Search

In recent years, aimed to promote the improvement of China’s new energy vehicle market, a series of incentive policies issued by the Chinese government: including the new energy vehicle subsidy policy, the double credit policy, and the charging pile infrastructure subsidy.Relevant research on new energy vehicle industry is mainly ground on multi-stage game, this paper employs multi-agent games theory, and summarizes the multi-agent decision-making optimization method in differential game based on dynamic programming and reinforcement learning. Then, in the context of new energy vehicles, research and improve the industrial policy of new energy vehicles through this method.A multi-agent differential game decision-making optimization framework is proposed. Complex multi-agent differential game decisions can be solved using the dynamic programming solver or deep reinforcement learning solver in this framework. Case studies and some observations will be given in the end.

The elimination of gaseous sulfur-containing volatile organic compounds (S-VOCs) by a microbubble-assisted Fenton-like process is an innovative strategy. Herein, we established a microbubble-assisted Fenton-like process to eliminate malodorous microbubble CH

Biological control is an effective measure in the green control of rice diseases. To search for biocontrol agents with broad-spectrum and high efficiency against rice diseases, in this study, a strain of antagonistic bacterium BR-01 with strong inhibitory effect against various rice diseases was isolated from

Organosulfur compounds (OrgSs), especially organosulfates, have been widely reported to be present in large quantities in particulate organic matter found in various atmospheric environments. Despite hundreds of organosulfates and their formation mechanisms being previously identified, a large fraction of OrgSs remain unexplained at the molecular level, and a better understanding of their formation pathways and critical environmental parameters is required to explain the variations in their concentrations. In this study, the abundance and molecular composition of OrgSs in fine particulate samples collected in Guangzhou were reported. The results revealed that the ratio of the annual average mass of organic sulfur to total particulate sulfur was 33 ± 12 %, and organic sulfur had positive correlations with SO2 (r=0.37, p) and oxidant (NOx + O3, r=0.40, p). A Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analysis revealed that more than 80 % of the sulfur-containing formulas detected in the samples had the elemental composition of o/(4s+3n)≥1, indicating that they were largely in the form of oxidized organosulfates or nitrooxy organosulfates. Many OrgSs that were previously tentatively identified as having biogenic or anthropogenic origins were also present in freshly emitted aerosols derived from combustion sources. The results indicated that the formation of OrgSs through an epoxide intermediate pathway could account for up to 46 % of OrgSs from an upper bound estimation, and the oxidant levels could explain 20 % of the variation in the mass of organic sulfur. The analysis of our large dataset of FT-ICR MS results suggested that relative humidity, oxidation of biogenic volatile organic compounds via ozonolysis, and NOx-related nitrooxy organosulfate formation were the major reasons for the molecular variation of OrgSs, possibly highlighting the importance of the acid-catalyzed ring-opening of epoxides, oxidation processes, and heterogeneous reactions involving either the uptake of SO2 or the heterogeneous oxidation of particulate organosulfates into additional unrecognized OrgSs.

The lower Cambrian Niutitang/Qiongzhusi shale gas in the Middle-Upper Yangtz Block had been regarded as a very promising unconventional natural gas resource due to its high total organic carbon, great thickness, and large areal distribution. However, no commercial shale gas fields have yet been reported. From the northwest to the southeast there are considerable differences in the sedimentary environments, lithology, and erosive nature of the underlying interval (the floor interval) of the Niutitang shale. However, systematic research on whether and how these regional differences influence shale petrophysical properties and shale gas preservation in the Niutitang shale is lacking. A comparison of Niutitang shale reservoirs as influenced by different sedimentary and tectonic backgrounds is necessary. Samples were selected from both the overmature Niutitang shales and the floor interval. These samples cover the late Ediacaran and early Cambrian, with sedimentary environments varying from carbonate platform and carbonate platform marginal zone facies to continental shelf/slope. Previously published data on the lower Cambrian samples from Kaiyang (carbonate platform), Youyang (carbonate platform marginal zone) and Cen’gong (continental shelf/slope) sections were integrated and compared. The results indicate that the petrophysical properties of the floor interval can affect not only the preservation conditions (sealing capacity) of the shale gas, but also the petrophysical properties (pore volume, porosity, specific surface area and permeability) and methane content of the Niutitang shale. From the carbonate platform face to the continental shelf/slope the sealing capacity of the floor interval gradually improves because the latter gradually passes from high permeability dolostone (the Dengying Formation) to low permeability dense chert (the Liuchapo Formation). In addition, in contrast with several unconformities that occur in the carbonate platform face in the northern Guizhou depression, no unconformity contact occurs between the Niutitang shale and the floor interval on the continental shelf/slope developed in eastern Chongqing Province and northwestern Hunan Province. Such regional differences in floor interval could lead to significant differences in hydrocarbon expulsion behaviour and the development of organic pores within the Niutitang shale. Therefore, shale gas prospects in the Niutitang shales deposited on the continental shelf/slope should be significantly better than those of shales deposited on the carbonate platform face.

