. In contrast, flash pyrolysis of lyophilized microalgal biomass resulted in lower concentrations of these compounds, with 40.9% oxygen and 17.3% nitrogen. Upgrading volatile pyrolysis products from SPR led to volatile products comprised of only hydrocarbons, while completely removing oxygen and nitrogen-containing compounds. This was achieved by utilizing a low-cost HZSM-5 catalyst within a catalytic bed at 500 °C. Catalytic experiments also indicate the potential conversion of SPR into a bio-oil rich in monocyclic aromatic hydrocarbons, primarily BETX, with toluene comprising over one-third of its composition, thus presenting a sustainable pathway for producing an aromatic hydrocarbon-rich bio-oil derived from SPR. Another significant finding was that 97.8% of the hydrocarbon fraction fell within the gasoline range (C5-C12), and 35.5% fell within the jet fuel range (C8-C16). Thus, flash catalytic pyrolysis of SPR exhibits significant promise for application in drop-in biofuel production, including green gasoline and bio-jet fuel, aligning with the principles of the circular economy, green chemistry, and bio-refinery.

Demonstration of a scalable process for remediation of petroleum-impacted soil using electron beam irradiation.

Petroleum-impacted soils pose several hazards and require fast, effective, and versatile remediation techniques. Electron beam irradiation provides a novel means of heating soil and inducing non-equilibrium chemical reactions and has previously been applied to environmental remediation. In this work a scalable process for remediation of petroleum-impacted soils using a 100 kW, 3 MeV industrial electron beam is investigated. The process involves conveying impacted soil through a beam at a controllable rate to achieve a desired dose of approximately 1000 kGy. Reductions to less than 1% Total Petroleum Hydrocarbon (TPH) content from an initial TPH of 3.3% were demonstrated for doses of 710-1370 kGy. These reductions were achieved in in conditions equivalent to 4 m3 per hour, demonstrating the applicability of this technique to remediation sites. TPH reduction appeared to be temperature-dependent but not heavily dependent on dose rate, with reductions of 96% achieved for a dose of 1370 kGy and peak temperature of 540 °C. The performance of the process at high dose rates suggests that it can be incorporated into remediation of sites for which a high rate of material processing is required with a relatively small device footprint.

Bioremediation of hydrocarbon by co-culturing of biosurfactant-producing bacteria in microbial fuel cell with Fe2O3-modified anode.

The most common type of environmental contamination is petroleum hydrocarbons. Sustainable and environmentally friendly treatment strategies must be explored in light of the increasing challenges of toxic and critical wastewater contamination. This paper deals with the bacteria-producing biosurfactant and their employment in the bioremediation of hydrocarbon-containing waste through a microbial fuel cell (MFC) with Pseudomonas aeruginosa (exoelectrogen) as co-culture for simultaneous power generation. Staphylococcus aureus is isolated from hydrocarbon-contaminated soil and is effective in hydrocarbon degradation by utilizing hydrocarbon (engine oil) as the only carbon source. The biosurfactant was purified using silica-gel column chromatography and characterised through FTIR and GCMS, which showed its glycolipid nature. The isolated strains are later employed in the MFCs for the degradation of the hydrocarbon and power production simultaneously which has shown a power density of 6.4 W/m3 with a 93% engine oil degradation rate. A biogenic Fe2O3 nanoparticle (NP) was synthesized using Bambusa arundinacea shoot extract for anode modification. It increased the power output by 37% and gave the power density of 10.2 W/m3. Thus, simultaneous hydrocarbon bioremediation from oil-contamination and energy recovery can be achieved effectively in MFC with modified anode.

Ingenious use of autocatalytic hydrodeoxygenation for the separation and recovery of oil and iron from rolling oil sludge.

