埋藏成岩作用的温压条件下，白云岩溶解过程的实验模拟研究

埋藏成岩作用的温度与压力条件（７５℃～１３０℃，２０ＭＰａ～３０ＭＰａ）下，乙酸对白云岩的溶蚀实验证明，随着温度与压力的升高，白云岩的溶解速率迅速增大。Ｃａ、Ｍｇ释放合量由７５℃、２０ＭＰａ条件下的３２.９８ｍｇ/Ｌ增至１３０℃、３０ＭＰａ条件下的３３７.９ｍｇ/Ｌ，增加了一个数量级。在各种温压条件中，１００℃、２５ＭＰａ溶蚀效果最好。实验结果说明，深埋藏条件下，白云岩溶解形成的次生孔隙将比其在浅部的表生环境中更为发育，因而２０００ｍ以下的深埋藏成岩环境中，白云岩储层比浅部地层更为发育。     

石膏对白云岩溶解影响的实验模拟研究

表生到埋藏成岩作用的温度与压力（４０-１３０℃、常压－３０ＭＰａ）条件下，含膏与不含膏白云岩的溶解实验证明:在表生与相对浅埋藏的温压条件（低于７５℃，２０ＭＰａ）下，石膏（或硬石膏）的存在可不同程度地加速白云岩的溶解，随着实验温度和压力的升高，石膏（或硬石膏）对白云岩溶解的这种积极作用逐渐降低。在相对深埋藏的温压条件（高于７５℃、２０ＭＰａ）下，石膏（或硬石膏）的存在显著阻止白云岩的溶解，随着实验温度和压力的继续升高，石膏（或硬石膏）对白云岩溶解的这种消极作用也逐渐增加。从实验的这种结果可以预测，在近地表条件下和埋藏成岩作用的早期阶段，由溶解作用造成的含膏白云岩地层的次生孔隙将比不含膏的白云岩地层更为发育，因而在经历了古风化作用的地层中，含膏白云岩层更易形成良好的储层；与之相反，在相对高温高压的深埋藏成岩阶段，不含膏的白云岩地层中将更容易因酸性水的溶解作用而形成次生孔隙。因而在非蒸发沉积环境中形成的白云岩体（如正常海沉积环境的灰岩中的白云岩透镜体）更易因深埋藏溶蚀作用而形成良好的储层。     

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。     

四川盆地西南部震旦系白云岩成岩过程中的孔隙演化

我国南方,特别是西南地区震旦系白云岩具有良好的油气储集潜力。四川盆地西南部震旦系白云岩储层多集中分布在灯影组的中、上部,储集空间以次生成因的孔、洞、缝为主。这些孔隙的形成与演化受多种因素的影响,其中成岩作用的控制明显,压实作用和多期白云岩的胶结作用使原生孔隙基本消失,而重结晶作用和溶解作用促进了次生孔隙的形成,但多期白云石和硅质的充填作用又导致次生孔隙缩小,局部消失。总之,震旦系白云岩储层内的孔隙是在长达六亿年左右的地质历史中,由各种成岩作用及其它因素相互影响下的最终产物。     

Diagenesis of the Khuff Formation (Permian–Triassic), northern United Arab Emirates

