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Abstract: The physical properties of tissue engineering scaffolds such as microstructures play important roles in controlling cellular behaviors and neotissue formation. Among them, the pore size stands out as a key determinant factor. In the present study, we aimed to fabricate porous scaffolds with pre-defined hierarchical pore sizes, followed by examining cell growth in these scaffolds. This hierarchical porous microstructure was implemented via integrating different pore-generating methodologies, including salt leaching and thermal induced phase separation (TIPS). Specifically, large (L, 200–300μm), medium (M, 40–50μm) and small (S, <10μm) pores were able to be generated. As such, three kinds of porous scaffolds with a similar porosity of ~90% creating pores of either two (LS or MS) or three (LMS) different sizes were successfully prepared. The number fractions of different pores in these scaffolds were determined to confirm the hierarchical organization of pores. It was found that the interconnectivity varied due to the different pore structures. Besides, these scaffolds demonstrated similar compressive moduli under dry and hydrated states. The adhesion, proliferation, and spatial distribution of human fibroblasts within the scaffolds during a 14-day culture were evaluated with MTT assay and fluorescence microscopy. While all three scaffolds well supported the cell attachment and proliferation, the best cell spatial distribution inside scaffolds was achieved with LMS, implicating that such a controlled hierarchical microstructure would be advantageous in tissue engineering applications. [Copyright &y& Elsevier]

Abstract: A recently developed protocol, “microtissue assembly” holds great promise to address the issue of limited mass transfer within engineered large tissue replacements (macrotissues), wherein small “building blocks” (microtissues) are prepared and then assembled into macrotissues. Previous studies suggested that aggregation behavior of microcarrier-based microtissues were very important for macrotissue engineering. However, a systematic study on the aggregation behavior of microtissues is still missing. In this study, to examine the aggregation behavior of microtissues, effects of key operation parameters in dynamic culture including cell seeding density, microcarrier concentration, l-ascorbic acid 2-phosphate (V c) and agitating speed were investigated. The aggregation process could be divided into three phases (i.e., lag, growth and stable). Aggregation efficiency (S) was found to be modulated by cell seeding density, microcarrier concentration, addition of V c and agitating speed. A mathematical model correlating the operation parameters with S at different phases of aggregation was developed and experimentally proved to be able to predict S with varied operation parameters. In the end, a cylindrical macrotissue (diameter×height: 2.0cm×0.8cm) with fairly good integrity and cellularity and uniform cell distribution was successfully engineered through perfusion assembling microtissues with controlled S under selected culture conditions. Our study showed that aggregation of microtissues could be precisely modulated, which would definitely facilitate engineering macrotissues with high quality. [Copyright &y& Elsevier]

The article offers a study related to the way of predicting production state by carbon isotope fractionation in the fuling shale gas field, Southeast Sichuan Basin. Topics discussed include well gas samples and shale core samples of the Longmaxi Formation were collected from the well and field analysis, gas composition and carbon isotope test were completed. Article concludes that desorption gas in Fuling area has a favorable indication effect on the enrichment of shale gas.

Since the 1950s, major breakthroughs have been made in the field of carbonate oil and gas exploration, and large reservoirs have been found in carbonate strata in many countries; however, the validity of highly evolved carbonate source rocks has been controversial. Because of the loss of organic carbon during acid-solution processing in conventional total organic carbon (TOC) determination, we decided to use a new method of reducing acid-solution losses in order to more effectively quantify acid-soluble organic matter in carbonate rock samples. Different levels of acid-soluble organic matter were present in different types of samples, and there was no positive correlation between the content of acid-soluble organic matter and conventionally measured TOC values. However, the thermal evolutionary maturity of samples with high acid-soluble organic matter content is relatively low, and the high hydrocarbon generation conversion rate of acid-soluble organic matter and conventional TOC in carbonate rocks is an important reason for the low residual TOC in highly evolved carbonate rocks. The new method is helpful in re-evaluating the abundance of organic matter in carbonate rocks and in providing evidence for studying hydrocarbon generation and the hydrocarbon capacity of carbonate source rocks. [ABSTRACT FROM AUTHOR]