This paper introduces a transformative hydrodeoxygenation process for the simultaneous recovery of oil and iron from hazardous rolling oil sludge (ROS). Leveraging the inherent catalytic capabilities of iron/iron oxide nanoparticles in the sludge, our process enables the conversion of fatty acids and esters into hydrocarbons under conditions of 4.5 MPa, 330 °C, and 500 rpm. This reaction triggers nanoparticle aggregation and subsequent separation from the oil phase, allowing for effective resource recovery. In contrast to conventional techniques, this method achieves a high recovery rate of 98.3% while dramatically reducing chemical reagent consumption. The reclaimed petroleum and iron-ready for high-value applications-are worth 3910 RMB/ton. Moreover, the process facilitates the retrieval of nanoscale magnetic Fe and Fe0 particles, and the oil, with an impressive hydrocarbon content of 87.8%, can be further refined. This energy-efficient approach offers a greener, more sustainable pathway for ROS valorization.

Chemical Weathering Patterns of Diluted Bitumen Spilled into Freshwater Limnocorrals.

Due to the sudden nature of oil spills, few controlled studies have documented how oil weathers immediately following accidental release into a natural lake environment. Here, we evaluated the weathering patterns of Cold Lake Winter Blend, a diluted bitumen (dilbit) product, by performing a series of controlled spills into limnocorrals installed in a freshwater lake in Northern Ontario, Canada. Using a regression-based design, we added seven different dilbit volumes, ranging from 1.5 to 180 L, resulting in oil-to-water ratios between 1:71,000 (v/v) and 1:500 (v/v). We monitored changes in the composition of various petroleum hydrocarbons (PHCs), including n-alkanes, polycyclic aromatic hydrocarbons (PAHs), and oil biomarkers in dilbit over time, as it naturally weathered for 70 days. Depletion rate constants (kD) of n-alkanes and PAHs ranged from 0.0009 to 0.41 d-1 and 0.0008 to 0.38 d-1, respectively. There was no significant relationship between kD and spill volume, suggesting that spill size did not influence the depletion of petroleum hydrocarbons from the slick. Diagnostic ratios calculated from concentrations of n-alkanes, isoprenoids, and PAHs indicated that evaporation and photooxidation were major processes contributing to dilbit weathering, whereas dissolution and biodegradation were less important. These results demonstrate the usefulness of large scale field studies carried out under realistic environmental conditions to elucidate the role of different weathering processes following a dilbit spill.

Remediating petroleum hydrocarbons in highly saline-alkali soils using three native plant species.

Phytoremediation of total petroleum hydrocarbons (TPHs) contamination is a process that uses the synergistic action of plants and rhizosphere microorganisms to degrade, absorb and stabilize pollutants in the soil, and has received increasing attention in recent years. However, this technology still has some challenges under certain conditions (e.g., highly alkaline and saline environments). The present study was selected three native plant species (alfalfa, tall fescue, and ryegrass) to remediate petroleum pollutants in greenhouse pot experiments. The results indicate that TPH contamination not only inhibited plant growth, soil chemical properties and soil fertility (i.e. lower plant biomass, chlorophyll, pH, and electrical conductivity), but also increased the malondialdehyde, glutathione, and antioxidant enzyme activities (catalase and polyphenol oxidase). Further, correlation analysis results illustrated that TPH removal was strongly positively correlated with chlorophyll, soil fertility, and total organic carbon, but was negatively correlated with dehydrogenase, polyphenol oxidase, pH, and electrical conductivity. The highest TPHs removal rate (74.13%) was exhibited by alfalfa, followed by tall fescue (61.79%) and ryegrass (57.28%). The degradation rates of short-chain alkanes and low rings polycyclic aromatic hydrocarbons (PAHs) were substantially higher than those of long-chain alkanes and high rings PAHs. The findings of this study provide valuable insights into petroleum decontamination strategies in the highly saline - alkali environments.

Fast degradation of macro alkanes through activating indigenous bacteria using biosurfactants produced by Burkholderia sp.