This diagenetic study (including fieldwork, petrographic, fluid inclusion, and stable isotope investigations) deals with the outcrop of Upper Permian–Lower Triassic carbonate rocks, which are equivalent to the Khuff Formation. The studied succession, which outcrops in the Ras Al Khaimah region, northern United Arab Emirates, comprises three formations, including the Bih, the Hagil, and the Ghail formations. The study focuses on unraveling the conditions and fluid compositions encountered during diagenesis of the succession. Emphasize is also made on linking diagenesis to major stratigraphic surfaces and to highlight reservoir property evolution and heterogeneity of the studied rocks. The evolution of fluids and related diagenetic products can be summarized as follows: (1) formation of near-surface to shallow burial, fine-crystalline dolomite (dolomite matrix) through pervasive dolomitization of carbonate sediments by modified marine pore waters; (2) formation of coarse-crystalline dolomite cement by highly evolved marine pore waters (13–23 wt.% NaCl eq.) at elevated temperatures (120–208°C), and (3) calcite cementation by highly saline fluid (20–23 wt.% NaCl eq.) at high temperature (170–212°C). A final calcite cement generation has been formed by the percolation of meteoric fluids during uplift. Fracture- and vug-filling diagenetic minerals are mainly restricted to the mid-Bih breccia marker level, suggesting preferential focused fluid flow through specific stratigraphic surfaces as well as along tectonic-related structures. Reservoir properties have been evolved as result of the interplay of the original sedimentary texture and the diagenetic evolution. Porosity is higher in the Bih Formation, which is dominated by dolomitized packstones and grainstones, than in the Hagil and Ghail formations, consisting mainly of dolomitized mudstones and wackestones. Image analyses were used to quantify the visual porosity in thin sections. The highest porosity values were measured in the Bih Formation, which is characterized by significant amounts of vug- and fracture-filling cements. This feature is attributed to the increase of porosity owing to substantial dissolution of abundant intergranular and vug-filling cements. In contrast, the Hagil and Ghail formations, which consist of finer-grained rock than the Bih Formation, were less cemented, and thus, the porosity enhancement by cement dissolution was insignificant.     

四川盆地西南部震旦系白云岩成岩过程中的孔隙演化

我国南方,特别是西南地区震旦系白云岩具有良好的油气储集潜力。四川盆地西南部震旦系白云岩储层多集中分布在灯影组的中、上部,储集空间以次生成因的孔、洞、缝为主。这些孔隙的形成与演化受多种因素的影响,其中成岩作用的控制明显,压实作用和多期白云岩的胶结作用使原生孔隙基本消失,而重结晶作用和溶解作用促进了次生孔隙的形成,但多期白云石和硅质的充填作用又导致次生孔隙缩小,局部消失。总之,震旦系白云岩储层内的孔隙是在长达六亿年左右的地质历史中,由各种成岩作用及其它因素相互影响下的最终产物。     

Multiphase dolomitization of deeply buried Cambrian petroleum reservoirs,Tarim Basin,north‐west China

Cambrian dolostone reservoirs in the Tarim Basin, China, have significant potential for future discoveries of petroleum, although exploration and production planning is hampered by limited understanding of the occurrence and distribution of dolomite in such ancient rocks buried to nearly 8 km. The study herein accessed new drill core samples which provide an opportunity to understand the dolomitization process in deep basins and its impact on Cambrian carbonate reservoirs. This study documents the origin of the dolostone reservoirs using a combination of petrology, fluid‐inclusion microthermometry, and stable and radiogenic‐isotopes of outcrop and core samples. An initial microbial dolomitization event occurred in restricted lagoon environments and is characterized by depleted δ¹³C values. Dolomicrite from lagoonal and sabkha facies, some fabric‐retentive dolomite and fabric‐obliterative dolomite in the peloidal shoal and reef facies show the highest δ¹⁸O values. These dolomites represent relatively early reflux dolomitization. The local occurrence of K‐feldspar in dolomicrite indicates that some radiogenic strontium was contributed via terrigenous input. Most fabric‐retentive dolomite may have precipitated from seawater at slightly elevated temperatures, suggested by petrological and isotopic data. Most fabric‐obliterative dolomite, and medium to coarse dolomite cement, formed between 90°C and 130°C from marine evaporitic brine. Saddle dolomite formed by hydrothermal dolomitization at temperatures up to 170°C, and involved the mixing of connate brines with Sr‐ enriched hydrothermal fluids. Intercrystalline, moldic, and breccia porosities are due to the early stages of dolomitization. Macroscopic, intergranular, vuggy, fracture and dissolution porosity are due to burial‐related dissolution and regional hydrothermal events. This work has shown that old (for example, Cambrian or even Precambrian) sucrosic dolomite with associated anhydrite, buried to as much as 8000 m, can still have a high potential for hosting substantial hydrocarbon resources and should be globally targeted for future exploration.     