Graptolite-rich shale is the main layer of shale gas resources in the southern marine sedimentary basin. Recently, shale gas resources were discovered in the Ordovician marine graptolite-rich strata in the Ordos Basin. The graptolite shale in the study area is different from the marine graptolite shale in the Yangtze plate in southern China, and further exploration is needed. This paper presents core samples of the graptolite-rich shale of the Pingliang Formation in the southwest Ordos Basin as research objects. The graptolite genus and graptolite shale characteristics were studied using core observation, electron microscopy, scanning electron microscopy, and geochemical analysis. We determined the role of the sedimentary environment and thermal maturation of graptolite shale in hydrocarbon formation and explored the possibility of hydrocarbon generation. Many graptolite epidermises provide buried organic matter. The quiet sea and low-energy marine environment create favorable conditions for preserving organic matter. The tectonic process resulted in the evolution stage in the oil generation window. Different types of pores formed the spaces of hydrocarbons. Therefore, the shale of the Pingliang Formation has shale oil exploration potential, which complements the shale gas in the northwestern margin of the basin, and provides new venues for shale oil and gas exploration in northern China. [ABSTRACT FROM AUTHOR]

• The carbon isotope curve index (CICI) summarizes the isotope ratios of C 1 - C 3. • Carbon-isotope curves can be divided into Convex, Linear, Concave and Reversed. • In Normal-type gas, leakage and preferential propane biodegradation increase CICI. • In Normal-type gas, migration and mixing with microbial methane decrease CICI. The carbon isotope curve (δ13C n versus 1/n) is often used to evaluate the origin and secondary alteration of hydrocarbon gases, but the factors that influence the carbon isotope curve are not fully understood, limiting its practical application. We define a carbon isotope curve index (CICI) to quantitatively characterize the curve type. Four general curve types are defined: a Normal (δ13C 1 < δ13C 2 < δ13C 3) type and three Reversed types consisting of R 1 (δ13C 1 > δ13C 2 > δ13C 3), R 2 (δ13C 1 < δ13C 2 > δ13C 3), and R 3 (δ13C 1 > δ13C 2 < δ13C 3). CICI is defined as arctan (3Δ13C 3-2 /Δ13C 2-1) × 180/π for Normal and R 2 , –180 + arctan (3Δ13C 3-2 /Δ13C 2-1) × 180/π for R 1 , and 180 + arctan (3Δ13C 3-2 /Δ13C 2-1) × 180/π for R 3. CICI ranges from 0 to 90 for Normal, –180 to –90 for R 1 , –90 to 0 for R 2 , and 90 to 180 for R 3. Normal gases can be divided into three categories: Linear (CICI = 45), Convex (CICI 0 to < 45), and Concave (CICI > 45 to 90). The influence of kerogen type and maturity on CICI is investigated by comparing thermogenic gases generated from different kerogens in both sedimentary basins and pyrolysis experiments. Curves for low-maturity lacustrine and low-to-high-maturity coal gases are mainly Convex. In contrast, curves for high maturity to overmature marine gases are more Concave. The curve type of thermogenic gas changes from Convex to Concave with increasing maturity, and the mixing of gases generated from kerogen-cracking and oil-cracking results in the Concave type. The effect of post-generation alteration processes on CICI was elucidated using data from three field studies. In Normal-type gas, preferential biodegradation of propane and leakage increase CICI, while migration and mixing with microbial methane decrease CICI. Preferential biodegradation of propane and leakage are two other reasons for the Concave type. [ABSTRACT FROM AUTHOR]

