Experimental investigation on thermochemical sulfate reduction by H2S initiation

Hydrogen sulfide (H₂S) is known to catalyze thermochemical sulfate reduction (TSR) by hydrocarbons (HC), but the reaction mechanism remains unclear. To understand the mechanism of this catalytic reaction, a series of isothermal gold-tube hydrous pyrolysis experiments were conducted at 330 °C for 24 h under a constant confining pressure of 24.1 MPa. The reactants used were saturated HC (sulfur-free) and CaSO₄ in the presence of variable H₂S partial pressures at three different pH conditions. The experimental results showed that the in-situ pH of the aqueous solution (herein, in-situ pH refers to the calculated pH of aqueous solution under the experimental conditions) can significantly affect the rate of the TSR reaction. A substantial increase in the TSR reaction rate was recorded with a decrease in the in-situ pH value of the aqueous solution involved. A positive correlation between the rate of TSR and the initial partial pressure of H₂S occurred under acidic conditions (at pH ∼3-3.5). However, sulfate reduction at pH ∼5.0 was undetectable even at high initial H₂S concentrations. To investigate whether the reaction of H₂S_(aq) and occurs at pH ∼3, an additional series of isothermal hydrous pyrolysis experiments was conducted with CaSO₄ and variable H₂S partial pressures in the absence of HC at the same experimental temperature and pressure conditions. CaSO₄ reduction was not measurable in the absence of paraffin even with high H₂S pressure and acidic conditions. These experimental observations indicate that the formation of organosulfur intermediates from H₂S reacting with hydrocarbons may play a significant role in sulfate reduction under our experimental conditions rather than the formation of elemental sulfur from H₂S reacting with sulfate as has been suggested previously (Toland W. G. (1960) Oxidation of organic compounds with aqueous sulphate. J. Am. Chem. Soc.82, 1911-1916).Quantification of labile organosulfur compounds (LSC), such as thiols and sulfides, was performed on the products of the reaction of H₂S and HC from a series of gold-tube non-isothermal hydrous pyrolysis experiments conducted at about pH 3 from 300 to 370 °C and a 0.1-°C/h heating rate. Incorporation of sulfur into HC resulted in an appreciable amount of thiol and sulfide formation. The rate of LSC formation positively correlated with the initial H₂S pressure. Thus, we propose that the LSC produced from H₂S reaction with HC are most likely the reactive intermediates for H₂S initiation of sulfate reduction. We further propose a three-step reaction scheme of sulfate reduction by HC under reservoir conditions, and discuss the geological implications of our experimental findings with regard to the effect of formation water and oil chemistry, in particular LSC content.     

Formation and abundance of doubly-substituted methane isotopologues (CH3D) in natural gas systems

Formation of the Carbon-13 (¹³C) and deuterium (D) doubly-substituted methane isotopologues (¹³CH₃D) in natural gases is studied utilizing both first-principle quantum mechanism molecular calculation and direct FTIR laboratorial measurements of specifically synthesized high isotope concentration methane gas. For ¹³CH₃D, the symmetrically breathing mode A₀ emerges as IR-detectable attributed to the molecular symmetry lowering to C_3v from T_d of the non-isotopic methane (CH₄), along with a large vibrational frequency shift from ∼3000 to ∼2250 cm⁻¹. Our studies also indicate that the concentration of ¹³CH₃D is dependent on the environmental temperature through isotope exchanges among methane isotopologues; and the Gibbs’ Free Energy difference due to Quantum Mechanics Zero-Point vibrational motions has the major contribution to this temperature dependency. Potential geologic applications of the ¹³CH₃D measurement to natural gas exploration and assessments are also discussed. In order to detect the ¹³CH₃D concentration change of each 50 °C in the natural gas system, a 10⁻⁹ resolution is desirable. Such a measurement could provide important add-on information to distinguish natural gas origin and distribution.     

Identifying China’s leading world city: a network approach

This paper reports our research on China’s world cities. Formal network analysis of air passenger linkages for recent years among China’s most populous cities and among many of the world’s largest cities allows us to identify the country’s leading world city from among the leading Mainland candidates, Beijing, Shanghai and Guangzhou. We theorize our findings about China’s world cities in relation to both global forces (and China’s increasing entanglement with them) and the policies and actions of the national state. We examine the national and global urban network through a longitudinal, two-level analysis of airline passenger travel for four time points between about 1990 and 2005. We show that Beijing was China’s leading world city at the beginning of the time period, a status it lost nationally in as early as 1995, and then globally 10 years later. On the other hand Shanghai became China’s leading world city, and it acquired this status first nationally in 2000, and then globally in 2005. The changing status of the Chinese capital corresponds to the country’s increasing involvement with the capitalist world economy. Shanghai’s ascendance as the leading world city in China may indicate that global forces have come to play an increasingly important role relative to that of the developmental state.

Biogeochemical characteristics of the Hetai goldfield, Guangdong Province, China

In the Hetai goldfield, Guangdong Province, China, samples including rocks, soils and leaves of four plants (Pinus massoniana, Rhodomyrms tomenlosa, D. linearis var. dichotoma and Embelia laeta) collected from the gold mineralization zone and the background area were analyzed for Au, Ag, Cu, Pb, Zn, Hg, As and physiological parameters. The objective of this investigation is to study the geochemical and biogeochemical characteristics of studied plants, aiming at biogeochemical methods in Au exploration. The goldfield region shows geochemical and biogeochemical anomalies. Abundances of Au in rocks, soils, plants and the leaf pigments in the mineralized area are much higher than those in the surrounding region. The plants display unhealthy physiological and ecological characteristics in the Hetai goldfield area. The cell structures of the goldfield plants were anomalous and aberrant, and there were many nano-metal particles diffused in mitochondria and chloroplasts. Macro- and microscopic evidences of the vegetation in the goldfield areas are distinctly different from the background regions. The strongly anomalies in responses to Au are profound in further geochemical and botanic exploration studies.     