Paleofluid analysis from fracture-fill cements in the Asmari limestones of the Kuh-I-Mond field, SW Zagros, Iran

Kuh-I-Mond field in the Zagros foreland basin is a conventional heavy oil resource and is composed of fractured carbonates whose fractures were filled by calcite, dolomite, and anhydrite cements. Oil inclusions occurred within the fracture-fill cements indicate that fractures were open and played an active role during oil migration and charge. The highest measured values for secondary porosities belong to fractures in Asmari Formation, which is characterized by significant amounts of vug- and fracture-filling cements. Fractures facilitated fluid circulation and subsequently dissolution of allochems and high Mg carbonates. In contrast, fine-grained carbonate facies were less cemented, and thus, porosity enhancement by cement dissolution was insignificant. Temperature profiles of oil inclusions in the dolomite, calcite, and anhydrite minerals characterized by distinct variations in the homogenization temperatures (Th) that are divided into two ranges below 50°C in anhydrites and from 45°C to 125°C in dolomites and calcites. The lower Th ranges for anhydrite suggests that it may have formed at shallower burial depths during early to middle diagenesis. The oil inclusions display trend for increasing temperature downward which conform to Formation geothermal gradient. In other word, the decreasing trend of Th temperatures upward within Asmari Formation that can be observed in Th versus depth plot is consistent with the uplift events at Late Miocene time and later that caused removal of about 1,300 m of the crest of the Kuh-I-Mond anticline. Vitrinite reflectance data from source rock intervals in the field area do not support vertical migration of locally generated hydrocarbons into the Kuh-I-Mond accumulation, and long-distance lateral oil migration and charge from a source kitchen to the southwest is proposed. Vitrinite reflectance data from this dolomite and limestone reservoir suggest low maturation levels corresponding to paleotemperatures less than 50°C. The observed maturation level (<0.5% Ro) does not exceed values for simple burial maturation based on the estimated burial history. Also, homogenization temperatures from fluid inclusion populations in calcite and dolomites show expected good correlation with reflectance-derived temperatures. The Th data represent pore fluids became warmer and more saline during burial. As aqueous fluid inclusions in calcite veins were homogenized between 22°C and 90°C with a decrease in salinity from 22 to 18 eq.?wt.% NaCl. The Th values suggest a change in water composition and that dolomite and calcite cements might have precipitated from petroleum-derived fluids. The hydrocarbon fluid inclusions microthermometry data suggest that the reservoir was being filled by heavy black oils in reservoir during Cenozoic. Aqueous fluid inclusions hosted by calcite equant sparry/fossil cavity fills suggest low cementation temperatures (<45°C) and high salinities (19 eq.?wt.% NaCl), while those in dolostones are characterized by highly variable homogenization temperature (52°C to 125°C) and salinities (6.5 to 20 eq.?wt.% NaCl).     

鄂尔多斯盆地南部奥陶系碳酸盐储层的胶结作用

鄂尔多斯盆地南部奥陶系马家沟组主要由原始沉积的碳酸盐岩和岩溶角砾岩组成。储集空间以次生孔隙为主。中奥陶世沉积作用之后不久,即发生了溶解作用、白云石沉淀、干化脱水作用、机械压实作用、岩溶作用和胶结作用。胶结作用很普遍,主要发生在中石炭世之后的埋藏条件下,是对储层重要的破坏作用。充填于硬石膏结核溶模孔和非组构选择性溶蚀孔、洞、缝的方解石和白云石是最常见的胶结物。这些方解石和白云石胶结物具泥晶、嵌晶状或粒状晶粒结构。泥晶白云石基质的δ18O值-10.98‰~-0.8‰,平均-5.54‰;δ13C值-4.76‰~5.77‰,平均1.51‰。充填于溶蚀孔、缝中的白云石的δ18O值-12.54‰~-2.67‰,平均-7.34‰;δ13C值-5.56
‰~3.48‰,平均0.28‰。充填于溶蚀孔、缝方解石的δ18O值-15.42‰~-6.02‰,平均-9.51‰;δ13C值-12.44‰~1.33‰,平均-3.20‰。总的来说,白云石和方解石胶结物的δ18O和δ13C值低于泥晶白云石基质的,原因是形成晚,受淡水淋滤、埋藏作用和有机质影响较大。泥晶白云石基质的Na含量0~350 μg/g,平均59 μg/g; Sr含量0~380 μg/g,平均10 μg/g;Fe含量0~14 570 μg/g,平均1 040 μg/g;Mn含量0~4 670 μg/g,平均183 μg/g。充填于次生孔隙中的胶结物的Na、Sr、Mn含量与泥晶白云石基质的差别不大,因这些元素含量均低。充填于次生孔隙的碳酸盐胶结物较泥晶白云石基质有明显高的Fe含量。胶结物包裹体的均一温度在90℃~140℃范围内。胶结物沉淀于埋藏较深,温度较高的还原条件下。流体包裹体的气相成分以CH4最为普遍,液相成分以H2O占绝大多数。早期胶结物形成于天然气形成前,晚期胶结物形成于天然气形成之后。岩溶洼地是胶结作用最发育的地带。     