Kerogen can release both liquid and gaseous hydrocarbons during thermal maturation. In this study, the maturation and hydrocarbon generation of a low-maturity type II kerogen were simulated via tem...

This study demonstrates a new system for the degradation of emerging pharmaceutical contaminants (e.g., ibuprofen) in water by coupling the naturally occurring ilmenite with hydroxylamine (HA) and persulfate (PS). Ilmenite was able to activate persulfate to generate sulfate radicals (SO4−·) and hydroxyl radicals (HO·). The radical generation was greatly improved by adding small amount of hydroxylamine into the solution, due to the efficient Fe(III)/Fe(II) cycle on the ilmenite surface promoted by HA, which was confirmed by X-ray photoelectron spectroscopy and electron paramagnetic resonance (EPR) spectroscopy analysis. SO4−· and HO· contributed comparably to ibuprofen degradation, which was verified by the radical scavenging tests. The degradation was enhanced with increasing ilmenite, PS and HA dosages, but the HA exhibited strong scavenging effect at its high concentrations. The ilmenite/PS/HA process worked well in the real treated wastewater, because the surface-controlled radical generation was less affected by the water matrix. However, the formation of bromate in the bromide-containing water by this process should be concerned. Ibuprofen was partially mineralized, and the degradation products were identified by ESI-tqMS. A radical-induced degradation pathway was proposed based on the product identification. This work provides the mechanistic insights on persulfate activation based on the surface-controlled catalytic processes. It also offers a new strategy to degrade emerging contaminants in water and sheds light on the environmental functions of natural minerals.

The oxygen vacancy in MnO2 is normally proved as the reactive site for the catalytic ozonation, and acquiring a highly reactive crystal facet with abundant oxygen vacancy by facet engineering is advisable for boosting the catalytic activity. In this study, three facet-engineered α-MnO2 was prepared and successfully utilized for catalytic ozonation toward an odorous CH3SH. The as-synthesized 310-MnO2 exhibited superior activity in catalytic ozonation of CH3SH than that of 110-MnO2 and 100-MnO2, which could achieve 100% removal efficiency for 70 ppm of CH3SH within 20 min. The results of XPS, Raman, H2-TPR, and DFT calculation all prove that the (310) facets possess a higher surface energy than other facets can feature the construction of oxygen vacancies, thus facilitating the adsorption and activate O3 into intermediate peroxide species (O2-/O22-) and reactive oxygen species (•O2-/1O2) for eliminating adjacent CH3SH. In situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS) revealed that the CH3SH molecular was chemisorbed on S atom to form CH3S-, which was further converted into intermediate CH3SO3- and finally oxidized into SO42- and CO32-/CO2 during the process. Attributed to the deep oxidation of CH3SH on 310-MnO2 via efficient cycling of active oxygen vacancies, the lifetime of 310-MnO2 can be extended to 2.5 h with limited loss of activity, while 110-MnO2 and 100-MnO2 were inactivated within 1 h. This study deepens the comprehension of facet-engineering in MnO2 and presents an efficient and portable catalyst to control odorous pollution.