Abstract A series of thermochemical sulfate reduction (TSR) simulation experiments were carried out involving different organic matter (crude oil, solid bitumen, type II kerogen, type III kerogen) and different sulfate species (anhydrite and MgSO 4) to address the chemical and carbon isotopic variations of the hydrocarbon, H 2 S and CO 2. The increase of main peak carbons of residual saturated hydrocarbon and the decrease of gaseous hydrocarbons from control treatment to corresponding sulfate treatments suggest that TSR promote the consumption of both liquid and gaseous hydrocarbons. The δ13C 1 -3 values generally shift positively from control treatment to sulfate treatments and the (δ13C ethane -δ13C methane) values in sulfate treatments are higher than that in control treatments. The variation of δ13C 1 -3 in TSR is controlled by the isotope fractionation during the generation and consumption of C 1 -3 in TSR. MgSO 4 is more reactive than anhydrite in TSR. A certain amount of H 2 S is incorporated into solid bitumen as the result of secondary alteration. We believe that the reactivity order of different organic matter in TSR is crude oil > solid bitumen > type II kerogen > type III kerogen. The reactivity of organic matter in TSR depends on the hydrocarbon generation kinetics of each organic matter. The dissolution/decomposition and precipitation of carbonate control the yield of CO 2 in sour reservoirs. The negative shift of δ13CO 2 with increasing TSR extent is mainly due to the inheritance effect of carbon isotope from hydrocarbons. Inorganic CO 2 sourced from the thermal decomposition or acid dissolution of carbonate mineral impose significant influence on δ13CO 2. The H 2 S yields decrease with CH 4 yields and increase with δ13CH 4 value, the δ13CH 4 values increase with residual amount of gaseous alkane (1- H 2 S/(residual alkane + H 2 S)), suggesting that methane acted as reactant in TSR. The (δ13CO 2 -δ13CH 4) values decrease significantly with increasing temperature, and the δ13CO 2 is even more negative than δ13CH 4 in 450 °C MgSO 4 treatments involving type II and type Ⅲ kerogen. Accordingly, methane acted as a predominant reactant in 450 °C sulfate treatments in our experiment. It is possible for natural gas with high gas dryness to experience methane-dominated TSR in geological reservoirs. Highlights • Organic matter type imposes significant influence on TSR. • Dissolution and precipitation of carbonate control CO 2 yield in TSR. • δ 13CO 2 shift negatively with increasing TSR extent due to the inheritance of 13C/12C. • Methane can act as predominant reactant in TSR. [ABSTRACT FROM AUTHOR]

Original organisms are the biological precursors of organic matter in source rocks. Original organisms in source rocks are informative for oil‐source rock correlation and hydrocarbon potential evaluation, especially for source rocks which have high‐over level of thermal maturity. Systematic identification of original organism assemblages of the Lower Paleozoic potential source rocks and detailed carbon isotopic composition of kerogen analyses were conducted for four outcrop sections in the Tarim basin. Results indicated that the original organism assemblages of the lower part of the Lower Cambrian were composed mainly of benthic algae, whereas those of the Upper Cambrian and the Ordovician were characterized by planktonic algae. Kerogen carbon isotopic data demonstrated that the δ13Ckerogen values of source rocks dominated by benthic algae are lower than –34‰, whereas the δ13Ckerogen values of source rocks dominated by planktonic algae are higher than –30‰ in general. We tentatively suggested that the carbon species those are utilized by algae and the carbon isotopic fractionation during photosynthesis are the major controls for the δ13Ckerogen values in the Lower Paleozoic source rocks in the Tarim basin. Correlating the δ13C values of oils exploited in the Tarim basin, the original organism assemblages, and δ13Ckerogen values of source rocks, it implied that the Lower Paleozoic oils exploited in the Tarim basin should be sourced from the source rocks with original organism assemblages dominated by planktonic algae, and the hydrocarbon sourced from the Cambrian benthic algae should be of great exploration potential in future. Original organism assemblages in source rocks can provide important clues for oil‐source rocks correlation, especially for the source rocks with high thermal maturity. [ABSTRACT FROM AUTHOR]

A physical model was developed to quantify 4 He accumulation in gas reservoirs. Both radiogenic 4 He from external crustal flux and in situ 4 He production were calculated with this model. Considering the time-accumulation effect of 4 He, the formation time of a gas reservoir can be estimated. The proposed method was applied to Puguang gas reservoir in southwest China's Sichuan Basin, the formation time of which was estimated as 32.5 Ma, which corresponds to the Oligocene epoch and to the mid-Himalayan movement, and which is consistent with gas formation and accumulation history. This result indicates that the proposed model based on 4 He accumulation can be a useful tool for studying the formation time of gas reservoirs. [ABSTRACT FROM AUTHOR]

The mechanism of hydrogen sulfide (HS) generation plays a key role in the exploration and development of marine high-sulfur natural gas, of which the major targets are the composition and isotope characteristics of sulfur-containing compounds. Hydrocarbon source rocks, reservoir rocks, natural gases and water-soluble gases from Sichuan Basin have been analyzed with an online method for the content of HS and isotopic composition of different sulfur-containing compounds. The results of comparative analysis show that the sulfur-containing compounds in the source rocks are mainly formed by bacterial sulfate reduction (BSR), and the sulfur compounds in natural gas, water and reservoir are mainly formed by thermal sulfate reduction (TSR). Moreover, it has been shown that the isotopically reversion for methane and ethane in high sulfur content gas is caused by TSR. The sulfur isotopic composition of HS in natural gas is inherited from the gypsum or brine of the same or adjacent layer, indicating that the generation and accumulation of HS have the characteristics of either a self-generated source or a near-source. [ABSTRACT FROM AUTHOR]