Frictional properties of simulated anhydrite-dolomite fault gouge and implications for seismogenic potential

The frictional properties of anhydrite-dolomite fault gouges, and the effects of CO₂ upon them, are of key importance in assessing the risks associated with CO₂ storage in reservoir formations capped by anhydrite-dolomite sequences, and in understanding seismicity occurring in such formations (such as the Italian Apennines). Therefore, we performed velocity-stepping direct-shear experiments on simulated dolomite, anhydrite and 50:50 anhydrite/dolomite gouges, at representative in-situ conditions (120 °C and σ_n^e = 25 MPa). They were conducted under vacuum, or else using water or CO₂-saturated water as pore fluid (P_f = 15 MPa). Friction coefficients varied between 0.55 and 0.7. All dry samples exhibited velocity-weakening behavior, whereas all wet samples exhibited velocity-strengthening behavior, without or with CO₂. This is consistent with trends previously reported for such gouges. A compilation of literature data shows that the transition from velocity-strengthening to velocity-weakening occurs in these materials between 80 and 120 °C when dry, and between 100 and 150 °C when wet. This implies little seismogenic potential for wet dolomite, anhydrite and mixed gouges under CO₂ storage conditions at 2–4 km depth. Seismic slip in the Italian Apennines at depths of ∼6 km and beyond may be explained by the velocity-weakening behavior expected in anhydrite and especially dolomite at temperatures above 150 °C.     

Carbonate diagenesis of the upper Jurassic successions in the west of Binalud — Eastern Alborz (NE Iran)

The upper Jurassic carbonate settings in Iran are widely exposed in north and northeastern parts. Five stratigraphic columns were selected in the north eastern Iran. Their thickness ranges from 330 to 500 m. The various diagenetic processes identified include, micritization, cementation, compaction (physical and chemical), dissolution, neomorphism, pyritization, hematitization, silicification and dolomitization, which affected these carbonates. Elemental and stable isotopes analysis indicated that these deposits have undergone both meteoric and burial diagenesis in a relatively open system with moderate water-rock interaction. The positive trend between trace elements and oxygen isotope depletion also support these burial conditions. Lighter δ^l8O values of the dolomite samples may be related to an increase in temperature during the burial, which correspond to coarser euhedral crystals. Relatively higher δ¹⁸O values in finer dolomite crystals indicate their formation at lower burial depths relative to coarser crystals. Petrographic evidences such as coarse euhedral crystals with bright and dull zonation prove this interpretation. Chert nodules also have lighter ¹⁸O values relative to carbonate host rock, thus indicating the influence of burial diagenetic processes in their formation. The average environmental palaeotemperature was estimated to be 26°C on the basis of oxygen isotope values of less altered lime-mudstones.     