Unlike the deep understanding of highly oxygenated organic molecules (HOMs) driving continental new particle formation (NPF), little is known about the organic compounds involved in coastal and open-ocean NPF. On the coastline of China we observed intense coastal NPF events initiated by iodine nucleation, but particle growth to cloud condensation nuclei (CCN) sizes was dominated by organic compounds. This article reveals a new group of C18,30HhOoNn and C20,24,28,33HhOo compounds with specific double-bond equivalents and oxygen atom numbers in new sub 20 nm coastal iodine particles by using ultrahigh-resolution Fourier transform–ion cyclotron resonance mass spectrometry (FT-ICR-MS). We proposed these compounds are oxygenated or nitrated products of long-chain unsaturated fatty acids, fatty alcohols, nonprotein amino acids or amino alcohols emitted mutually with iodine from coastal biota or biologically active sea surface. Group contribution method estimated that the addition of –ONO2, –OH and –C=O groups to the precursors reduced their volatility by 2–7 orders of magnitude and thus made their products condensable onto new iodine particles in the coastal atmosphere. Nontarget MS analysis also provided a list of 440 formulas of iodinated organic compounds in size-resolved aerosol samples during the iodine NPF days, which facilitates the understanding of unknown aerosol chemistry of iodine.

Organosulfur compounds (OrgSs), especially organosulfates, have been widely reported at large quantities in particulate organic matter found in various atmospheric environments. Despite various kinds of organosulfates and their formation mechanisms being previously identified, a large fraction of OrgSs remain unexplained at the molecular level, impeding further knowledge on additional formation pathways and critical environmental parameters that help to explain their concentrations. In this work, the abundance and molecular composition of OrgSs in fine particulate samples collected in Guangzhou was reported. Our results revealed that organic sulfur can averagely contribute to 30 % of total particulate sulfur, and showed positively correlations with the SO2 (r = 0.37, p < 0.05) and oxidants (NOx+O3, r = 0.40, p < 0.01). Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) results presented that more than 80 % by number of the detected OrgSs in our samples have the elemental composition of O/(4S+3N) ≥ 1, indicating that they were largely in the form of oxidized organosulfates and/or nitrooxy organosulfates. Many OrgSs, which are tentatively attributed to previously identified biogenic and anthropogenic origins, were also present in aerosols derived from freshly-emitted combustion sources. Results show that the formation of OrgSs through an epoxide intermediate pathway could be as much as 46 %, and the oxidants levels could explain 20 % variation of organic sulfur mass. The analysis from our large FT-ICR MS dataset suggests that relative humidity, oxidation of biogenic volatile organic compounds via ozonolysis, and NOx-related nitrooxy organosulfate formations were the major reasons for the molecular variation of OrgSs, possibly highlighting the importance of heterogeneous reactions involving either the uptake of SO2 or the heterogeneous oxidations of particulate organosulfates into additional unrecognized OrgSs.

Characterizing the molecular composition of cloud water could provide unique insights into aqueous chemistry. Field measurements were conducted at Mt. Tianjing in southern China in May, 2018. There are thousands of formulas (C$_{5-30}$H$_{4-55}$O$_{1-15}$N$_{0-2}$S$_{0-2}$) identified in cloud water by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). CHON formulas (formulas containing C, H, O, and N elements; the same is true for CHO and CHOS) represent the dominant component (43.6 %���65.3 % of relative abundance), followed by CHO (13.8 %���52.1%). S-containing formulas constitute ���5 %���20 % of all assigned formulas. Cloud water has a relative-abundance-weighted average O/C of 0.45���0.56, and the double bond equivalent of 5.10���5.70. Most of the formulas (>85 %) are assigned as aliphatic and olefinic species. No statistical difference in the oxidation state is observed between cloud water and interstitial PM$_{2.5}$. CHON with aromatic structures are abundant in cloud water, suggesting their enhanced in-cloud formation. Other organics in cloud water are mainly from biomass burning and oxidation of biogenic volatile organic compounds. The cloud water contains more abundant CHON and CHOS at night, which are primarily contributed by ���N$_{2}$O$_{5}$ function and organosulfates, demonstrating the enhanced formation in dark aqueous or multi-phase reactions. While more abundant CHO is observed during the daytime, likely due to the photochemical oxidation and photolysis of N- or S-containing formulas. The results provide an improved understanding of the in-cloud aqueous-phase reactions.

