硒对华贵栉孔扇贝碱性磷酸酶的酶动力学及理化性质研究

探讨了微量硒(Se~(4+))对华贵栉孔扇贝(Chlamys nobilis(Reeve))碱性磷酸酶(AKP)的作用。以催化动力学原理研究了不同缓冲系统中微量硒时AKP的影响。结果表明,Se~(4+)对谈酶的作用与酶所处的环境有关。在0.05 mol/L Na_2CO_3-NaHCO_3(pH 9.0)缓冲溶液中Se~(4+)浓度小于12.5 mmol/L时呈现出激活作用;Se~(4+)浓度大于12.5 mmol/L时呈现出非竞争性的抑制作用,其抑制常数为6.81×10~(-2)mol/L。在0.05 mol/L Tris-HCl缓冲系统(pH 9.0)中,微量Se~(4+)对AKP具有强烈竞争性抑制作用,其抑制常数为3.79×10~(-1)mol/L。经紫外吸收光谱、荧光发射光谱和圆二色谱的实验表明,微量Se~(4+)与AKP作用后,该酶的构象已发生了变化。研究发现海水环境中若含有微量Se~(4+)(SeO_3~(2-)),可以促进扇贝AKP的水解。利于贝类的生长发育和外壳的形成,并有益于贝类的繁殖。     

赣杭构造带灵山花岗岩体黑云母的矿物化学特征及其对岩石成因的指示意义

灵山花岗岩体在平面上为一环状分布的侵入体,中心为角闪石黑云母花岗岩,外围为黑云母花岗岩。在角闪石黑云母花岗岩中分布有大量的暗色镁铁质微粒包体。黑云母是大多数中酸性火成岩中比较重要的一种镁铁质矿物,它能很好地反映寄主岩浆的属性和成岩时的物理、化学条件,因此,本文对这两种花岗岩及镁铁质微粒包体中的黑云母开展了系统的岩相学观察和电子探针化学组成研究,探讨灵山岩体的物质来源、成岩条件和岩浆的混合作用过程。研究结果表明两种花岗岩体的黑云母具有不同化学成分,而暗色镁铁质微粒包体中黑云母的化学成分则变化较大。三种黑云母均在低氧逸度条件下晶出。两种花岗岩中的黑云母均富Fe贫Mg,属于铁质黑云母,含铁系数[(Fe~(3+)+Fe~(2+))/(Fe~(3+)+Fe~(2+)+Mg~(2+))]分别为0.65~0.70,0.72~0.78,FeOT/MgO均接近7.04。MF值[2×Mg/(Fe~(2+)+Mg+Mn)]分别为0.64~0.76和0.48~0.60,指示两种花岗岩的物质来源都是以壳源为主。镁铁质微粒包体中黑云母的MF值变化范围比较大,为0.63~1.06,为铁质黑云母到镁质黑云母,暗示包体岩浆经历过不同程度的岩浆混合作用。镁铁质微粒包体中部分黑云母与角闪石黑云母花岗岩中黑云母的结晶条件相似,而部分则有明显差异,推测是由于基性的镁铁质包体岩浆注入到酸性的花岗岩浆是一个连续多阶段的过程。     

Heating rate dependency of petroleum-forming reactions: implications for compositional kinetic predictions

The generation of bulk petroleum, liquid and gaseous hydrocarbons from the Duvernay Formation was simulated by heating immature kerogens in a closed system (MSSV pyrolysis) at four different heating rates (0.013, 0.1, 0.7 and 5.0 K/min). Using the established parallel reaction kinetic model, temperature and compositional predictions were tested to be suitable for geological conditions by comparing the laboratory results with natural changes in source bitumens and reservoir oil maturity sequences from the Duvernay Formation. In the case of bulk liquid and gaseous hydrocarbons, the above kinetic calculations can be considered valid because their maximum yields are independent of laboratory heating rates. In contrast, the contents of paraffins, aromatics and sulfur compounds show a pronounced heating rate dependence. Extrapolated to geological heating rates, the compositional predictions are consistent with the bulk composition of natural products in the Duvernay-petroleum system showing an increase of paraffinicity and hydrogen content. In contrast to that, the “hump” decreases with decreasing heating rate, a trend which is confirmed by the low amounts of unresolved compounds in natural high maturity products. Because of these heating-rate dependent compositional changes, geological predictions of natural molecular composition by the commonly used kinetic models are not suitable.     

