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The fragmentation of normal alkanes during the cracking of oil under geochemical conditions with high thermal stress is important for the preservation of crude oils in reservoirs and the formation of gaseous hydrocarbons. In this study, the kinetics behavior, cracking mechanisms, and products of n-tetradecane pyrolysis were investigated using reactive molecular dynamics (ReaxFF MD) simulations at high temperatures (2000K∼3000 K). The pyrolysis process itself, its main products and intermediates, and kinetic behavior were analyzed at an atomic/molecular level. Low molecular weight (C1–C5) alkanes and olefins, together with H2, were the predominant intermediates and products of the simulations. Three distinct stages—a stable stage, initial decomposition, and secondary pyrolysis—can be distinguished during the decomposition process. The reactant n-tetradecane was exhausted when the simulation temperature reaches ∼2250 K, accompanied by a rapid increase in hydrocarbons with molecular numbers C1–C5. The yield of C2–C5 peaked at ∼2500 K and then decreased. The number of CH4 molecules increased continuously throughout the entire simulation process because of the contribution of secondary pyrolysis. The Arrhenius parameters obtained from ReaxFF MD simulations, on the basis of first-order kinetic analysis of n-tetradecane, were reasonably consistent with experimental data and generally in agreement with results from pyrolysis experiments on crude oils in the laboratory. The pyrolysis process and reaction mechanism of n-tetradecane were also reasonably consistent with laboratory pyrolysis experiments on whole oils and their individual components. ReaxFF molecular dynamics simulation is therefore considered to be a valid approach for the study of thermal cracking of subsurface crude oils.

Methylated 2-methyl-2-(4,8,12-trimethyltridecyl)chromans are salinity-sensitive biomarkers that have been detected in immature – early mature petroleum and sediments. In this study, the occurrence and distribution patterns of 2-methyl-2-(4,8,12-trimethyltridecyl)chromans were investigated in a set of lacustrine sediments from Nördlinger Ries of southern Germany and marine sediments from the South China Sea. Among all of the 2-methyl-2-(4,8,12-trimethyltridecyl)chroman isomers detected, 8-Me-2-methyl-2-(4,8,12-trimethyltridecyl)chroman presented with high abundance in sediments deposited in hypersaline environments, while absent in samples from normal marine environments. In contrast, 5,7,8-triMe-2-methyl-2-(4,8,12-trimethyltridecyl)chroman was more enriched in sediments from marine environments. This study also showed that the ratio of 5,7,8-triMe-/5,8-diMe-2-methyl-2-(4,8,12-trimethyltridecyl)chroman can be applied as a potential salinity indicator on account of a positive correlation with other 2-methyl-2-(4,8,12-trimethyltridecyl)chroman salinity indicators. This ratio can be an alternative indicator of paleosalinity when 8-Me-2-methyl-2-(4,8,12-trimethyltridecyl)chroman is absent or present in quite low abundance. The content of 2-methyl-2-(4,8,12-trimethyltridecyl)chroman isomers may be affected by freshwater supply and lithology. Molecular simulations showed that 5,8-diMe-2-methyl-2-(4,8,12-trimethyltridecyl)chroman has a higher thermal dynamic stability than 7,8-diMe-2-methyl-2-(4,8,12-trimethyltridecyl)chroman. Thus, the ratio of 5,8-diMe-2-methyl-2-(4,8,12-trimethyltridecyl)chroman/7,8-diMe-2-methyl-2-(4,8,12-trimethyltridecyl)chroman may be a potential maturity parameter for sediments at a low thermal mature stage.

Oil reservoirs have been discovered in the Mesoproterozoic strata in the Liaoxi Depression, NE China. In order to determine the source of oil shows of the Mesoproterozoic Gaoyuzhuang Formation and their organic geochemical characteristics, eight source rocks and reservoir cores from the Mesoproterozoic Gaoyuzhuang Formation and four source rocks from the overlying Middle Jurassic Haifanggou Formation were geochemically analysed. The distribution patterns of normal alkanes, acyclic isoprenoids, hopanes, steranes and triaromatic steroids of the Mesoproterozoic hydrocarbons from Well N-1 are consistent with those of source rock extracts from the Mesoproterozoic Gaoyuzhuang Formation in the Well L-1. The molecular marker compositions of source rock extracts from the overlying Middle Jurassic Haifanggou Formation are distinctively different from those of the Mesoproterozoic hydrocarbons. The results suggest that the Mesoproterozoic source rocks have significant petroleum generation potential. The Mesoproterozoic paleo-reservoir may be prospecting exploration targets in the Liaoxi Depression, NE China.

