Theoretical study on the reactivity of sulfate species with hydrocarbons

The abiotic, thermochemically controlled reduction of sulfate to hydrogen sulfide coupled with the oxidation of hydrocarbons, is termed thermochemical sulfate reduction (TSR), and is an important alteration process that affects petroleum accumulations in nature. Although TSR is commonly observed in high-temperature carbonate reservoirs, it has proven difficult to simulate in the laboratory under conditions resembling nature. The present study was designed to evaluate the relative reactivities of various sulfate species in order to provide greater insight into the mechanism of TSR and potentially to fill the gap between laboratory experimental data and geological observations. Accordingly, quantum mechanics density functional theory (DFT) was used to determine the activation energy required to reach a potential transition state for various aqueous systems involving simple hydrocarbons and different sulfate species. The entire reaction process that results in the reduction of sulfate to sulfide is far too complex to be modeled entirely; therefore, we examined what is believed to be the rate limiting step, namely, the reduction of sulfate S(VI) to sulfite S(IV). The results of the study show that water-solvated sulfate anions are very stable due to their symmetrical molecular structure and spherical electronic distributions. Consequently, in the absence of catalysis, the reactivity of is expected to be extremely low. However, both the protonation of sulfate to form bisulfate anions () and the formation of metal-sulfate contact ion-pairs could effectively destabilize the sulfate molecular structure, thereby making it more reactive.Previous reports of experimental simulations of TSR generally have involved the use of acidic solutions that contain elevated concentrations of relative to . However, in formation waters typically encountered in petroleum reservoirs, the concentration of is likely to be significantly lower than the levels used in the laboratory, with most of the dissolved sulfate occurring as , aqueous calcium sulfate ([CaSO₄]_(aq)), and aqueous magnesium sulfate ([MgSO₄]_(aq)). Our calculations indicate that TSR reactions that occur in natural environments are most likely to involve bisulfate ions () and/or magnesium sulfate contact ion-pairs ([MgSO₄]_CIP) rather than ‘free’ sulfate ions () or solvated sulfate ion-pairs, and that water chemistry likely plays a significant role in controlling the rate of TSR.     

Effect of indigenous bacteria on geochemical behavior of arsenic in aquifer sediments from the Hetao Basin, Inner Mongolia: Evidence from sediment incubations

Incubation studies were carried out using 5 freshly collected sediments from shallow aquifers of the Hetao Basin, Inner Mongolia. The aquifer sediments covering a range of redox conditions, as indicated by their deep grey to yellow color were mixed with degassed artificial As solution or degassed deionized water at a ratio of solid to water of about 1:10 (wt./wt.). Suspensions which were either amended with glucose or autoclaved, were incubated in parallel with unamended suspensions. Five microcosm cultures of unamended sediments gradually release the equivalent of 0.03–0.30 μg/g As to the dissolved phase. The addition of glucose as a potential electron donor results in a marked stimulation in the mobilization of As (0.71–3.81 μg/g) in the amended incubations for all sediments. The quantity of As released accounts for 60–70% of As bound to Fe/Mn oxides in the original sediments. The microbially mediated mobilization of As with the organic nutrient as an electron donor is strongly associated with the As bound to Fe/Mn oxides, as well as the exchangeable As. During the incubations amended with glucose, 2–4% of the sediment Fe is released. The results suggest that the introduction of labile dissolved organic C into the yellowish sediment aquifers with As-free groundwater would reduce a significant proportion of the Fe(III) oxyhydroxides mediated by anaerobic bacteria respiration and increase groundwater As concentrations.     

Iodine in Chinese coals and its geochemistry during coalification

To determine the I distribution in Chinese coals, a nationwide survey was undertaken based on the distribution, periods of formation, rank and production yields of various coal deposits. A total of 305 coal samples were collected and their I contents were determined by catalytic spectrophotometry with pyrohydrolysis. The geochemistry of I during coalification (including both peat diagenesis and coal metamorphism) was assessed. It was found that the I contents of Chinese coals range from 0.04 mg kg^–1 to 39.5 mg kg^–1 and exhibit a lognormal distribution, with a geometric mean of 1.27 mg kg^–1. Statistical correlation analysis and the observation that I contents increase with coal rank indicate that coal I is chalcophile in nature, and not generally organically bound. When peat developed into lignite through diagenesis, 95–99.9% of the original I was lost. The composition and structure of clay minerals present in the coal were controlled by the original depositional environment. The higher the I content of coals, the more likely the original sediments were affected by a marine environment. Iodine contents increased from lignite through sub-bituminous and bituminous coals to anthracite. This indicates that coal absorbed excess I from hydrothermal fluids during metamorphism (including geothermal metamorphism and telemagmatic metamorphism). The telemagmatic metamorphism was caused by magmatic activities that depended on the specific geological structure of the region. In China, most high-rank coals were formed by telemagmatic metamorphism.     