东营凹陷民丰地区天然气生成机理与化学动力学研究

民丰地区天然气存在源岩热解和原油裂解成因的争议。本文采用高压釜封闭体系对该区烃源岩和原油样品分别进行了热模拟实验,从烃类气体生成过程、气态烃与部分单体烃生成动力学特征讨论了二者的生气机理,认为原油裂解比源岩热解生气活化能高30～40 kJ/mol,原油比源岩生气需要更高的热力学条件。模拟实验证实,成熟阶段源岩热解气与原油裂解气相比,以环烷烃和芳烃相对含量低为特征,与民丰地区产出的天然气组成更接近,据此认为该区天然气主要为源岩热解成因。     

低Peclet数下剪切流中气溶胶粒子的传质率

本文研究了低Péclet数下剪切流中气溶胶粒子的传质率。Péclet数(Pe)是物质浓度的对流输送项对分子扩散项的比。它等于Reynolds数(Re)与Schmidt数的(Sc)之积。本文应用奇异扰动方法得到了无因次传质率Nu(Nusselt数)在小Péclet数条件下的四项渐近展式，因而?改进了前人的结果。     

光催化降解乐果的动力学研究

采用30 W石英紫外灯作为光源,研究了乐果在二氧化钛悬浮体系中光催化降解反应的动力学规律。考察了乐果起始浓度、TiO2用量、溶液pH值及温度对乐果光催化降解速率的影响,结果表明,乐果光催化降解符合表观零级动力学规律。由于速率常数k与乐果起始浓度有关,表明乐果光催化降解反应不是一个简单的零级反应。     

From an initial transient-state to a steady-state in metamorphic reactions: An experimental approach in the system dolomite-quartz-H2O

Abstract We carried out hydrothermal experiments in the system dolomite‐quartz‐H₂O to track the temporal change in reaction rates of simultaneous reactions during the development of reaction zones. Two types of configurations for the starting materials were prepared: dolomite single crystals + quartz powder + water and quartz single crystals + dolomite powder + water, both sealed separately in gold capsules. Runs at 0.1GPa and 600°C with cold seal pressure vessels gave the following results. (i) In short duration (45–71 h) runs metastable layer sequences involving wollastonite and talc occur in the reaction zone, whereas they disappear in longer duration (168–336 h) runs. (ii) The layer sequence of the reaction zones in short duration runs differs from place to place on the dolomite crystal even in the same run. (iii) The diversity of layer sequences in the short duration runs merges into a unique layer sequence in the longer duration runs. (iv) The reaction zone develops locally on the dolomite crystal, but no reaction zone was observed on the quartz crystal in any of the runs. The lines of evidence (i)–(iii) show that the system evolves from an initial transient‐ to a steady‐state and that the kinetic effect is important in the development of reaction zones. A steady diffusion model for the unique layer sequence Qtz/Di/Fo + Cal/Dol + Cal/Dol shows that the Dol + Cal layer cannot be formed by diffusion‐controlled process and that the stability of the layer sequence Qtz/Di/Fo + Cal/Dol depends not only on L‐ratios (a = /L_CaOCaO and b = /L_MgOMgO) but also on the relative rate P = (−2ξ₁ − ξ₂)/(–ξ₁ − 2ξ₂) of competing reactions: Dol + 2Qtz = Di + 2CO₂ (ξ₁) and 2Dol + Qtz = Fo + 2Cal + 2CO₂ (ξ₂). For smaller P the stability field will shift to higher values of a and b. The steady diffusion model also shows that the apparent‐non‐reactivity on the quartz surface can be attributed to void formation in a large volume fraction in the diopside layer.     

吐哈盆地低熟气评价的化学动力学方法及其应用

针对目前尚无公认的有效方法评价低熟气生成量的难题,本文从低熟气的（低温）热成因机理出发,认为被广泛、成功应用于成熟的热成因天然气生成量评价的化学动力学理论仍然应该是评价低熟气生成量的有效方法。在此基础上,建立并标定了吐哈盆地代表性泥岩、煤岩干酪根成气的化学动力学模型,与可能部分成为低熟气先质的非烃、沥青质的化学动力学模型一起,构成了评价低熟气生成量的方法。标定结果表明,盆地内有机质成气的平均活化能低于其成油的活化能,而且成气过程中低活化能组分的含量也高于成油过程。这可能正是吐哈盆地的有机质在大量生油之前的低成熟阶段,能开始规模性地生成低熟气、从而导致工业性的低熟气聚集的内因所在。应用表明,吐哈盆地低熟气的总生成量可观,达到632．15×10^11 m^3,而且生气强度较高,最高达到100×10^8m^3／km^2以上。吐哈盆地低熟气资源量约为3．16×10^11～12．62×10^11 m^3。可见,盆地内低熟气具有可观的勘探潜力。本文所建立的方法应该可被推广应用到其他含低熟气盆地的低熟气的评价当中。