Kinetics of Hydrothermal Reactions of Minerals in Near-critical and Supercritical Water

This work presents new experimental results on the kinetics of mineral dissolution in near-critical and supercritical water in a temperature range (T) from 25 to 400℃ and a constant pressure of 23 MPa. Kinetic experiments were carried out by using a flow reactor (packed bed reactor) of an open system. The dissolution rates of albite and magnetite were measured under these experimental conditions. Na, Al and Si release rates for albite dissolution in water were measured as a function of the temperature and flow velocity in the reaction system. The maximum release rates of Na, AI and Si of albite dissolution in the hydrothermal flow systems under different flow velocities were always obtained at 300℃, that is to say, the maximum albite dissolution rates in the flow systems, regardless of different flow rates, were repeatedly measured at 300℃. Results indicate a wide fluctuation in albite dissolution rates occurring close to the critical point of water. The dissolution rates increased when the temperatu     

Fluid–rock interactions associated with regional tectonics and basin evolution

An integrated approach consisting of fracture analysis, petrography, carbon, oxygen and strontium‐isotope analyses, as well as fluid‐inclusion micro‐thermometry, led to a better understanding of the evolution of fluid–rock interactions and diagenesis of the Upper Permian to Upper Triassic carbonates of the United Arab Emirates. The deposited carbonates were first marked by extensive early dolomitization. During progressive burial, the carbonates were affected by dolomite recrystallization as well as precipitation of vug and fracture‐filling dolomite, quartz and calcite cements. After considerable burial during the Middle Cretaceous, sub‐vertical north–south oriented fractures (F1) were cemented by dolomite derived from mesosaline to hypersaline fluids. Upon the Late Cretaceous maximum burial and ophiolite obduction, sub‐vertical east–west fractures (F2) were cemented by dolomite (Dc2) and saddle dolomite (Ds) derived from hot, highly saline fluids. Then, minor quartz cement has precipitated in fractures from hydrothermal brines. Fluid‐inclusion analyses of the various diagenetic phases imply the involvement of increasingly hot (200°C) saline brines (20 to 23% NaCl eq.). Through one‐dimensional burial history numerical modelling, the maximum temperatures reached by the studied rocks are estimated to be in the range of 160 to 200°C. Tectonically‐driven flux of hot fluids and associated diagenetic products are interpreted to have initiated during the Late Cretaceous maximum burial and lasted until the Oligocene–Miocene compressional tectonics and related uplift. The circulation of such hydrothermal brines led to partial dissolution of dolomites (Dc2 and Ds) and to precipitation of hydrothermal calcite C1 in new (mainly oriented north–south; F3) and pre‐existing, reactivated fractures. The integration of the obtained data confirms that the diagenetic evolution was controlled primarily by the interplay of the burial thermal evolution of the basin and the regional tectonic history. Hence, this contribution highlights the impacts of regional tectonics and basin history on diagenetic processes, which may subsequently affect reservoir properties.     

鲕粒白云岩内部溶蚀及孔隙非均质性演化研究

在地表和埋藏条件下溶蚀作用形成的次生孔隙是碳酸盐岩油气储层重要的储集空间。为探究孔隙的溶蚀改造机理及其控制因素,通过柱塞样,开展了0.2%的乙酸环境中鲕粒白云岩的溶蚀实验,实验温度和压力范围分别为40~160 ℃和10~50 MPa。实验采取连续取样获得溶液中Ca²⁺与Mg²⁺离子含量,通过CT 成像技术获取溶蚀反应前后孔隙图像并运用分形与多重分形方法定量分析孔隙在二维和三维空间上的非均质性。研究表明,溶蚀过程中,鲕粒白云岩溶蚀液中[Ca²⁺+Mg²⁺]浓度在实验开始时最低,之后稳步上升并在120 ℃、40 MPa时达到最大值,而后缓慢下降,溶蚀窗范围出现在70 ℃(20 MPa)~120 ℃(40 MPa)之间。二维和三维微观孔隙结构在空间上的分布具有显著的多重分形特征,溶蚀作用使得孔隙的不规则性减少、孔隙的奇异范围缩减。这些结果对于认识近地表和深埋藏条件下溶蚀作用对碳酸盐岩储层孔隙的改造强度及孔隙的动态演化规律具有重要的理论及实际意义。     