The Paleogene lacustrine mudstone is one of the most important sets of source rocks in Termit Basin, Niger. However, studies on the Paleogene source kitchen are scarce. In this study, the source rock types, spatial distribution and their hydrocarbon generative potential within the Paleogene Sokor-1 and LV formations are systematically evaluated. A total of two third-order sequences (SSQ1 and SSQ2, from the bottom to top) and six systems tracts were identified in the Sokor-1 Formation, while the LV Formation mainly comprises pure shale and is regarded as a compositive stratigraphic sequence with no need of subdivision. Six types of source rocks could be distinguished within the three depositional environments of the sequence stratigraphic framework: (1) deep lake mudstones and shale deposited in the lacustrine deep-water facies, (2) shallow lake mudstones and carbonaceous mudstones occurring in the shallow lake environment, and (3) deltaic-front mudstones and prodeltaic mudstones developed in the deltaic facies. Deep lake mudstones/shale, which mainly occurred in the SSQ1-TST (transgressive systems tract), SSQ2-TST and LV Formation, are considered organic-rich source rocks with oil-prone generative potential. The shallow lake mudstones and deltaic mudstones were predominantly distributed in the tectonic slope and marginal areas of the Agadem Block within the lowstand systems tract and high stand systems tract of the SSQ1 and SSQ2. Nevertheless, geochemical results indicated that the deltaic mudstones are good gas-prone source rocks but the shallow lake mudstones were classified as poor potential source rocks. The variance in organic matter accumulation and preservation conditions within different depositional facies and the fluctuation of relative lake level are the controlling factors for the occurrence and distribution of high-quality source rocks. The effective Paleogene source kitchen is limitedly distributed around the depocenter of the Dinga Depression within a small scale, and therefore exploration for oil and gas resources from the Paleogene source kitchen should focus on the eastern Dinga fault-step zone adjacent to the depocenter of the Dinga Depression.

Fluorene (FL), dibenzothiophene (DBT) and dibenzofuran (DBF) and their alkylated homologues are important polycyclic aromatic compounds in crude oils and source rock extracts. They share the similar chemical structure and may have genetic relationships. The parent compounds (unsubstituted), methyl-, dimethyl- and ethyl-substituted isomers are identified by comparison with retention indices reported in literatures and correlation with co-injection of internal standards in gas chromatography-mass spectrometry (GC-MS) analysis. Therefore, their relative concentrations can be determined. Based on the large data sets, this paper preliminarily establishes a ternary diagram to interpret the depositional environment/lithology for oils and related source rocks. Five typical depositional environments/lithologies are distinguished on this ternary diagram. Data points from typical marine carbonate, fluvial/deltaic/fresh lacustrine shale and swamp fall into the DBTs, FLs and DBFs end-members, respectively. Oils from marine shale have subequal contents of FLs and DBFs and lie between the zones of fluvial/deltaic/fresh lacustrine shale and swamp, but have a little higher abundance of DBTs. The oils from brackish/saline lacustrine have intermediate contents of DBTs with a wide variety and some degree overlap with that of marine shale. On the basis of the ternary diagrams, two petroleum systems in the cratonic region of the Tarim basis are defined. The majority of discovered oils were derived from the Middle-Upper Ordovician carbonate source rocks. Whereas, some oils from wells TD2, T904, LK1 and TZ62 originated from the Cambrian and Lower Ordovician source rocks. Therefore, the ternary diagram of FLs, DBTs and DBFs is a useful method to interpret depositional environment/lithology for oils and related source rocks and to definite petroleum systems as well.

The Kashi Sag is an area with abundant gas/oil shows in the Tarim Basin of China. Identification of the sources of its oil and gas sources is important for petroleum exploration. We have applied molecular comparisons of oil sand extracts and two sets of potential source rocks from the Kashi Sag to appraise the source of the oil. The oil sand we studied is from the north limb of the Kelatuo Anticline. One of the potential source rocks is a Middle and Lower Jurassic silt-sand mudstone from Kuzigongsu Profile in the northern part of the basin, and the other is a Lower Carboniferous black shale from the Xilibili Profile in the southern part. The molecular source indicators used are the steranes, terpanes, and sesquiterpenoids in the saturated hydrocarbon fraction and the triaromatic steroids in the aromatic hydrocarbon fraction. Because great differences exist between the molecular compositions of the oil-sand extract and the Middle and Lower Jurassic mudstone, whereas the extract and the Lower Carboniferous black shale are similar, we conclude that the black shale of the Xilibili Profile in the southern part of the basin is the source rock of the sand oil.