The noble gases He and Ar are trace components in natural gas. Although their genesis is significantly different from that of hydrocarbon gases, they can provide key information on the accumulation and preservation of natural gas. In this paper, the relative and absolute abundances of He and Ar in lower Paleozoic shale gas samples from different areas of southern China were systematically analyzed, and the relationships between the concentrations of noble gases and the accumulation and expulsion of shale gas were evaluated. The evolution of He and Ar concentrations in shale gas system can be divided into three phases: the early accumulation stage, the hydrocarbon dilution stage and the preservation and enrichment stage. The generation of a large amounts of methane in the shale leads to the lowest relative concentrations of He and Ar in the hydrocarbon dilution stage. After that, the tectonic uplift causes the partial loss of the shale gas, and methane is no longer generated, but He and Ar are still produced. The concentrations of He and Ar present in shale gas are mainly controlled by the conditions of the preservation and enrichment stage. Tectonic uplift is the main reason for the loss of shale gas, and later uplift often results in higher gas content, which also leads to relatively low concentrations of He and Ar. The absolute abundance of residual Ar atm and the He/Ar ratio of a shale gas can indirectly reflect the preservation conditions of that shale gas. • No evidence was found of external sources of He or Ar in the shale gas systems. • The relative abundances of He and Ar can reflect the accumulation and expulsion process of the shale gas. • The He/Ar ratio is related to the time available for diffusion and the sealing capabilities of the shale system. [ABSTRACT FROM AUTHOR]

Abstracts Hydrous pyrolysis experiments were conducted on immature petroleum source rocks containing different types of kerogen (I and II) at a temperature range of 250–550 °C to investigate the role of kerogen type in petroleum formation at high temperature. At temperatures less than 350 °C, the bulk results and biomarker compositions were quite similar and show negligible variations for different kerogen types. However, at high-temperature, above 400 °C (400–550 °C), unexpected results were observed. The initial and peak temperature of the hydrocarbon generation of type II sources rocks is lower than the type I. The tricyclic terpenes were common in samples above 400 °C. The T s / T m values did not show a linear relationship with the temperature increase. The C 31 22 S /( S + R ) values did not show significant change with temperature increase. However, a good correlation between the sterane maturity parameters and the thermal maturity were shown, especially for type I kerogen. Temperature increase resulted in significant variation in the relative contents of C 27 , C 28 and C 29 steranes, suggesting that the distribution of steranes is greatly affected by thermal maturity. [ABSTRACT FROM AUTHOR]

Fourteen gases and their associated oils were collected at the surface from production wells in the Shahejie Formation, Dongying Formation, and Archean in six zones around the Qingshui Sub-sag of the Liaohe Depression, Bohai Bay Basin. The molecular compositions and carbon and hydrogen isotopic compositions of natural gas were measured. The origin, migration, accumulation, and secondary alteration of natural gas were studied based on the lateral and vertical comparison of natural gas geochemical characteristics. The natural gases include humic-type (δ13C 2 > −29.0‰, δ13C 1 > −43.0‰), sapropelic-type (δ13C 2 < −29.0‰, δ13C 1 > −43.0‰), and secondary microbial (δ13C 1 of −48.5‰, C 1 /(C 2 +C 3) of 46.3, δ13CO 2 of −1.5‰) gases. The humic-type and sapropelic-type gases were derived from the source rocks in the third and fourth members of the Shahejie Formation, respectively. The humic-type gases dominate. The biodegradation level of natural gas in the study area varies, and biodegraded gases are characterized by high Δ13C(C 3 –C 2), low C 3 /C 2 , and low C 3 /iC 4 and are associated with biodegraded oils. The vertical migration of natural gas in the west and east of the Qingshui Sub-sag is limited. There are good additional exploration prospects for humic-type gas, derived from high-maturity source rocks of the third member of the Shahejie Formation in the deep layers (depth >4.5 km) of the Qingshui Sub-sag. Secondary microbial gas is a potential exploration target in the shallow layers (depth <2.5 km). • Humic-type gas is from the source rock of the 3rd member of Shahejie Formation. • Sapropelic-type gas is from the source rock of the 4th member of Shahejie Formation. • Biodegraded gas: 13C-rich propane, depletion of propane and n-butane. • Secondary microbial gas: 13C-rich carbon dioxide and 13C-depleted methane. • Natural gas mainly accumulates near the source rock. [ABSTRACT FROM AUTHOR]