Diagenetic evolution of the Carnian Wetterstein platforms of the Eastern Alps

The carbonate platforms of the Wetterstein Formation of the Eastern Alps (Drau Range and Northern Calcareous Alps) show a distinct facies zonation of reefs and lagoons. While some lagoonal areas were episodically emerged and formed lagoonal islands, others remained permanently flooded. The scale of near surface, meteoric or marine diagenesis was related to this lagoonal topography. At shallow burial depth, cementation was dominated by altered marine solutions, which additionally caused recrystallization of metastable constituents of the sediment and earlier marine cements (high magnesian calcite, aragonite) connected with a carbon and oxygen isotopic change to more negative values. Deeper burial cementation shows a succession with two types of saddle dolomite and three types of blocky calcite. Carbon and oxygen isotopic values of these cements show a trend towards more negative values from the first to the last generation, in the following succession: clear saddle dolomite—zoned blocky calcite—cloudy saddle dolomite—post-corrosion blocky calcite—replacive blocky calcite. Fluid inclusion studies of the carbonate cements are interpreted to indicate a deeper burial temperature development that first increases from 175 to 317°C, followed by a temperature decrease to 163–260°C, and subsequent increase up to 316°C, whereby the samples of the Drau Range always show the lowest values. Calculations of the isotopic composition of the water, from which the carbonate cements were precipitated, yielded positive δ¹⁸O values from 6.66 to 17.81%o (SMOW), which are characteristic for formation and/or metamorphic waters. Also, the isotopic compositions of the palaeofluids probably changed during deeper burial diagenesis, following the temperature development.     

Determining fluid source and possible pathways during burial dolomitization of Maryville Limestone (Cambrian), Southern Appalachians, USA

Detailed petrographic analyses along a depositional transect from a carbonate platform to shale basin reveals that dolomite is the principal burial diagenctic mineral in the Maryville Limestone. This study examines the role of burial dolomitization of subtidal carbonates. Dolomite occurs as a replacement of precursor carbonate and as inter- and intraparticle cements. Four different types of dolomite are identified based on detailed petrographic and gcochemical analyses. Type I dolomite occurs as small, irregular disseminations typically within mud-rich facies.Type II dolomite typically occurs as inclusions of planar euhedral rhombs (ferroan), 5–300 μm in size, in blocky clear ferroan calcite (meteoric) spar. Type II dolomite is non-luminescent. Type I and II dolomite formed during shallow to intermediate burial diagenesis. Type III dolomite consists of subhedral to anhedral crystals 10–150 μm in size occurring as thin seams along stylolites and as thick bands a few millimetres in width. This dolomite consists of dominantly non-luminescent rhombs and, less commonly, orange luminescent and zoned rhombs. Type IV dolomite consists of baroque or saddle-shaped, 100–1500 μm crystals, and is non-luminescent. Type IV dolomite formed during the period of maximum burial. Types III and IV dolomite increase in abundance downslope. Type III dolomite contains 1.2–2.6 wt% Fe and a maximum of 1000 ppm Mn. The distribution of these elements displays no distinct vertical or lateral trends. In contrast, Fe and Mn distributions in Type IV dolomite exhibit distinct spatial trends, decreasing from 3.5–4.5 wl% Fe and 0.1–0.3 wt% Mn in the west (slope/basin) to 1.5–2.5 wt% Fe and less than 600 ppm Mn in the east (shelf margin), a distance of approximately 60 km. Spatial trends in Fe and Mn distributions in Type IV saddle dolomite, suggest a west-east fluid flow during late burial diagenesis. Types III and IV dolomite have a mean δ¹⁸O value of - 7.8%₀₀ and a mean δ¹³C value of + 1.1%₀₀ (relative to the PDB standard). Based on a range of assumed basinal water composition of 2.8%₀₀ SMOW, temperatures calculated from δ¹⁸O values of Types III and IV dolomite range between 75 and 160°C. ⁸⁷Sr/⁸⁶Sr data for Types III and IV dolomite range from 0.7111 to 0.7139. These values are radiogenic when compared to Cambrian marine values and are consistent with the presence of a diagenetic fluid that interacted with siliciclastic sediments. The distribution of Palaeozoic facies in the southern Appalachians indicates a Cambrian shale source for the fluids, whilst burial curves suggest a Middle Ordovician age for burial fluid movement.     