Soil bacteria that produce biosurfactants can use total petroleum hydrocarbons (TPHs) as a carbon source. This study demonstrated that biosurfactants produced by Burkholderia sp. enhanced the recovery and synergism of soil microbial community, resulting in fast degradation of macro alkanes. Experiments were carried out by applying bio-stimulation after pre-oxidation to investigate the effects of nutrient addition on biosurfactant production, TPH degradation, and microbial community succession in the soil. The results presented that bio-stimulation could produce biosurfactants in high C/N (32.6) and C/H (13.3) conversion after pre-oxidation and increased the total removal rate of TPH (10.59-46.71%). The number of total bacteria had a rapid increase trend (2.94-8.50 Log CFU/g soil). The degradation rates of macro alkanes showed a 4.0-fold (48.07 mg/kg·d-1 versus 186.48 mg/kg·d-1) increase, and the bioremediation time of degrading macro alkanes saved 166 days. Further characterization revealed that the biosurfactants produced by Burkholderia sp. could activate indigenous bacteria to degrade macro alkanes rapidly. A shift in phylum from Actinomycetes to Proteobacteria was observed during bioremediation. The average relative abundance of the microbial community increased from 36.24 to 64.96%, and the predominant genus tended to convert from Allorhizobium (8.57%) to Burkholderia (15.95%) and Bacillus (15.70%). The co-occurrence network and Pearson correlation analysis suggested that the synergism of microbial community was the main reason for the fast degradation of macro alkanes in petroleum-contaminated soils. Overall, this study indicated the potential of the biosurfactants to activate and enhance the recovery of indigenous bacteria after pre-oxidation, which was an effective method to remediate petroleum-contaminated soils.

A sustainable approach to enhance heavy hydrocarbons removal in landfarming treatment.

The present study aimed to evaluate the best strategy to enhance the degradation rate of heavy petroleum hydrocarbons (HPH) contaminated soil in a landfarming plant. Samples of real contaminated soil, further spiked with HPH, were treated in mesocosm reactors simulating the landfarming system. One reactor was operated without any modification compared to the real landfarming plant. The other three reactors were operated with different strategies to improve the removal rate: biostimulation (BS) through the addition of nitrogen and phosphorus; bioaugmentation (BA) with the inoculation of sludge produced in the treatment of the process water from the oil re-fining plant of the same industrial area; combination of biostimulation and bioaugmentation (BAS). The biostimulation (BS) was the most effective strategy, leading to a reduction of the remediation time by 35% as compared to the traditional treatment. Bioaugmentation (BA) also provided positive effects leading to a reduction of the remediation time by 24%; its performance improved further when the addition of sludge was combined with the increase of phosphorous (BAS). Therefore, the key tool was represented by the phosphorous availability, whereas the application of sludge was most useful to provide waste with a new possibility of reuse, thus fulfilling the principles of the circular economy. The final characterization showed that the treated soil was suitable for reuse in industrial areas according to the legislation in force.

Experimental investigation on electromagnetic induction thermal desorption for remediation of petroleum hydrocarbons contaminated soil.

A novel electromagnetic induction low temperature thermal desorption treatment (EMI LTTD) for petroleum hydrocarbons contaminated soil was introduced in this work. The removal rate of total petroleum hydrocarbons (TPH) under various factors, the morphology changes of soils as well as removal mechanism were investigated. Results suggested that increasing the heating temperature significantly increased the removal rate of TPH. At the beginning of 20 min, most of hydrocarbons (93.44-96.91 wt%) was removed with the temperature ranged from 200 °C to 300 °C. Besides, the initial contaminants concentration, particle size and thickness of soil slightly influenced the removal rate of TPH. Desorption kinetic study demonstrated that first-order model was well-described for desorption behavior. Response surface methodology analysis showed the temperature of 216 °C, the residence time of 21 min and the moisture content of 18% was an optimum condition recommended for potentially practical application. Under this condition, the results for the composition of hydrocarbons based on carbon number fractions indicated that the fractions of C10∼C16, C17∼C22 still existed in soil, while C23∼C28 was not detected after EMI LTTD treatment. Proposed mechanism was both hydrocarbons removed by evaporation at any temperature, while parts of heavy hydrocarbons was cracked within the soil close to induction medium, resulting in re-adsorption of light hydrocarbons. A buckwheat germination and growth test indicated that soil treated by EMI LTTD was potential in reutilization for planting.

The fate and behavior of petroleum biomarkers in diluted bitumen and conventional crude oil exposed to natural sunlight in simulated seawater.

