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.     

碳酸盐岩裂缝与岩溶作用研究

从构造与非构造作用角度出发,突出研究断层对裂缝的控制作用、断裂与岩溶的关系和裂缝与岩溶之间的关系,揭示碳酸盐岩裂缝与岩溶的发育规律。研究表明：构造裂缝为岩溶发育提供岩溶作用进行的有利通道,非构造裂缝则可以加速溶蚀作用的进行,促进岩溶的发育;裂缝与岩溶之间的关系始终是相辅相成、相互促进的关系。     

The age of the Nantuo Formation and Nantuo glaciation in South China

A U–Pb sensitive high‐resolution ion microprobe (SHRIMP) age of 654.5 ± 3.8 Ma from an ash bed immediately below the Nantuo Formation in South China provides the lowest age constraint for the Nantuo glaciation, which has been correlated with the global ‘Marinoan’ glaciation. A U–Pb SHRIMP age of 636.3 ± 4.9 Ma from a fallout tuff within the basal layer of the Nantuo Formation, along with the existing age of 635.2 ± 0.6 Ma from its overlying Doushantuo cap carbonate, suggests that the traditionally defined Nantuo Formation may have been deposited in a short time period at the end of the Nantuo glaciation. In combination with available ages globally, the data support a relatively short duration and rapid termination of ‘Marinoan’ glaciations.     

青藏高原西部赛利普中新世火山岩源区:地球化学及Sr-Nd同位素制约

青藏高原拉萨地块西部赛利普地区新生代火山岩依据主量元素可划分为超钾质、钾质和钙碱性系列,主要的岩石类型为粗面安山岩、粗面岩,一个超钾质岩石的40Ar-39Ar年龄为17.58Ma,指示出火山活动为中新世.超钾质、钾质和钙碱性火山岩都显示出富集LREE及LILE(Th、U)、亏损HFSE(Nb、Ta、Ti)的特征.超钾质火山岩具有较高的K2O(6.31%～8.55%)、MgO(6.75%～8.96%)、Cr(270.7×10-6～460.4×10-6)、Ni(142.3×10-6～233.9×10-6)含量,较高的(87Sr/86Sr)i(0.71883～0.72732)和较低的εNd(-14.78～-15.37),指示可能起源于一个前期亏损并经后期俯冲作用改造的富钾的方辉橄榄岩富集地幔源区.钾质火山岩具有比超钾质火山岩低的K2O、MgO、Cr、Ni含量以及高的Ba、Sr含量,初始87Sr/86Sr为0.71553～0.71628,初始143Nd/144Nd为0.51197～0.51198,在空间上与超钾质火山岩共生,可能是前者母岩浆的演化产物.钙碱性火山岩具有较高的Sr(881.7×10-6～1309.2×10-6)、Sr/Y比值(50～108)和较低的Y(12.05×10-6～18.02×10-6),明显亏损重稀土Yb(0.93×10-6～1.30×10-6),类似于典型的埃达克质岩成分特征但相对高钾,并具有相对低的(87Sr/86Sr);(0.70928～0.71374)以及高的εNd(-7.90～-10.91),指示起源于富钾增厚下地壳物质的部分熔融.区域上拉萨地块超钾质岩、钾质岩与N-S向地堑系在空间上共存、时间上相吻合,由此本文认为拉萨地块中新世钾质.超钾质岩和南北向地堑系的形成可能与中新世早期北向俯冲的印度大陆岩石圈断离有关.     

青藏高原东南木里地区二叠纪苦橄岩的Os-Sr-Nd同位素地球化学研究

本文报道了在青藏高原东南木里地区发现的二叠纪苦橄岩和与其共生玄武岩的主微量元素地球化学特征以及Os-Sr-Nd同位素组成。苦橄岩和与其共生玄武岩受地壳混染作用影响较小。根据苦橄岩的Ti/Y比值和初始的Os同位素组成,将木里苦橄岩分为两类:高Ti/Y型苦橄岩和低Ti/Y型苦橄岩,其中高Ti/Y型苦橄岩具有高的γ_(Os)= 5.3～ 10.7和ε_(Nd)= 5.9～ 6.4,与全球典型洋岛玄武岩的Os和Nd同位素组成接近,代表了地幔柱源区的同位素特征;而低Ti/Y型苦橄岩具有低的γ_(Os)=-4.1～ 1.2和ε_(Nd)= 3.2～ 5.0,可能表明受到了SCLM(大陆岩石圈地幔)源区物质的混染。与其共生的玄武岩具有低的γ_(Os)=-3.5～-1.6和ε_(Nd)=-0.6～ 0.7,表明其来自于不同于低Ti/Y型苦橄岩也有异于高Ti/Y型苦橄岩的地幔源区,但是也可能受到了SCLM物质的混染。基于Nd-Os同位素的地幔柱与SCLM的二端元混合模型显示:低Ti/Y型苦橄岩可能是SCLM物质组分与地幔柱起源的苦橄质原始岩浆混合形成的;与苦橄岩共生的玄武岩可能是由地幔柱来源的玄武质岩浆与SCLM小比例熔融的熔体混合形成的。     