The light-absorbing organic aerosol referred to as brown carbon (BrC) affects the global radiative balance. The linkages between its molecular composition and light absorption properties and how environmental factors influence BrC composition are not well understood. In this study, atmospheric dissolved organic matter (ADOM) in 55 aerosol samples from Guangzhou was characterized using Fourier transform ion cyclotron resonance mass spectrometry and light absorption measurements. The abundant components in ADOM were aliphatics and peptide-likes (in structure), or nitrogen- and sulfur-containing compounds (in elemental composition). The light absorption properties of ADOM were positively correlated with the levels of unsaturated and aromatic structures. Particularly, 17 nitrogen-containing species, which are identified by a random forest, characterized the variation of BrC absorption well. Aggregated boosted tree model and nonmetric multidimensional scaling analysis show that the BrC composition was largely driven by meteorological conditions and anthropogenic activities, among which biomass burning (BB) and OH radical were the two important factors. BrC compounds often accumulate with elevated BB emissions and related secondary processes, whereas the photolysis/photooxidation of BrC usually occurs under high solar radiance/•OH concentration. This study first illuminated how environmental factors influence BrC at the molecular level and provided clues for the molecular-level research of BrC in the future.

To evaluate petroleum generation and expulsion processes, pyrolysis experiments that simulate increased overburden pressures were conducted on an immature organic-rich shale with type-II kerogen. Expelled oils and residual rocks with different maturities covering the oil window were recovered from the experiments. The residual rocks were then subjected to stepwise extraction in conjunction with stepwise dissolution of the carbonate and silicate minerals to obtain free and bound bitumen fractions. The compositions of acidic and neutral compounds in both expelled oils and bitumen fractions were investigated by negative-ion electrospray (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Neutral nitrogen compounds were found to only exist in expelled oil and free bitumen, while acidic compounds (typically contain carboxylic functional group(s)) were prevalent in bound bitumen. Oxygen-containing functional groups with high polarity in oxygen-containing compounds and oxygenated nitrogen/sulfur compounds are proposed to be the dominant bonding forces that facilitate the interaction between bitumen and mineral matrix or kerogen. Semiquantitative results of acidic compounds reveal that the distributions of acidic compounds in both free and bound bitumens vary throughout the oil window stage, especially for those in the bound phase after an intense oil expulsion from the shale at Easy%Ro > 0.9. During maturation, acidic compounds in free and bound bitumens gradually decreased in their abundances. However, oil expulsion from the shale brought about a significant redistribution of acidic compounds among expelled oil, free and bound bitumens. These results indicate that polar components in shales are closely related to thermal maturation of organic matter and oil expulsion from the shales in a petroleum system.

[Image: see text] Petroleum generation–expulsion thermal simulation experiments on a low-maturity type I source rock were carried out. The composition of hydrocarbons and heteroatom-containing compounds in both expelled and residual oils was characterized by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry and gas chromatography-mass spectrometry. A thorough analysis of fractionation effects was presented between expelled and residual oils. The oil composition strongly depended on the pyrolysis temperature. A significant difference in the molecular composition was found between expelled and residual oils at various pyrolysis temperatures. The difference in maturity for expelled and residual oils could be revealed clearly by the difference in the molecular composition of heteroatom-containing compounds. Carboxylic acids in the residual oil cracked quickly with the pyrolysis temperature above 350 °C (% Ro = 1.0) but part of them would survive if they were expelled out of the source rock timely. The variations between the relative abundance of oxygen compounds and nitrogen compounds indicated that the thermostability of oxygen-containing nitrogen compounds was lower than that of neutral nitrogen compounds. The variation trends in double bond equivalents and carbon number distributions of O(1), O(2), and N(1) class species were similar. The aromaticity of heteroatom-containing polar species increased with maturity.

