埋藏条件下碳酸盐岩实验室溶蚀作用模拟的热力学模型与地质勘探方向——以陕甘宁盆地下奥陶统马家沟组第五段为例

陕甘宁盆地下奥陶统马家沟组五段为潮坪相碳酸盐岩夹蒸发盐沉积。马五段经历了多期复杂的成岩作用,其中溶蚀作用对马五段影响深刻。首次引用热力学理论对埋藏条件下碳酸盐岩溶蚀作用进行了理论分析和计算。其结果表明碳酸盐岩在埋藏成岩的不同温度压力条件下,酸性介质中溶解反应的吉布斯自由能均为负值,说明反应可自动向方解石、白云石溶解的方向进行,并随着温压的升高溶解的趋势增大.而且白云石溶解的趋势比方解石更大.碳酸盐岩溶蚀作用是受热力学规律支配的自然地质作用。碳酸盐岩溶蚀实验模拟的热力学数学模型对陕甘宁盆地油气田勘探具有重大的理论意义和实际应用价值。     

埋藏条件下碳酸盐岩实验室溶蚀作用模拟的热力学模型与地质勘探方向——以陕

陕甘宁分下奥陶统马家沟组段为湖坪相碳酸盐岩夹蒸发盐沉积，马五段经历了多期复杂的成岩作用，其中溶蚀作用对马五段影响深刻，首次引用热力学理论对埋藏条件下碳酸盐岩溶蚀作用进行了理论分析和计算，其结果表明碳酸盐在埋藏成岩的不同温度压力条件下，酸性介质中溶解反应的吉布斯自由能均为负值，说明反应可自动向方解石，白云石溶解的方向进行，并随着温压的升温溶解的趋势增大，而且白云石溶解的趋势比方解石更大，碳酸盐岩溶蚀     

地层水条件下碳酸盐矿物热力学平衡条件及其在克拉2气田的应用

基于热力学平衡理论及库车盆地的实际,建立了该区地层水温度、压力条件下方解石溶解、白云石对方解石交代作用的热力学平衡条件,并根据地层水介质特征探讨了该区方解石溶解、白云石交代方解石的具体成岩反应状况,认为该区地层水条件下正进行着方解石溶蚀及白云石对方解石的交代作用,方解石的溶蚀是形成该区深层次生孔隙的根本因素。      

油气储层埋藏成岩过程中的地球化学热力学

成岩作用是影响油气储层质量的重要因素,而对于埋藏过程中各种化学成岩作用的有效预测直接关系到储层的评价和预测。为了探索油气储层埋藏成岩过程中主要成岩作用对储层质量影响的预测方法,本文利用地球化学热力学的理论,分析了影响储层质量的主要化学成岩作用,包括砂岩中长石的溶解作用、碳酸盐矿物的溶解与沉淀作用和方解石—白云石的转化作用,建立其埋藏条件下溶解—沉淀的地球化学热力学模型。通过这些模型,试图利用地球化学趋势定量地预测砂岩储层次生孔隙的发育趋势、碳酸盐岩埋藏岩溶—充填趋势和埋藏白云石化趋势,为储层评价预测提供理论依据。     

方解石和白云石溶蚀实验热力学模型及地质意义

通过碳酸盐（方解石、白云石）溶蚀作用实验室模拟研究，建立了溶蚀作用的热力学模型方程，对埋藏成岩的3种不同温压条件下（348．15K，Mpa ,373．15K，25Mpa，403．15K，30MPa）碳酸盐溶蚀作用进行了定量研究。提出随着温度和压力的升高，碳酸盐溶解反应的吉布春播由能降低，因而溶解反应增强；在相同温度和压力的地质条件下，白云石较方解石更易溶蚀并形成次生孔隙，这为油气生成运移提供了有利的地下空间和通道。     