Extreme oxygen isotope signature of meteoric water in magmatic zircon from metagranite in the Sulu orogen, China: Implications for Neoproterozoic rift magmatism

Unusual ¹⁸O depletion, with δ¹⁸O values as negative as −10‰ to −4‰ relative to VSMOW, was reported in zircons from ultrahigh-pressure eclogite-facies metamorphic rocks in the Dabie-Sulu orogenic belt, China. But it is critical for the negative δ¹⁸O zircons to be distinguished between magmatic and metamorphic origins, because the ¹⁸O depletion can be acquired by high-T eclogite-facies metamorphism of meteoric-hydrothermally altered low δ¹⁸O rocks. While zircon O diffusion kinetics has placed a reasonable constraint on this, zircon trace element compositions can provide a straightforward distinction between the magmatic and metamorphic origins. This paper reports our finding of unusual ¹⁸O depletion in zircon from granitic gneiss in the northeastern end of the Sulu orogen. Zircon δ¹⁸O values vary from −7.8‰ to −3.1‰ along a profile of 50 m length at Zaobuzhen. They are close to extremely low δ¹⁸O values of −9.0‰ to −5.9‰ for metagranite at Qinglongshan and adjacent areas in the southwestern end of the Sulu orogen. CL imaging suggests that the low δ¹⁸O zircons at Zaobuzhen are primarily of magmatic origin, but underwent different degrees of metamorphic modification. Zircon U-Pb dating yields middle Neoproterozoic ages of 751 ± 27 to 779 ± 25 Ma for protolith crystallization and Triassic ages of 214 ± 10 to 241 ± 33 Ma for metamorphic resetting. However, no metamorphic modification occurs in zircon REE patterns that only indicate magmatic recrystallization and hydrothermal alteration, respectively. Thus, the negative δ¹⁸O zircons are interpreted as crystallizing from negative δ¹⁸O magmas due to melting of meteoric-hydrothermally altered negative δ¹⁸O rocks in an active rift setting at about 780 Ma. The variation in zircon δ¹⁸O values indicates considerable O isotope heterogeneity in its granitic protolith. Zircon Lu-Hf isotope analyses give positive ε_Hf(t) values of 1.6-4.1 and Hf model ages of 1.18-1.30 Ga. This suggests that the granitic protolith was derived from the mid-Neoproterozoic reworking of late Mesoproterozoic juvenile crust. The metagranites at Zaobuzhen and Qinglongshan, about 450 km apart, are two known occurrences of the unusually low δ¹⁸O zircons below −6‰ so far reported in the Sulu orogen. They are similar to each other in both protolith and metamorphic ages, so that they share the same nature of both Neoproterozoic protolith and Triassic metamorphism. Therefore, the locally negative δ¹⁸O zircons may register centers of low δ¹⁸O magmatism during the supercontinental rifting.     

The geochemical characteristics and origin of crude oils in the Kekeya Oilfield,Xinjiang, China

GC/MS and GC/MS/MS techniques were employed to describe the characteristics of biomarker assemblages in two sets of hydrocarbon source rocks, Jurassic and Permian, in southwestern Tarim, and the parameters for the classification of the two sets of hydrocarbon source rocks have been established. It is found that diahopane and C30-unknown terpane are abundant in Permian samples, the contents of diahopane in Jurassic samples are relatively low, and terpenoids have been detected in Jurassic samples but not in Permian source rock samples. Kekeya crude oils are abundant in diahopane and C30-unknown terpane. The results of fine oil-rock correlation indicated that Kekeya crude oils were derived mainly from the Permian hydrocarbon source rocks. However, a small amount of diterpenoid was detected in the crude oils, indicating that the Jurassic hydrocarbon source rocks also made a certain contribution to Kekeya crude oils.     

Dynamical downscaling of regional climate over eastern China using RSM with multiple physics scheme ensembles

Theoretical and Applied Climatology - The parameterization of physical processes is one of the critical elements to properly simulate the regional climate over eastern China. It is essential to...     