Given that the physicochemical properties of diluted bitumen (dilbit) can differ from those of conventional crude oil, understanding the fate and behavior of this petroleum product in the environment becomes vital. This study involves the analysis of the photolytic behavior of some representative petroleum biomarkers, bicyclic sesquiterpanes (BSs), admantanes (ADs), diamantanes (DAs), and mono- and triaromatic steranes (MASs and TASs), by exposing Cold Lake Blend (CLB) and Alberta Sweet Mixed Blend (MSW) to winter and summer insolation after being spilled onto artificial brines. Aromatic steranes in all control samples remained relatively stable, whereas the biomarkers of BSs, ADs, and DAs were less stable. Similar to the exhaustive loss of the C10-C17 alkanes, 91%-99% of BSs, ADs, and DAs were lost after five days of insolation, especially in summer. Both MASs and TASs were lost gradually in most scenarios, although both of them were lost faster in MSW than observed for CLB. The removal of MASs and TASs did not differ significantly from each other, although their loss was less than observed for PAHs having similar number of rings and greater than for the C21-C33n-alkanes. Therefore, photooxidation, not evaporation or biodegradation, was the main factor responsible for oxidizing these aromatic steranes. However, biomarkers of BSs, ADs and DAs were mostly lost through evaporation. Therefore, aromatic steranes have the potential to be utilized to evaluate the photolytic behavior of petroleum hydrocarbons, while BSs, ADs, and DAs should not be used for this purpose.

Degradation of alkane hydrocarbons by Priestia megaterium ZS16 and sediments consortia with special reference to toxicity and oxidative stress induced by the sediments in the vicinity of an oil refinery.

Petroleum hydrocarbon is a critical ecological issue with impact on ecosystems through bioaccumulation. It poses significant risks to human health. Due to the extent of alkane hydrocarbon pollution in some environments, biosurfactants are considered as a new multifunctional technology for the efficient removal of petroleum-based contaminants. To this end, Yamuna river sediments were collected at different sites in the vicinity of Mathura oil refinery, UP (India). They were analysed by atomic absorption spectrophotometry and gas chromatography-mass spectrometry (GC-MS) for heavy metals and organic pollutants. Heptadecane, nonadecane, oleic acid ester and phthalic acid were detected. In total 107 bacteria were isolated from the sediments and screened for biosurfactant production. The most efficient biosurfactant producing strain was tested for its capability to degrade hexadecane efficiently at different time intervals (0 h, 7 d, 14 d and 21 d). FT-IR analysis defined the biosurfactant as lipopeptide. 16S rRNA gene sequencing identified the bacterium as Priestia megaterium. The strain lacks resistance to common antibiotics thus making it an important candidate for remediation. The microbial consortia present in the sediments were also investigated for their capability to degrade C16, C17 and C18 alkane hydrocarbons. By using gas chromatography-mass spectrophotometry the metabolites were identified as 1-docosanol, dodecanoic acid, 7-hexadecenal, (Z)-, hexadecanoic acid, docosanoic acid, 1-hexacosanal, 9-octadecenoic acid, 3-octanone, Z,Z-6,28-heptatriactontadien-2-one, heptacosyl pentafluoropropionate, 1,30-triacontanediol and decyl octadecyl ester. Oxidative stress in Vigna radiata L. roots was observed by using Confocal Laser Scanning Microscopy. A strong reduction in seed germination and radicle and plumule length was observed when Vigna radiata L. was treated with different concentrations of sediment extracts, possibly due to the toxic effects of the pollutants in the river sediments. Thus, this study is significant since it considers the toxicological effects of hydrocarbons and to degrade them in an environmentally friendly manner.

Pollution characteristics of groundwater in an agricultural hormone-contaminated site and implementation of Fenton oxidation process.