表生和埋藏成岩作用的温压条件下不同组成碳酸盐岩溶蚀成岩过程的实验模拟

表生到埋藏成岩作用的温度与压力（４０～１００℃，常压～２５ＭＰａ），方解石、白云石相对含量不同的碳酸盐岩的溶蚀证明，在表生与相对浅埋藏的温压条件（低于７５℃、２０ＭＰａ）下，方解石的溶解速率大大超过白云石，随着温度和压力的升高，两者溶解速率的差值变小。在相对深埋藏的温压条件（高于７５℃、２０ＭＰａ）下，白云石的溶解速率已超过方解石，在１００、２５ＭＰａ的温压条件下，微晶白云石（白云石/方解石＝９８/２）的溶解速率已是含云灰岩（白云石/方解石＝１６/８４）的２倍，造成这种现象的原因是白云石的温度、压力效应大大超过方解石之故。根据实验的结果可以预测:表生与相对浅埋藏的温压条件下，石灰岩的岩溶作用较白云岩发育；但在深埋藏阶段，由溶解作用造成的白云岩次生孔隙应比方解石更为发育，这是埋藏深度大于２０００ｍ的地层中，白云岩储层多于石灰岩的重要原因。     

表生和埋藏成岩作用的温压条件下不同组成碳酸盐岩溶蚀成岩过程的实验模拟

表生到埋藏成岩作用的温度与压力（４０～１００℃，常压～２５ＭＰａ），方解石、白云石相对含量不同的碳酸盐岩的溶蚀证明，在表生与相对浅埋藏的温压条件（低于７５℃、２０ＭＰａ）下，方解石的溶解速率大大超过白云石，随着温度和压力的升高，两者溶解速率的差值变小。在相对深埋藏的温压条件（高于７５℃、２０ＭＰａ）下，白云石的溶解速率已超过方解石，在１００、２５ＭＰａ的温压条件下，微晶白云石（白云石／方解石＝９８／２）的溶解速率已是含云灰岩（白云石／方解石＝１６／８４）的２倍，造成这种现象的原因是白云石的温度、压力效应大大超过方解石之故。根据实验的结果可以预测：表生与相对浅埋藏的温压条件下，石灰岩的岩溶作用较白云岩发育；但在深埋藏阶段，由溶解作用造成的白云岩次生孔隙应比方解石更为发育，这是埋藏深度大于２０００ｍ的地层中，白云岩储层多于石灰岩的重要原因。     

鄂尔多斯盆地奥陶系不同组构碳酸盐岩埋藏溶蚀实验

鄂尔多斯盆地奥陶系碳酸盐岩储层受埋藏溶蚀作用控制明显,而地层深部复杂的水-岩反应造成埋藏溶蚀研究难度较大,并进而影响了储层的评价与预测。分别利用CO₂溶液和乙酸溶液为流体介质进行溶蚀模拟实验,探讨埋藏条件下温度、压力、流体等因素对不同矿物及组构碳酸盐岩溶蚀作用的影响。结果表明:1）随着温度与压力升高,碳酸盐岩样品在乙酸溶液中的溶解速率均相应提高,在CO₂溶液中的溶解速率则先增加后减小,且在110℃~130℃区间内溶蚀速率最大;深埋藏环境下,各岩类溶蚀速率差异减小,并趋于一致;2）岩石矿物成分和组构,原岩初始孔隙度的大小及其连通关系,以及晶体的产状对成岩后期的埋藏溶蚀作用也具有重要的影响。不溶组分含量低、颗粒/灰泥比高、矿物成分复杂的碳酸盐岩由于组构选择性溶蚀作用而更易被溶蚀;碳酸盐岩的溶蚀速率随方解石含量的增加而增加,但深埋藏环境下,矿物成分含量差异对溶蚀速率的影响作用减弱;硬石膏与白云岩相伴生时,可优先溶蚀形成膏模孔,并促进白云石的溶解,改善储层效果。不同岩性,总体上灰岩较白云岩及过渡岩类更易发生埋藏溶蚀作用。结合研究区实际地质条件分析,砂屑灰岩、膏质白云岩等埋藏溶蚀强度较大,通过对原岩早期组构选择性溶蚀形成孔隙的继承和调整,叠加埋藏期岩溶作用后,可形成规模优质储层。     

