Theoretical investigation of intrinsic point defects and the oxygen migration behavior in rare earth hafnates

In this work, the composition-dependent point defect types and formation energies of RE₂Hf₂O₇ (RE = La, Ce, Pr, Nd, Pm, Sm, Eu and Gd) as well as the oxygen diffusion behavior are systematically investigated by first-principles calculations. The possible defect reactions and dominant defect complexes under stoichiometric and non-stoichiometric conditions are revealed. It is found that O Frenkel pairs are the predominant defect in stoichiometric pyrochlore hafnates. Hf-RE cation anti-site defects, accompanied by RE vacancies and/or oxygen interstitials, are stable in the non-stoichiometric case of HfO₂ excess. On the other hand, RE-Hf anti-site defects together with oxygen vacancies and/or RE interstitials are preferable in the case of RE₂O₃ excess. The energy barriers for the migration along the V_O48f - V_O48f pathway of pyrochlore hafnates were calculated to be between 0.81 eV and 0.89 eV. Based on these results, a defect engineering strategy is proposed and the pyrochlore hafnates investigated here are predicted to exhibit potential oxygen ionic conductivity.     

Efficient utilization of silanol group in rice husk to promote the synthesis of Ni-phyllosilicate for CO2 methanation

It is a challenge to prepare Ni-phyllosilicate catalysts deriving from the reaction of nickel salts and biomass-based silica with high Ni contents. In order to efficiently synthesize nickel phyllosilicate, the acid-treated rice husk without calcination (P-R) was directly used as the raw material. The as-synthesized Ni-phyllosilicate (N/P-R) exhibited high nickel content of 46.7 wt% owing to utilization of the abundant silanol group in the fresh rice husk. On the contrary, the Ni content of Ni-phyllosilicate sample (N/R–S) prepared using the calcinated rice husk-based silica was only 4.8 wt% because of the loss of silanol group during calcination process. As a result, N/P-R displayed much higher catalytic activity for CO₂ methanation than N/R–S. It was found that the silanol group was in favour of forming the important intermediate Si(OH)₄, and thereby facilitated the formation of nickel phyllosilicate. In addition, the N/P-R catalyst demonstrated superior stability and excellent anti-sintering ability in the long lifetime test. In short, the proposed method in this work could not only efficiently synthesize nickel phyllosilicate with high Ni content, but also reduce energy consumption and operation steps compared to the one prepared using biomass-based silica.     

RESERVOIR PROPERTIES OF BARREMIAN – APTIAN URGONIAN LIMESTONES,SE FRANCE,PART 1: INFLUENCE OF STRUCTURAL HISTORY ON POROSITY-PERMEABILITY VARIATIONS

Upper Barremian – Lower Aptian inner platform “Urgonian” limestones in the Mont de Vaucluse region, SE France, consist of alternating metre-scale microporous and tight intervals. This paper focuses on the influence of structural deformation on the reservoir properties of the Urgonian limestone succession in a study area near the town of Rustrel. Petrographic, petrophysical and structural data were recovered from five fully-cored boreholes, from the walls of a 100 m long underground tunnel, and from a 50 m long transect at a nearby outcrop. The data allowed reservoir property variations in the Urgonian limestones to be studied from core to reservoir scale. Eleven Reservoir Rock Types (RRTs) were identified based on petrographic features (texture, grain size), reservoir properties (porosity, permeability), and the frequency of structural discontinuities such as fractures, faults and stylolites. Tight and microporous reservoir rock types were distinguished. Tight reservoir rock types were characterised by early cementation of intergranular pore spaces and by the presence of frequent structural discontinuities. By contrast microporous reservoir rock types contained preserved intragranular microporosity and matrix permeability, but had very few structural discontinuities. Observed vertical alternations of microporous and tight rock types are interpreted to have been controlled by the early diagenesis of the Urgonian carbonates. Deformation associated with regional-scale tectonic phases, including Albian – Cenomanian “Durancian” uplift (∼105 to 96 Ma) and Pyrenean compression (∼55 to 25 Ma), resulted in the modification of the initial petrophysical properties of the Urgonian limestones. An early diagenetic imprint conditioned both the intensity of structural deformations and the associated circulations of diagenetic and meteoric fluids. Evolution of the Reservoir Rock Types is therefore linked both to the depositional conditions and to subsequent phases of structural deformation.     