松辽盆地三肇凹陷葡萄花油层成藏模式初探

运用源控含油气系统理论与综合分析技术,按成藏“层次分析”方法,通过对生、储、盖、圈(闭)静态要素及其内生、排、运、聚、散(失)动态过程的综合研究,对松辽盆地中央坳陷的三肇凹陷葡萄花油层成藏条件进行探讨,提出了以次级凹陷为中心、不同类型的油气聚集带紧邻并围绕次级凹陷最低部位呈环带状分布的大型凹陷内成藏模式,并进一步提出永乐次级凹陷中心及其三级聚油环带及徐家围子次级凹陷以西为"网式"运聚特征;在凹陷级成藏模式的指导下,通过对大面积密井网开发区综合解剖,提出三级构造带中单个的局部构造圈闭(群)、单个的(局部构造——)岩性圈闭(群)控油和成藏规律,为认识本区基本控油单元、油水分布规律、油气勘探及扩大新探区提供重要的理论依据。     

无定河流域下游段河冰形成演变的数学模型研究

冰凌是北方河流冬春季常见的现象, 由于环境因素的变化, 河道冰情也在不断的变化, 甚至在一些地区出现凌汛灾害. 根据冰塞形成发展的机理, 利用水力学模型和热力学模型模拟研究了无定河流域下游段丁家沟至白家川的每年春季河流水位、封河日期和开河日期. 模拟结果较为理想, 并分析了形成凌汛的原因, 旨在给该区域水循环研究、水资源的开发利用、水土保持等工作提供有力的科学技术支持.     

河南洛宁段河金矿流体包裹体研究和矿床成因

河南省洛宁县段河石英脉型金矿主要包括石寨沟和岭东两个矿区,分别由3～4条含金石英脉构成。矿化过程从早到晚包括石英-黄铁矿、石英-多金属硫化物和石英-碳酸盐等3个阶段．其中中阶段金矿化最强,次为早阶段。各阶段石英中流体包裹体以气液两相包裹体为主．次为纯液体包裹体。激光拉曼测试表明,气液两相包裹体的液相为H2O,气相主要为Ho和CO2混合、纯H2O,次为纯CO2;纯液体包裹体为纯H2O。石寨沟矿区包裹体均一温度从早到晚依次为240．9～315．9℃．188．7～304．5℃,137．3～259．3℃：流体盐度变化依次为（6．74～12．85）wt%NaCl．eq,（2．41～8．68）wt％NaCl．eq,（2．24-7．86）wt%NaCl．eq。岭东矿区均一温度从早到晚依次为303．7-343．1℃,251．8-325．4℃,305．7～355．0℃：流体盐度变化依次为（5．11～11．70）wt％NaCl．eq,（2．74-10．11）wt％NaCl．eq,（0．53-6．74）wt％NaCl．eq。两矿区主成矿期流体均为中温、低盐度,早阶段流体为改造热液和变质热液的混合体,含一定量CO2,且流体CO2含量和盐度从早到晚逐渐降低。石寨沟矿区包裹体均一温度逐渐降低,而岭东矿区包裹体均一温度先降后升,加之岭东矿区各阶段成矿温度均高于石寨沟矿区．表明成矿流体系统主要受岩浆热驱动,岭东矿区更靠近岩体,且在晚阶段又有脉动性的岩浆加热．段河金矿区南部存在隐伏岩体。     

中国对虾血细胞酶细胞化学的初步研究

运用电镜酶细胞化学技术 ,对中国对虾 (Penaeus chinensis)的血细胞和血清中的酚氧化酶、酸性磷酸酶、碱性磷酸酶和过氧化物酶的酶活性部位进行标记。实验结果显示 :酚氧化酶主要以酶原形式存在于大颗粒细胞的颗粒体中 ,酸性磷酸酶和碱性磷酸酶以酶原形式存在于小颗粒细胞的颗粒体中。健康虾和患病虾血细胞中酶活性的表现形式不尽相同 ,在病理情况下 ,颗粒细胞能以细胞解体的方式 ,排出细胞内的颗粒 ,转化成有活性的酶 ,以此提高血淋巴中这几种酶的活性。透明细胞可以吞噬排放颗粒后的颗粒细胞 ,透明细胞中由高尔基体合成的酸性磷酸酶等溶酶体酶主要用于透明细胞的细胞内消化作用。研究认为 :3种血细胞因含有不同的免疫酶以及酶的作用方式不同而具有不同的免疫功能     

固定式海洋平台利用TLD的减震研究

本文研究固定式海洋平台利用调谐液体阻尼器（ＴｕｎｅｄＬｉｑｕｉｄＤａｍｐｅｒ，简称ＴＬＤ）减小地震反应的方法。首先探讨了调谐频率比、激磁频率比对减震效果的影响，在此基础上建立了ＴＬＤ——平台系统的力学模型和运动方程，通过数值计算验证了该方法的有效性