The groundwater polluted by an agricultural hormone site was taken as the research object, and a total of 7 groundwater samples were collected at different locations in the plant. The main pollutants in the research area were determined to be extractable petroleum hydrocarbons (C10-C40); 1,2-dichloroethane; 1,1,2-trichloroethane; carbon tetrachloride; vinyl chloride, and chloroform; the maximum content of these pollutants can reach 271 mg/L, 1.68 × 107 µg/L, 1.56 × 104 µg/L, 9.53 × 104 µg/L, 6.58 × 104 µg/L, and 4.81 × 104 µg/L, respectively. Aiming at the problems of groundwater pollution in this area, two sets of oxidation experiments have been carried out. The addition of NaHSO3 modified Fenton oxidation system was used in this contaminated water, which enhanced (2.2 ~ 46.7%) chemical oxygen demand (COD) removal rate. The highest removal rate of extractable petroleum hydrocarbons (C10-C40) can reach 99%. And the degradation rate of chlorinated hydrocarbon pollutants can reach 99% to 100%, which almost achieved the purpose of complete removal. In the NaHSO3 modified Fenton oxidation system, the addition of NaHSO3 accelerates the cycle of Fe3+/Fe2+ and ensures the continuous existence of Fe2+ in the reaction system, thereby producing more ·OH and further oxidizing and degrading organic pollutants. Our work has provided important insights for this economically important treatment of this type water body and laid the foundation for the engineering of this method.

Exploring quantitative structure-property relationship models for environmental fate assessment of petroleum hydrocarbons.

The rate and extent of biodegradation of petroleum hydrocarbons in the different aquatic environments is an important element to address. The major avenue for removing petroleum hydrocarbons from the environment is thought to be biodegradation. The present study involves the development of predictive quantitative structure-property relationship (QSPR) models for the primary biodegradation half-life of petroleum hydrocarbons that may be used to forecast the biodegradation half-life of untested petroleum hydrocarbons within the established models' applicability domain. These models use easily computable two-dimensional (2D) descriptors to investigate important structural characteristics needed for the biodegradation of petroleum hydrocarbons in freshwater (dataset 1), temperate seawater (dataset 2), and arctic seawater (dataset 3). All the developed models follow OECD guidelines. We have used double cross-validation, best subset selection, and partial least squares tools for model development. In addition, the small dataset modeler tool has been successfully used for the dataset with very few compounds (dataset 3 with 17 compounds), where dataset division was not possible. The resultant models are robust, predictive, and mechanistically interpretable based on both internal and external validation metrics (R2 range of 0.605-0.959. Q2(Loo) range of 0.509-0.904, and Q2F1 range of 0.526-0.959). The intelligent consensus predictor tool has been used for the improvement of the prediction quality for test set compounds which provided superior outcomes to those from individual partial least squares models based on several metrics (Q2F1 = 0.808 and Q2F2 = 0.805 for dataset 1 in freshwater). Molecular size and hydrophilic factor for freshwater, frequency of two carbon atoms at topological distance 4 for temperate seawater, and electronegative atom count relative to size for arctic seawater were found to be the most significant descriptors responsible for the regulation of biodegradation half-life of petroleum hydrocarbons.

The effect of temperature on hydrocarbon profiles and the microbial community composition in North Saskatchewan River water during mesoscale tank tests of diluted bitumen spills.

Despite many studies of diluted bitumen (DB) behavior during spills in saltwater, limited information is available on DB behavior in fresh water. This study examined the collective weathering processes on changes of fresh DB spilled in the North Saskatchewan River water and sediment mixture in a mesoscale spill tank under average air/water temperatures of 14 °C/15 °C and 6 °C/2 °C. Temporal changes of the hydrocarbon and microbial community compositions in the water column were assessed during the two 35-day tests under intermittent wave action. The contents of total organic carbon (TOC), benzene/toluene/ethylbenzene/xylenes (BTEX) and polycyclic aromatic hydrocarbons (PAHs) in water decreased with time during both tests. The final contents remained at higher values in warm water (15 °C) than in cold water (2 °C) after the collective weathering processes. A quick response of the main phyla, Proteobacteria and Actinobacteria, was observed, where the members of Proteobacteria enriched during both DB spills. In contrast, the members of Actinobacteria reduced with time. The microbial shifts coincided with the changes of PAHs in the waters at both temperatures. A comparison of the physical properties and chemical compositions of fresh and weathered DBs at both temperatures showed that the oil had undergone weathering that increased oil density and viscosity due to losing the light oil fraction with boiling points < 204 °C and emulsifying with water. This corresponded to losses of 19.0 wt% and 17.2 wt% of the fresh DB at 15 °C and 2 °C tests, respectively. For organic compounds in the DB with boiling points > 204 °C, there were small losses of saturates and 2- & 3-ring PAH aromatics (more during the 15 °C test than the 2 °C test), and negligible losses in the subfractions of resins and asphaltenes by the ends of the tests. <1.0 wt% of the DB was recovered from the bottom sediment, regardless of the temperature.