碳酸盐岩溶解-沉淀热力学模型及其在塔北地区的应用

 碳酸盐岩作为一种化学岩类其物性受成岩作用的影响十分明显,溶解作用是否发育直接关系到碳酸盐岩储层质量的好坏。碳酸盐矿物在埋藏环境中的溶解度与地层水的化学成分、环境的温度、pH等有着密切的关系。利用地层水化学资料,根据化学热力学的理论,通过方解石及白云石与地层水作用的平衡反应,计算吉布斯自由能变化ΔG,以此来判断方解石及白云石的溶解趋势,并建立了封闭系统中这两种矿物与水作用的热力学模型。根据这个理论模型,对塔北地区159口井奥陶系及6口井的寒武系地层水进行了ΔG的计算,结果显示,塔北地区碳酸盐岩与地层水反应的ΔG基本为负值,表明该地区总体处于碳酸盐岩溶解的环境,寒武系白云岩反应的自由能小于奥陶系灰岩,即在这种深埋条件下白云岩比灰岩更易溶解,这一点在实际岩芯资料上及前人的实验模拟中均有显示。塔北于奇地区自由能的计算结果也为负值,说明该地区强烈的充填作用并非发生在现今条件下,于奇地区现今的埋藏环境是有利于碳酸盐矿物溶解的,这一结论也在该地区奥陶系及寒武系岩芯上得到了验证。
      

陕甘宁盆地中部气田奥陶系碳酸盐岩储层溶蚀及充填作用特征

陕甘宁盆地中部气田产于奥陶系顶部古风化壳碳酸盐岩储集体中,碳酸盐岩储集空间的形成是不同期次的溶蚀作用和充填作用相互作用的结果。根据盆地发展演化阶段不同,大致可以分出四期:第一期为近地表早期成岩溶蚀作用与充填作用(O₁);第二期为风化壳岩溶作用及充填作用(O₂-C₁);第三期为浅埋藏期溶蚀作用与充填作用(C₂);第四期为深埋藏期溶蚀作用与充填作用(P-Q)。化学充填作用形成的自生矿物主要有方解石、白云石、粘土矿物、石英,石膏等.根据充填顺序,地球化学特征等的不同,判别了自生矿物生成顺序及期次。最后论述了不同期次溶蚀作用和充填作用对储集空间形成的建设与破坏作用。     

Calculation of equilibrium distributions of chemical species in aqueous solutions by means of monotone sequences

A numerical method for the calculation of equilibrium distributions of chemical species in aqueous solutions of electrolytes is presented. This method is constructed by transforming the problem of determining the set of unknown concentrations satisfying the mass balance and mass action equations into the equivalent problem of finding the limits of certain well-behaved mathematical sequences in a multivariable direct iteration scheme. The total (analytical) concentrations are taken as the starting estimates, and the recursive equations are constructed from the starting equations. It is shown that the sequences so constructed are both monotonic and bounded, hence convergent in an orderly fashion by a mathematical axiom. Each unknown free ion concentration (that is, each limit) is approached simultaneously from above and from below, being effectively sandwiched in an ever tightening manner. Strict error bounds therefore are easily constructed. The method has been found to be exceedingly efficient in practice, with the error bound (maximum fractional error in taking the upper estimate as the final answer) decreasing in an approximately exponential fashion with respect to iteration number, commonly 0.5–1.5 orders of magnitude per iteration. Correction for nonideality is presented, and the possibility of this giving rise to more than one solution is discussed in connection with three examples of natural waters of low-, medium-, and high-ionic strengths.     

Monotone Regression and Correction for Order Relation Deviations in Indicator Kriging

The indicator kriging (IK) is one of the most efficient nonparametric methods in geo-statistics. The order relation problem in the conditional cumulative distribution values obtained by IK is the most severe drawback of it. The correction of order relation deviations is an essential and important part of IK approach. A monotone regression was proposed as a new correction method which could minimize the deviation from original quintiles value, although, ensuring all order relations.     