Atomic level Ag loaded MnO2 porous hollow microspheres (Ag/MnO2 PHMs) were prepared by redox precipitation method, and utilized for E. coli inactivation under solar light irradiation. Ag nanoparticles (NPs) can be downsized into single atoms, thereby realizing highly utilization of Ag element as well as achieving superior photothermocatalytic E. coli inactivation for Ag/MnO2 than MnO2 PHMs. Under attack by the optimal 0.3%Ag/MnO2 PHMs with atomic Ag, 7.11 log10 cfu/mL cells can be completely inactivated within 10 min, much faster than the 0.3%Ag/MnO2 PHMs with Ag cluster (3.3 log10 cfu/mL) prepared by photodeposition method, demonstrating the feasibility of redox precipitation to prepare efficient catalyst for water disinfection. Three effects are believed to contribute to this bacterial inactivation enhancement: (1) atomic Ag with high conductivity induces more formation of Mn3+ and oxygen vacancies in MnO2, which can efficiently accelerate the separation of hot electrons and holes generated by MnO2, collectively work with itself generated hot electrons to form into reactive species for photocatalysis; (2) atomic Ag exhibits strong local heating effect and induces higher reducibility for MnO2, considerably enhances the photothermal conversion and lattice oxygen activity of MnO2, thus promoting the thermocatalysis; and (3) the synergism of solar light driven photocatalysis and thermocatalysis through the activated OL. The highly efficient photothermocatalysis make the designed 3D atomic Ag/MnO2 PHMs have a promising antibacterial ability for cleaning the microbial contaminated water environment.

Rational design of sustainable, cost-efficient and highly efficient deionization electrodes is crucial for the practical applications of capacitive deionization (CDI). Mycelial pellet-derived nitrogen and sulfur heteroatom co-doped three-dimensional (3D) carbon nanosheets (NSHPC) with a hierarchical porous structure have been facilely fabricated via a simple one-step strategy by utilizing sustainable mycelial pellets as a carbon source, glutaraldehyde as a crosslinking agent, zinc chloride as a pore forming agent, and thiourea as a heteroatom supplier. The obtained biomass-derived NSHPC nanosheets, with interconnected hierarchical macro-meso-micropores and a lamellar structure, exhibit outstanding CDI performance with an electrosorption capacity of 18.71 mg g−1 in 500 mg L−1 NaCl solution and a high reversibility (stable up to 10 cycles). The performance of NSHPC significantly surpasses that of the bulk mycelial pellet-derived carbon without activation and modification. The efficient CDI performance of NSHPC can be attributed to its unique features, including the 3D network structure formed by bundled nanosheets to provide multi-dimensional ion diffusion pathways and interlayer ion storage, the hierarchical pores to assist efficient ion diffusion and capture, the surface functional groups derived from mycelial pellets, and the hydrophilicity contributed by the heteroatom co-doping. The design of NSHPC nanosheets paves an avenue for developing efficient sustainable materials for CDI applications.

Summary In this study, two liquid hydrocarbon collection methods were used to collect light hydrocarbons generated from the cracking of crude oil in closed system, and the characteristics of the products collected were compared. Relative to the liquid nitrogen direct freezing collection (LNDF) method, the traditional liquid hydrocarbon collection (TLH) method can cause the yield loss of 10%-75% of light hydrocarbons, especially low carbon number light hydrocarbons (such as nC6, nC7, benzene, toluene, and 3-methylhexane). Because the TLH method can lead to various degrees of loss for different compounds in light hydrocarbons, it can also lead to the deviation of some light hydrocarbon parameters representing oil-oil correlation, indicating the maturity of crude oil and reflecting secondary alteration of crude oil. In addition, the δ13C values of nC6, nC7, benzene, toluene and 3-methylhexane collected by TLH method are heavier. These compounds with heavier δ13C values are the ones that have suffered the most yield loss in the TLH method. Therefore, the LNDF method can more accurately reflect the yield, parameters and carbon isotopes of light hydrocarbons in closed system pyrolysis.