THE ORIGIN OF DOLOMITE IN THE ASMARI FORMATION (OLIGOCENE-LOWER MIOCENE), DEZFUL EMBAYMENT, SW IRAN

Dolomitisation is an important factor controlling reservoir quality in the Asmari Formation in many producing fields in SW Iran. Dolostones have higher average porosities than limestones. Petrographic and geochemical studies have been used to determine the causes of Asmari dolomitisation at the Bibi Hakimeh and Marun fields and at the Khaviz anticline. The formation is generally characterized by a large‐scale trend of upward‐decreasing accommodation. Basal strata were deposited under relatively open‐marine, high‐energy conditions, whereas the Middle to Upper Asmari succession was deposited in relatively protected settings with more frequent evidence of exposure and evaporitic conditions. There is a general upward increase in the abundance of both anhydrite (occurring as nodules and cement) and dolomite. Two main types of dolomite fabric are recognised, reflecting the textures of the precursor limestones: (1) finely crystalline pervasive dolomite (commonly <20μ) replacing mud‐rich facies; and (2) combinations of finely crystalline replacive dolomite and surrounding areas of coarser dolomite cement (crystals up to 100μ) in grain‐supported facies. Fluid inclusion data indicate that finely crystalline dolomites formed at low temperatures (ca. <50°C), while the coarser dolomite formed at higher temperatures (50–;140°C). Whole rock‐carbonate oxygen and carbon isotope analyses of pure dolostone samples show no apparent correlation with either depositional or diagenetic textures: δ¹⁸O is generally 0 to 2.7‰ PDB, and δ¹³C is ?1 to 4‰ PDB. The importance of evaporated seawater to Asmari dolomitisation is indicated by the ubiquitous occurrence of felty‐textured anhydrite nodules in dolostone beds and the presence of high‐salinity fluid inclusions in dolomite. The derivation of dolomitising fluids from contemporaneous seawater is supported by the general correspondence between age estimates derived from the strontium isotope composition of anhydrites and dolomites and those derived from stratigraphic considerations. This suggested synsedimentary dolomitisation. Dolomitisation of the upper half of the Asmari Formation may have occurred as a result of two syn‐sedimentary mechanisms: (1) by the reflux of evaporative brines concentrated in shallow lagoons or sabkhas, through immediately underlying strata (mainly during highstands); and (2) by the flushing of platform‐top carbonates by basinal evaporated waters during lowstand/early transgression. Continued dolomitisation during deeper burial is supported by the presence of high‐temperature fluid inclusions and iron‐rich crystal rims. Dolomite within the lower part of the Asmari Formation probably mostly formed during burial as a result of compaction of, and fluid exclusion from, the underlying Pabdeh marls and shales.     

苏6井区下石盒子组高分辨率层序地层学特征

以高分辨率层序地层学理论和技术方法为指导，在苏里格气田苏6井区地表露头、钻井岩心、测井、地震资料综合研究的基础上，通过基准面旋回结构、叠加样式的沉积动力学分析，将该井区下石盒子组划分为2个长期、5个中期和14个短期旋回层序；并较为详细地讨论了各期旋回层序特征；建立了以长期旋回层序界面和最大洪泛面为等时年代地层框架，以中期旋回层序为等时地层单元的高分辨率层序地层格架；通过分析，认为下石盒子组盒₈下段天然气储、盖条件最为有利；有利于储层发育的河道砂体主要出现在长、中期上升半旋回的中、下部，层序界面上相当短期旋回级别的单河道砂体是下石盒子组天然气勘探开发的主要目标。     

PREDICTING THE TIMING AND CHARACTERISTICS OF PETROLEUM FORMATION USING TAR MATS AND PETROLEUM ASPHALTENES: A CASE STUDY FROM THE NORTHERN NORTH SEA

The Northern Viking Graben area in the Norwegian North Sea was studied in order to investigate the petroleum formation characteristics of the Upper Jurassic Draupne Formation. In this area, the organofacies of the Draupne Formation, and consequently its petroleum generation characteristics, show significant variations. These variations represent a major risk, particularly in the context of basin modelling studies. Therefore, tar‐mat asphaltenes, oil asphaltenes and source‐rock samples from this area were studied in order to evaluate the use of migrated asphaltenes from petroleum reservoirs and tar mats in basin modelling. The samples were studied using bulk kinetic analysis, open‐system pyrolysis‐gas chromatography and elemental analyses, and the results were integrated into a basin modelling study. The results from these different sample materials were compared both to each other and to natural petroleum, in order to assess their significance for future petroleum exploration activities. We show that in cumulative petroleum systems, the transformation characteristics of the asphaltenes incorporate those of the individual source rock intervals which have contributed to the relevant reservoir system. Thus, the petroleum formation window predicted by the use of asphaltene kinetics is broad, and covers the majority of the formation windows predicted from the individual source rock samples. In addition, the molecular characteristics of asphaltene‐derived hydrocarbons show that compositional characteristics, such as aromaticity, correspond more closely to natural oils than to the respective source‐rock products. Our results confirm that the heterogeneous nature of the Draupne Formation results in a significantly broader petroleum formation window than is conventionally assumed. We propose that oil and tar‐mat asphaltenes from related reservoirs represent macromolecules which account for this heterogeneity in the source rock, since they represent mixtures of charges from the different organofacies. One conclusion is that the use of oil and tar‐mat asphaltenes in kinetic studies and compositional predictions may significantly improve definitions of petroleum formation characteristics in basin modelling.     