A peak-cluster assessment method for the identification of upland planation surfaces

Residual upland planation surfaces serve as strong evidence of peneplains during long intervals of base-level stability in the peneplanation process. Multi-stage planation surfaces could aid the calculation of uplift rates and the reconstruction of upland plateau evolution. However, most planation surfaces have been damaged by crustal uplift, tectonic deformation, and surface erosion, thus increasing the difficulty in automatically identifying residual planation surfaces. This study proposes a peak-cluster assessment method for the automatic identification of potential upland planation surfaces. It consists of two steps: peak extraction and peak-cluster characterization. Three critical parameters, namely, landform planation index (LPI), peak elevation standard deviation, and peak density, are employed to assess peak clusters. The proposed method is applied and validated in five case areas in the Tibetan Plateau using a Shuttle Radar Topography Mission digital elevation model (SRTM DEM) with 3 arc-second resolution. Results show that the proposed method can effectively extract potential planation surfaces, which are found to be stable with different resolutions of DEM data. A significant planation characteristic can be obtained in the relatively flat areas of the Gangdise–Nyainqentanglha Mountains and Qaidam Basin. Several vestiges of potential former planation areas are also extracted in the hilly-gully areas of the western part of the Himalaya Mountains, the northern part of the Tangula–Hengduan Mountains, and the northeastern part of the Kunlun–Qinling Mountains despite the absence of significant topographical features characterized by low slope angles or low terrain reliefs. Vestiges of planation surfaces are also identified in these hilly-gully upland areas. Hence, the proposed method can be effectively used to extract potential upland planation surfaces not only in flat areas but also in hilly-gully areas.     

HBV相关肝病患者外周血NK细胞PD-1、Tim-3表达及意义

目的 了解HBV相关肝病患者外周血NK细胞表面PD-1、Tim-3的表达情况,探讨PD-1和Tim-3的表达与血清HBV-DNA载量的相关情况。方法 选择HBV感染相关肝病患者74例,其中CHB患者30例,LC患者24例,HCC患者20例,健康对照18例。应用流式细胞术检测NK细胞表面PD-1、Tim-3表达,荧光定量PCR检测HBV-DNA量,ELISA法检测细胞因子分泌水平。统计各组患者PD-1和Tim-3的表达率,比较各组差异,分析其与病情的相关性。结果 CHB、LC、HCC组外周血NK细胞表面PD-1和Tim-3的表达率分别为34.46%±7.31%、59.09%±12.35%、61.49%±15.26%和19.18%±6.05%、28.64%±11.20%、31.24%±11.85%,均高于对照组（P<0.01）,LC组和HCC组明显高于CHB组（P<0.01）,LC组和HCC组比较无统计学差异。在CHB组,PD-1的表达率与HBV-DNA呈负相关关系（R=-0.437,P=0.033）。CHB、LC、HCC各组血清中细胞因子TNF-α和IFN-γ水平分别为0.66±0.63、0.75±0.66、0.85±0.71和1.76±0.88、1.83±1.23、1.60±0.53,均低于健康对照组（P<0.01）。结论 HBV相关肝病患者NK细胞表面PD-1、Tim-3表达均增加,且与病情严重程度有关,增加表达的PD-1与血清HBV-DNA载量存在负相关性,HBV肝病各组血清TNF-α、IFN-γ分泌减少。     

Frost-heave properties of saturated compacted silty clay under one-side freezing condition

In seasonally frozen regions, the frost-heave properties of soil play a significant role in its upper-structure performance and durability. To investigate the frost-heave behaviors of saturated, compacted silty clay soil widely used as subgrade material, a series of one-side freezing tests was carried out; and the freezing depth and frozen front effected by the compactness, temperature, overburden pressure, and water-supply condition were analyzed and discussed. The results show that the moving speed of the frozen front and growth rate of the frozen depth are positively correlated. The frost heave is maximum in the frost-heave stability condition. The frost ratio of saturated soil is proportional to the water supply and cooling temperature under a one-side freezing condition. The frost ratio of saturated soil is inversely proportional to the initial compactness of the soil specimen and the overburden pressure.     

祁连山地震带两次中强地震前的加卸载响应比异常

研究了祁连山地震带两次中强地震前的加卸载响应比异常特征，讨论了基于天然地震序列的样本条件对加卸载响应比计算结果的影响，提出处理序列中4．0级以上地震的新方法。