Summary Thick and organic-rich mudrocks occur in the lower Cretaceous Xiguayuan Formation of the Luanping Basin, Northern China. However, the studies concerning geochemical characteristics of the mudrocks were limited. Shale oil was first discovered in Well LT-1 in Cretaceous Formation of Luanping Basin, filling the gap in the discovery of Mesozoic hydrocarbon in the Yanshan Structural Belt. In this study, the core samples in Well LT-1 and several outcrop samples from stratigraphic sections were collected. A combined investigation of organic and inorganic geochemistry was carried out to study the geochemical characteristics and paleo-environment as well as the controlling factors for organic matter accumulation. The Rock-Eval and organic petrology results indicate that the mudrocks have good hydrocarbon generation potential. Additionally, the biomarkers and elements show that the mudrocks were formed in the anoxic lacustrine sedimentary environment with a stratified water column varying from brackish to high salinity. The paleoclimate was semiarid, the paleoproductivity was moderate and the sedimentary rate was fast. The main sources of organic matter are aquatic plankton, and terrestrial higher plant. Excellent preservation and moderate productivity are the major controlling factors for organic matter accumulation in the Xiguayuan Formation.

A novel process for S-VOCs degradation using wet scrubbing coupled with catalytic ozonation was developed for first time. We report redox-robust catalysts consisting of Ag(0)/Ag(I) species decorated rambutan-like MnO2 hollow microspheres (Ag/R-MnO2) with strong metal-metal oxide interaction (MMOI) exhibited superior catalytic ozonation performance for CH3SH elimination. The optimum Ag/R-MnO2 reached a significant improvement in CH3SH elimination of 96.9% conversion over pristine R-MnO2 under GHSV of 75,000 mL h−1 g−1, and O3 utilization rate of 92.3%. An outstanding stability of Ag/R-MnO2 under wet catalytic ozonation process was demonstrated, which outperformed that in gaseous system. CH3SH was captured by aqueous solution and preferentially chemisorbed on Ag, then deeply oxidized to the final products of SO42-/CO32- via catalytic ozonation by multivalent R-MnO2. The excellent performance can be ascribed to efficient electron replenishing interaction between Ag(0)/Ag(I) and multivalent R-MnO2, efficient O3 activation through oxygen vacancies-rich R-MnO2, and enhanced mass diffusion in wet scrubbing process.

The metamorphism of snow (snowmelt process) has a potential influence on chemical and physical process occurring within it. This study carried out a detailed study on the variation of dissolved organic matter (DOM) in different stages of snowmelt in a typical mountain glacier located at Tibetan Plateau through collecting four different surface snow/ice categories, i.e., fresh snow, fine firn, coarse firn, and granular ice during May to October in 2015. The dissolved organic carbon (DOC) was observed by lost 44% from fresh snow to fine firn and enriched 129% from fine firn to granular ice, reflecting the dynamic variability in DOC concentration during snow metamorphism. The absorbance properties of each snow category are positively correlated with DOC concentration. The result of excitation emission matrix fluorescence with parallel factor analysis (EEM-PARAFAC) and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) highlighted the domination of lipid- and protein-like compounds in glacial-derived DOM. The molecular composition of the DOM also exhibited a new N-containing molecular formula (CHON classes) that was enriched during snow metamorphism. This study suggests that snow metamorphism could induce a loss of DOM as well as enrich and modify the DOM.

Petroleum biomarkers could be altered to varying extents under the influence of biodegradation and thermal alteration in reservoir, and their respective influence has been well documented. However, the superimposed influence of successive biodegradation and thermal alteration has not been systematically studied so far. In this study, a sequence of crude oils and oil sands that are of identical origin but at different biodegradation levels from the Liaohe Basin of China were artificially matured via closed-system pyrolysis. The distributions of biomarkers such as steranes and hopanes in the variably biodegraded oil samples and in their pyrolyzates at varying artificial thermal maturities were compared. The results showed that the presence of normal (n-) alkanes in crude oil does not necessarily excludes the possibility of previous moderate–severe biodegradation as n-alkanes can be further generated under advanced thermal stress. Besides, biomarkers in the oils that have suffered superimposed alterations could be derived not only from the modifications of free biomarkers in the oils, but also from the release of biomarkers bound in the asphaltenes. The mix of these two sources complicated the biomarker profiles in this type of oils. Most source related parameters based on steranes and tri-, tetra- and penta-cyclic terpanes seem to be reliable only when the oil reservoir has suffered biodegradation not beyond moderate level and the maturity of the crude oil is below 0.91 Easy%Ro. The TT23/(TT23 + TT24) ratio, however, was found to remain constant even after severe biodegradation and thermal alteration, making it applicable in oil-source correlation in superimposed oil reservoirs. In addition, isomerization-based maturity parameters such as methylphenanthrene index of crude oils are reliable if subsequent thermal alteration reached above 0.91 Easy%Ro despite prior moderate–severe biodegradation, because the related isomerization reactions would approach the same level observed for the non-biodegraded oil after subsequent thermal alteration.