冈底斯新近纪钾质火山作用:消减沉积物折返的地球化学与Sr-Nd-Pb同位素证据

在冈底斯岩浆岩带的羊八井地区,林子宗火山岩系上部出现小规模的粗面质火山岩.岩石学与地球化学研究表明粗面岩与时空密切相关的大体积安山质-英安质-流纹质火山岩属于不同的火山岩系:碱性钾质系列与钙碱性系列.详细的地球化学研究证明林子宗晚期小体积钾质岩具有独立的岩浆源区,而非早期钙碱性系统低压岩浆过程演化的产物.粗面质熔岩SiO2含量为62.91%～64.63%,具有高K2O(7.52%～8.05%)、Al2O3(16.64%-17.35%)、低TiO2(0.59%～0.68%)与MsO(0.15%～0.77%).钾质熔岩富集LILE与LREE,亏损HFSE,具有高Rb/Sr(1.1～2.3)、Th/La(0.59～0.80)、Th/U(6.3～10.9)和低Ce/Pb(4.1～6.2)与Ba/Th(4.3～14.5)比值,其同位素组成变化范围分别是87Sr/86Sr(I)=0.7068～0.7075、143Nd/144Nd(I)=0.51241～0.51252、206Pb/204Pb=18.87～18.95、207Pb/204Pb=15.63～15.70和208Pb/204Pb=39.24～39.68.粗面岩的地球化学与同位素特征表明冈底斯新近纪钾质火山岩来源于角闪岩相的消减沉积物熔融.因此,羊八井新近纪钾质火山熔岩提供了印度-亚洲大陆碰撞早期消减沉积物折返的证据.     

An investigation of the size frequency resolution of an aerosol by the static method of diffusion

Summary Theoretical considerations are put forward for identifying the Dynamic and Static Methods of Diffusion measurements of aerosol particles. On the basic of this equality the Exhaustion Method of Diffusion developed byPollak andMetnieks for the size-frequency resolution of a heterogeneous aerosol by Dynamic Diffusion Methods should be applicable to Static Methods. This hypothesis is tested using a Pollak-Nolan nucleus counter as decay vessel. It is shown that turbulence in the counter is the most serious obstacle against this type of approach to finding the size components of an aerosol. The time involved, the high humidity in the counter and a hypothetical nucleus-free zone are other major difficulties for relatively large Aitken nuclei. It is established, however, that for particles whose diffusion coefficient is of the order of 10^–3 cm² sec^–1, the proposed method should be quite workable.     

分光光度法测定海洋河弧菌510脂多糖

本文研究了直接测定海洋河弧菌 (vibrio fluvailis) 5 10脂多糖的分光光度法。利用 1,9-二甲基亚甲蓝 (DMB) ,在适当条件下同脂多糖发生染色反应 ,在 5 5 0 nm波长下 ,反应体系的吸光值同脂多糖含量呈线性相关。相关系数为 0 .9993,最低检出限为 10 μg/m L,相对标准偏差为 1.6 2 ,平均回收率为 (10 5± 2 .18) %。     

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     

Effect of Cyclic Loading Frequency on Undrained Behaviors of Undisturbed Marine Clay

Based on a series of cyclic triaxial tests, the effect of cyclic frequency on the undrained behaviors of undisturbed marine clay is investigated. For a given dynamic stress ratio, the accumulated pore water pressure and dynamic strain increase with the number of cycles. There exists a threshold value for beth the accumulated pore water pressure and dynamic strain, below which the effect of cyclic frequency is very small, but above which the accumulated pore water pressure and dynamic strain increase intensely with the decrease of cyclic frequency for a given number of cycles. The dynamic strength increases with the increase of cyclic frequency, whereas the effect of cyclic frequency on it gradually diminishes to zero when the number of cycles is large enough, and the dynamic strengths at different frequencies tend to the same limiting minimum dynamic strength. The test results demonstrate that the reasons for the frequency effect on the undrained soil behaviors are beth the creep effect induced by the loading rate and the decrease of sample effective confining pressure caused by the accumulated pore water pressure.