积分中值函数ξ（x）的特性

本文研究了积分中值函数ξ（ｘ）的特性，得到了有关ξ（ｘ）单调、连续、可导的结果。     

The terrestrial fauna of the Late Triassic Pant-y-ffynnon Quarry fissures,South Wales,UK and a new species of Clevosaurus (Lepidosauria: Rhynchocephalia)

Pant-y-ffynnon Quarry in South Wales yielded a rich cache of fossils in the early 1950s, including articulated specimens of new species (the small sauropodomorph dinosaur Pantydraco caducus and the crocodylomorph Terrestrisuchus gracilis), but no substantial study of the wider fauna of the Pant-y-ffynnon fissure systems has been published. Here, our overview of existing specimens, a few described but mostly undescribed, as well as freshly processed material, provides a comprehensive picture of the Pant-y-ffynnon palaeo-island of the Late Triassic. This was an island with a relatively impoverished fauna dominated by small clevosaurs (rhynchocephalians), including a new species, Clevosaurus cambrica, described here from a partially articulated specimen and isolated bones. The new species has a dental morphology that is intermediate between the Late Triassic Clevosaurus hudsoni, from Cromhall Quarry to the east, and the younger C. convallis from Pant Quarry to the west, suggesting adaptive radiation of clevosaurs in the palaeo-archipelago. The larger reptiles on the palaeo-island do not exceed 1.5?m in length, including a small carnivorous crocodylomorph, Terrestrisuchus, and a possible example of insular dwarfism in the basal dinosaur Pantydraco.     

The effect of water on accessory phase solubility in subaluminous and peralkaline granitic melts

The solubilities of columbite, tantalite, wolframite, rutile, zircon and hafnon were determined as a function of the water contents in peralkaline and subaluminous granite melts. All experiments were conducted at 1035 °C and 2 kbar and the water contents of the melts ranged from nominally dry to approximately 6 wt.% H₂O. Accessory phase solubilities are not affected by the water content of the peralkaline melt. By contrast, solubilities are affected by the water content of the subaluminous melt, where the solubilities of all the accessory phases examined increase with the water content of the melt, up to 2 wt.% H₂O. At higher water contents, solubilities are nearly constant. It can be concluded that water is not an important control of accessory phase solubility, although the water content will affect diffusivities of components in the melt, thus whether or not accessory phases will be present as restite material. The solubility behaviour in the subaluminous and peralkaline melts supports previous spectroscopic studies, which have observed differences in the coordination of high field strength elements in dry vs. wet subaluminous granitic glasses, but not for peralkaline granitic glasses. Lastly, the fact that wolframite solubility increases with increasing water content in the subaluminous melt suggests that tungsten dissolved as a hexavalent species.     

Quaternary stresses revealed by calcite twinning inversion: insights from observations in the Savonnières underground quarry (eastern France)

Calcite samples were extracted both from the rock matrix and the superficial coating of a karstified fault plane of an underground quarry, located in the eastern border of the Paris basin. The karstification is dated as Quaternary. Analysis of mechanical calcite twinning reveals that only the calcite matrix has also undergone a compression trending WNW that can be attributed to the Mio-Pliocene alpine collision. Both coating and matrix have undergone a strike-slip regime with σ₁ roughly trending north–south, that could correspond to the regional present-day state of stress, a strike-slip compression rather trending NNW, modified by local phenomena. To cite this article: M. Rocher et al., C. R. Geoscience 335 (2003).     

HYDROGEOLOGY

正20141756 Chen Ruige(Mathematical College,China University of Geosciences,Beijing100083,China);Zhou Xun Numerical Simulation of Groundwater Level Fluctuation in a Coastal Confined Aquifer with Sloping Initial Groundwater Level Induced by the Tide(Geological Bulletin of China,ISSN1671-2552,CN11-4648/P,32(7),2013,p.1099-1104,6 illus.,16 refs.) Key words:confined water,groundwater level     

METAMORPHIC PETROLOGY

正20141408 Cai Jia(Institute of Geology,Chinese Academy of Geological Sciences,Beijing100037,China);Liu Fulai Petrogenesis and Metamorphic P-T Conditions of Garnet-Spinel-Biotitebearing Paragneiss in Danangou Area,Daqingshan-Wulashan Metamorphic Complex Belt(Acta Petrologica Sinica,ISSN1000-0569,CN11-1922/P,29(7),     

SERIALS

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GEOPHYSICAL EXPLORATION

正20142386An Guoying(China Aero Geophysical Survey and Remote Sensing Center for Land and Resources,Beijing 100083,China)Application of Satellite Remote Sensing in Regional Hydrogeological Investigation:Taking Cenozoic Strata in Wenquan Sheet(1∶250 000)of Karakoram Range as an Example(Geosci-