Variations in the stable carbon isotope signature of marine carbonate rocks (δ13C carb) are utilized as an indicator for changes in depositional environment and tracers of diagenetic alteration. Various petrologic (textural changes) and geochemical indicators (trace elements) have been used to evaluate the effect of diagenetic alteration on the δ13C carb signature. However, how diagenetic processes involving interactions between organic matter and minerals impact the δ13C carb records of marine carbonate rocks has not been investigated thoroughly. In this study, systematic stable carbon (δ13C carb) and oxygen (δ18O carb) isotope analyses were conducted on marine carbonates from the Middle Ordovician Majiagou Formation in the Ordos Basin, China to evaluate secondary overprint of the primary δ13C carb record. 496 carbonate samples from the gas reservoir (potential gas source rock) were selected from one well located in the natural gas exploration target—mid-east part of the Ordos Basin. A depleted δ13C carb excursion (i.e., a shift to more negative values) occurred in the 100 m-thick anhydrite-bearing carbonate sequence of this formation. The δ13C carb and δ18O carb values for the whole rock vary from −10.9‰ to 1.8‰ and −11.5‰ to −4.0‰, respectively. The calcite veins and vug-filling calcites also have depleted carbon isotope signature ranging between −21.1‰ and −4.4‰. The secondary calcites observed under the microscope were generated by the conversion from isotopically depleted organic matter and resulted in the depleted δ13C carb signature. The commonly occurring thermochemical sulfate reduction in the study area and the degradation of potentially enriched carboxylic acid salts in anhydrite-bearing carbonate setting are major factors contributing to the depleted δ13C carb values. The conversion from organic carbon to inorganic carbon through organic matter-involved diagenetic processes plays a significant role in explaining the genesis of depleted δ13C carb excursions in deeply buried marine carbonate sequences. [Display omitted] • High-amplitude depleted δ13C carb signatures were first found to occur in the Middle Ordovician carbonate sequence. • Diagenetic processes involving organic matter impacted the original δ13C carb record. • Organic-origin calcites generated by TSR resulted in the depleted δ13C carb signatures. [ABSTRACT FROM AUTHOR]

The total organic carbon of carbonate sediments includes a 5%–45% contribution from acid-soluble organic matter, particularly carboxylic acid salts. However, there is little information available on hydrocarbon generation from carboxylic acid salts. The objectives of this study were to investigate the extent and timing of hydrocarbon generation from calcium stearate. Thus, gold-tube nonhydrous pyrolysis experiments of calcium stearate were conducted from 250 to 600 °C at 50 MPa. Infrared spectroscopy and δ13C testing were also performed on solid pyrolysate and gaseous products, respectively, to trace changes of functional groups and stable carbon isotopes. Pyrolysis of calcium stearate produced hydrocarbons, CO 2 , CaO, CaCO 3 , coke, and other inorganic compounds of low molecular weight. A Van Krevelen diagram indicated that calcium stearate falls in the same region as hydrogen-rich type I kerogen. The maximum yield of methane generated from calcium stearate was as high as that from North Sea oil. Hydrocarbon generation from calcium stearate was related to cracking of the alkyl moiety and similar to that occurring in pyrolysis of n- C 18. As a consequence of kinetic carbon isotope fractionation, with increasing temperature CO 2 becomes enriched in 13C and CaCO 3 becomes enriched in 12C. Notably, CaCO 3 with very low δ13C values is probably an effective proxy indicating hydrocarbon generation from carboxylic acid salts, if no other CaCO 3 is produced via thermochemical sulphate reduction processes. The optimized kinetic parameters demonstrate that calcium stearate had higher methane generation activation energies than those of n -C 18 and type I kerogen. Hence, methane generation from calcium stearate is delayed when extrapolated to geological conditions. This retarded methane generation illustrates the vital role of carboxylic acid salts in the generation of deep oil and gas. Future research should concern the abundance of carboxylic acid salts in carbonate formations and the depositional environments that facilitate the formation of carboxylic acid salts. • Closed gold-tube pyrolysis of calcium stearate was conducted. • Calcium stearate had gas potential as high as crude oil. • Negative δ13C CaCO3 may indicate hydrocarbon generation from carboxylic acid salts. • Methane generation from calcium stearate was behind that of n- C 18. [ABSTRACT FROM AUTHOR]