Response of soil microbial communities to petroleum hydrocarbons at a multi-contaminated industrial site in Lanzhou, China.

Total petroleum hydrocarbon (TPH) contamination poses threats to ecological systems and human health. Many studies have reported its negative impacts on soil microbes, but limited information is known about microbial change and response to multiple TPH contamination events. In this study, we investigated TPH contamination level, microbial community structure and functional genes at a multi-contaminated industrial site in Lanzhou, where a benzene spill accident caused the drinking water crisis in 2014. TPHs distribution in soils and groundwater indicated multiple TPH contamination events in history, and identified the spill location where high TPH level (6549 mg kg-1) and high ratio of low-molecular-weight TPHs (>80%) were observed. In contrast, TPH level was moderate (349 mg kg-1) and the proportion of low-molecular-weight TPHs was 44% in soils with a long TPH contamination history. After the spill accident, soil bacterial communities became significant diverse (p = 0.047), but the dominant microbes remained the same as Pseudomonadaceae and Comamonadaceae. The abundance of hydrocarbon-degradation related genes increased by 10-1000 folds at the site where the spill accident occurred in multi-contaminated areas and was significantly related to 2-ring PAHs. Such changes of microbial community and hydrocarbon-degradation related genes together indicated the resilience of soil indigenous microbes toward multiple contamination events. Our results proved the significant change of bacterial community and huge shift of hydrocarbon-degradation related genes after the spill accident (multiple contamination events), and provided a deep insight into microbial response at industrial sites with a long period of contamination history.

Effects of mineral species and petroleum components on thermal desorption behavior of petroleum-contaminated soil.

Thermal desorption (TD) behavior of high-concentration petroleum-contaminated soil (PCS) is affected by soil composition, especially inorganic minerals. In this study, the TD behavior of petroleum-contaminated quartz (original mineral) and kaoline (clay mineral) were compared with those of pure petroleum (Petro-free); their "saturate, aromatic, resin, and asphaltenes" (SARA) fractions were investigated using thermogravimetry and differential thermogravimetry (TG-DTG). The modelling of the petroleum removal kinetics was also analyzed to provide insights into the mechanism. The results revealed that the limiting factor controlling the desorption of petroleum from quartz (Petro-Qtz) and kaoline (Petro-Kln) is the minerals, which increased the effective TD temperature by 200 °C and decreased TD efficiency by 2%. Compared to Petro-Qtz, Petro-Kln showed a lower desorption efficiency of 5% and the process was accomplished at a higher temperature of 100 °C. The investigation on SARA fractions indicated that polar fractions (i.e., aromatics, resins, and asphaltenes) were strongly captured by the minerals. The increment of the TD temperature of petroleum (resins-160 °C > aromatics-20 °C > saturates-5 °C) increased with the polarity of petroleum components. These results could be validated by thermogravimetry-gas chromatography/mass spectroscopy (TG-GC/MS) through the delayed desorption of naphthalene and acenaphthene. Furthermore, the increment of the TD temperature of SARA fractions on kaoline was higher than those on quartz. This makes sense because the kaoline decreased the diffusion of hydrocarbons due to its porosity features and higher specific surface area (kaoline 5.3300 m2 g-1, quartz 0.1153 m2 g-1). In addition, the analysis of the desorption kinetic models showed that the observed hysteresis was related to the diffusion barrier caused by chemisorption (n＜1). In consequence, the Petro-Kln showed a lower desorption efficiency, a slower desorption, and as a result, a higher energy consumption (0.476 kW h) for thermal remediation than Petro-Qtz (0.238 kW h).

Clays play a catalytic role in pyrolytic treatment of crude-oil contaminated soils that is enhanced by ion-exchanged transition metals.