营尔凹陷下白垩统油气勘探应避开高压水层

营尔凹陷下白垩统(K₁₎存在下沟组和赤金堡组2套源岩，目前它们已到成熟阶段。凹陷东侧长沙岭构造在下白垩统下沟组和赤金堡组储层中也发现油藏，但主要分布在高压水层的顶部及下部，而高压水层段存在良好的储层，并未发现油气。文章根据高压水层段的储层荧光特征，通过储层烃与源岩的对比，分析了下白垩统高压水层对油气运移的影响。研究结果表明：高压水层段，储层荧光弱，储层抽提物特征既不同于赤赤金堡组源岩，也不同于下构组源岩，为就近捕获的产物；高压水层未发生大规模的油气运移，其形成时间早于油气运移的时间。建议该区油气勘探目标的选择应避开高压水层，选择凹陷附近的圈闭、高压水层以下的层位。     

四川盆地及邻区上二叠统一下三叠统海槽的深水沉积特征

四川盆地及邻区广元-旺苍、城口-鄂西、开江-梁平海槽是上二叠统一下三叠统飞仙关组（P3-T1f）的深水碳酸盐沉积区。该区上二叠统上部大隆组是硅质岩、硅质泥岩、硅质灰岩组合，含放射虫、有孔虫等化石，厚125—29．0m，为海槽裂陷期凝缩沉积。三叠系飞仙关组下部为远洋沉积的暗色泥岩、微晶碎屑灰岩和重力流沉积的浊积岩、角砾灰岩组成的深水碳酸盐沉积，厚50．0～300．0m，是裂陷期后的海槽充填沉积。海槽相区沉积在晚二叠统世末达到最大海泛面沉积了大隆组。海平面缓慢下降期沉积了补偿充填性质的飞仙关组深水碳酸盐岩。海槽相区上二叠统一下三叠统飞仙关组构成了一个完整的三级层序。深水沉积物的有机碳平均值高达6．21％，是良好的烃源岩。但在海槽相区上二叠统不发育生物礁，飞仙关组缺乏鲕粒岩。     

东海西湖凹陷平湖油气田花港组高分辨率层序地层特征

通过岩心观察、测井与录井资料,对平湖油气田花港组河流相地层进行了高分辨层序地层分析,识别出2个中期旋回(MSC1与MSC2)与20个短期旋回,建立了研究区的层序地层格架。短期旋回分4种类型并以非对称旋回为主。两个中期旋回为非对称旋回,但MSC2对称性更大,反映了可容纳空间的持续增加。在基准面旋回的控制下,沉积相呈现有规律的辫状河曲流河辫状河曲流河交替演化,在每个中期旋回均以辫状河开端,以曲河流结束,由于中期旋回在长期旋回中的位置不同,曲流河的特征也有所不同。位于中期旋回上升半旋回中部的曲流河及底部的辫状河是研究区的有利砂体,尤其是前者最为有利。     

孤岛油田馆1+2砂层组湖相沉积的发现及其意义

分析胜利油区孤岛油田馆陶组上段连续取心井段的岩心,发现了存在浅水湖泊沉积的证据,据此认为馆1＋2砂层组属于浅水湖泊沉积,而非单一的河流相沉积.沉积期间,湖盆地形平坦、水体极浅,湖平面受气候影响频繁振荡式升降变化,沉积物表现为氧化、还原环境交替的红灰相间的细粒结构,湖泊沉积构造（如波状层理、浪成沙纹层理和波痕等）发育.根据岩性、沉积等特征,划分为水道、砂坪、混合坪、泥坪和沼泽等5种沉积微相类型,洪水期和枯水期各微相的发育特点和平面展布不同.馆1＋2砂层组属于湖相的观点为该区的勘探开发提供了新思路.图5参9