Identification and quantification of mixed sources of petroleum reservoirs as well as the sources of oil spills generally requires the molecular composition information about the mixture. In this study, the relative concentrations of a series of polar acidic compounds, semiquantified by negative ion ESI FT-ICR MS, were calculated using alternating least-squares (ALS) to unmix a group of oil mixtures prepared in the laboratory using three endmember oils. It was shown that the ALS results were accurate based on the relative concentrations of polar acidic compounds, regardless of whether endmember oils and several samples were removed from the sample set. ALS was able to accurately calculate the composition of endmember oils, regardless of whether they were included in the sample set. This method is relatively simple, efficient, time-saving, and has potential for geological source identification of mixed oils or oil spills.

Thick marine shales occur in the Wufeng Formation and Longmaxi Formation of Sanquan Town of the Nanchuan District, Chongqing Municipality, which is located on the southeast margin of the Sichuan Basin. However, few details of the characteristics of the Wufeng–Longmaxi shales in this area have been reported. In this study, a well approximately 100 m (∼328 ft) deep was drilled. A high-quality shale (total organic carbon [TOC] >2.0 wt. %, clay

Achieving an understanding of the biodegradation of organic sulfur compound(s) (OSC) in crude oils has been hampered by limitations in separation methods and analytical techniques. In this study, a simulated aerobic biodegradation experiment was performed on a sulfur-rich crude oil, from which a series of biodegraded oils from slight to moderate degrees of biodegradation were obtained. Molecular transformations in these biodegraded oils were investigated by gas chromatography–mass spectrometry (GC–MS) and Fourier transform ion cyclotron resonance mass spectrometry (FT–ICR MS) under both positive- and negative-ion electrospray ionization (ESI) modes. The variations in the distributions of saturated hydrocarbons, OSCs, and acidic components during aerobic biodegradation were studied. A gradual decrease of OSCs with alkyl chains during biodegradation, especially in those with few sulfur-containing or naphthenic/aromatic rings, was observed. In addition, sulfur-containing phenols with alkyl chains also exhibited a trend of gradual decrease similar to alkyl phenols, with fewer ring numbers being more susceptible to biodegradation. The biodegradation pathways for OSCs and sulfur-containing acids, as well as certain other heteroatomic compounds, are discussed. Terminal oxidation, rather than sulfur-specific degradation, is the more likely biodegradation pathway of these OSCs, as in the case of n-alkanes in this study. Sulfur-containing carboxylic acids may be the biodegradation products of these OSCs.

Organic sulfur compounds (OSCs) are abundant in immature crude oils, including “polar” OSCs that are defined here as compounds containing one or more heteroatom(s) in addition to sulfur atoms having sufficient polarity to be analyzable by electrospray ionization (ESI) without derivatization. An understanding of the origins of polar OSCs in crude oils has been hampered by limitations in their analytical characterization. In this paper, we employed a high field (9.4 T) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) coupled with ESI to study the sulfur-rich immature crude oils from the Jianghan Basin in China. The results show that the polar OSCs usually have non-sulfur counterparts, i.e., heteroatom-containing compounds without sulfur, with similar carbon number ranges, but slightly lower DBE (double bond equivalence) distributions. The similar or even identical carbon number distributions of the polar OSCs and their non-sulfur counterparts indicate their inheritance from the same precursors. The sulfur rings in polar OSCs are formed by intramolecular sulfurization that leads to the increases in DBEs compared to their non-sulfur counterparts. The results also indicate that the number of sulfur rings that can be formed in polar OSCs is largely controlled by the number of available reactive functional groups in their precursors. This paper extends our knowledge of intramolecular sulfurization during early diagenesis, especially for polar heteroatom-containing compounds.