Pyrolytic treatment of crude-oil contaminated soils offers great potential for rapid remediation without destroying soil fertility with lower energy requirements than incineration. Here, we show that clays impregnated with non-toxic transition metals (iron or copper) can be used as an amendment to decrease the required pyrolytic treatment temperature and time. Amending a weathered crude-oil contaminated soil with 10 % (by weight) of bentonite modified via ion-exchange with Fe or Cu, achieved 99 % removal of residual total petroleum hydrocarbons (TPH) at a pyrolysis temperature of 370 °C with 15-min contact time. Pyrolytic treatment of amended soils at the unprecedentedly low pyrolysis temperature of 300 °C resulted in 87 % TPH removal efficiency with Cu-bentonite and a 93 % with Fe-bentonite. We postulate that the transition metals catalyzed the pyrolysis reactions at lower onset temperatures. This hypothesis is supported by thermogravimetric analysis coupled with mass spectrometry, which revealed the release of hydrogen, methyl and propyl ion fragments (markers of pyrolytic degradation products of crude oil) at lower temperatures than those observed for unamended soil. Overall, this work shows proof of concept that metal-impregnated clays can enhance rapid pyro-catalytic treatment of crude-oil contaminated soils and encourages further work to understand the detailed reaction mechanisms and inform process design.

Evaluation of Neoproterozoic source rock potential in SE Pakistan and adjacent Bikaner-Nagaur Basin India.

Discoveries of heavy crude oil in the Neoproterozoic rocks (Infracambrian rock sequence) from the Bikaner-Nagaur Basin of India emphasize the significance of studying and exploring the Neoproterozoic source rock potential in the southeastern part of Pakistan. This study evaluates the potential of the source rock in the Infracambrian rock sequence (Salt Range Formation) based on surface geochemical surveys, Rock-Eval pyrolysis, source biomarkers, geophysical characterization, and seismic inversion using machine learning for maturity index estimation. Core samples of Infracambrian rock were extracted for Rock-Eval pyrolysis and biomarker characterization. Additionally, 81 geomicrobial soil and gas samples were collected from the surface to explore the petroleum system and potential source rocks in the subsurface. Advanced interpretation techniques were used to investigate the origin and concentration of hydrocarbon gases at the surface, including Rock-Eval pyrolysis, thermal maturity, source biomarkers, and the environment of deposition of organic matter. The results show that the investigated samples are characterized by restricted marine clay devoid of sedimentary carbonate facies with thermal maturity in the early stage of the oil generation window. The seismic inverted maturity index profile demonstrates a reasonable correlation of thermal maturity with the biomarkers and Rock-Eval pyrolysis. Further scrutiny of the surface geochemical samples confirms the presence of higher concentrations of thermogenic C2-C4 hydrocarbons in the vicinity of anticlinal structures, suggesting the existence of an effective migration path along deep-seated faults to the surface. This study concludes that the Infracambrian rocks on the eastern flank of Pakistan are thicker, thermally mature, and have deep-seated structural closures, indicating a greater probability of heavy and light oil in this area than in the Bikaner-Nagaur Basin, India.

Interaction and spatio-taxonomic patterns of the soil microbiome around oil production wells impacted by petroleum hydrocarbons.

Numerous onshore oil production wells currently exist, and the petroleum hydrocarbon contamination of the surrounding soil caused by oil production wells is not well understood. Moreover, the impact of the distribution of the total petroleum hydrocarbons (TPH) in the soil on the microbiota requires further investigation. Accordingly, in this study, the distribution of petroleum hydrocarbons in the soils around oil production wells was investigated, and their alteration of the microbiota was revealed. The results revealed that in the horizontal direction, the heavily TPH-contaminated soils were mainly distributed within a circle with a radius of 200 cm centered on the oil production well; and in the vertical direction, the heavily TPH-contaminated soils were distributed within the 0-50 cm soil layer. A significant positive correlation was found between the microbial abundance and the TPH concentration in the soil with relatively low total carbon contents. Heavy TPH contamination (TPH concentration of >3000 mg/kg) significantly reduced the microbial diversity and altered the microbiota compared with the light TPH contamination (TPH concentration of around 1000 mg/kg). In the heavily TPH-contaminated soils, the relative abundances of the Proteobacteria and Bacteroides increased significantly; the network complexity among the soil microorganisms decreased; and the co-occurrence patterns were altered. In summary, the results of this study have reference value in the remediation of soils around oil production wells and provide guidance for the construction of microbial remediation systems for petroleum contamination.