Experimental Study on Water‐rock Reactions with CO2 Fluid in a Deep Sandstone Formation under High Temperature and Pressure

Qiongdongnan Basin has a tectonic geological background of high temperature and high pressure in a deep reservoir setting,with mantle-derived CO2.A water-rock reaction device was used under high temperature and high pressure conditions,in conjunction with scanning electron microscope(SEM)observations,to carry out an experimental study of the diagenetic reaction between sandstone at depth and CO2-rich fluid,which is of great significance for revealing the dissolution of deep clastic rock reservoirs and the developmental mechanism of secondary pores,promoting deep oil and gas exploration.In this study,the experimental scheme of the water-rock reaction system was designed according to the parameters of the diagenetic background of the deep sandstone reservoir in the Qiongdongnan Basin.Three groups of single mineral samples were prepared in this experiment,including K-feldspar samples,albite samples and calcite samples.Using CO2 as a reaction solution,a series of diagenetic reaction simulation experiments were carried out in a semi-closed high temperature and high pressure simulation system.A field emission scanning electron microscope(SEM)was used to observe the microscopic appearance of the mineral samples after the water-rock reaction,the characteristics of dissolution under high temperature and high pressure,as well as the development of secondary pores.The experimental results showed that the CO2-rich fluid has an obvious dissolution effect on K-feldspar,albite and calcite under high temperature and high pressure.For the three minerals,the main temperature and pressure window for dissolution ranged from 150℃to 300℃and 45 MPa to 60 MPa.Scanning electron microscope observations revealed that the dissolution effect of K-feldspar is most obvious under conditions of 150℃and 45 MPa,in contrast to conditions of200℃and 50 MPa for albite and calcite.Through the comparative analysis of experimental conditions and procedures,a coupling effect occurred between the temperature and pressure change and the dissolution strength and calcite.Under high temperature and high pressure,pressure changed the solubility of CO2,furthermore,the dissolution effect and strength of the sandstone components were also affected.The experiment revealed that high temperature and high pressure conditions with CO2-rich fluid has a significant dissolution effect on aluminosilicate minerals and is conducive to the formation of secondary pores and effective reservoirs.Going forward with the above understanding has important implications for the promotion of deep oil and gas exploration.     

埋藏历史对碳酸盐溶解-沉淀的影响——以四川盆地东北部三叠系飞仙关组和塔里木盆地北部奥陶系为例

埋藏成岩过程中碳酸盐的溶解与沉淀强烈控制着深埋藏地层中碳酸盐岩储层质量,与之有关的地质过程是人们多年来不懈研究的热点领域。热流体沿断裂向上运移所造成的碳酸盐溶解成为近年人们普遍认可的模式,但这不能圆满解释大量存在的不与断裂伴生的深埋藏碳酸盐的溶解机制。基于四川盆地东北部和塔里木盆地北部深埋藏碳酸盐溶解与沉淀机制的研究,认为埋藏过程中盆地的沉降与抬升是碳酸盐溶解与沉淀以及次生孔隙发育的另一重要机制,在改变流体对碳酸盐饱和状况方面具有和热流体沿断裂向上运移相同的重要性。研究表明:与川东北飞仙关组类似的埋藏历史更有利于深埋藏成岩过程中碳酸盐的溶解,主要特点是当前埋藏深度不是最大埋藏深度,在最大埋藏深度附近发生热化学硫酸盐还原作用,其后盆地持续抬升造成温度降低和碳酸盐溶解,与之有关的次生孔隙形成所造成的岩石力学性质的变化与上覆载荷减小可以得到平衡,次生孔隙得以保存,岩石储层质量改善;塔里木盆地北部的奥陶系埋藏历史不利于深埋藏成岩过程碳酸盐的溶解,主要特点是当前埋藏深度是最大埋藏深度,古喀斯特发生之后盆地持续沉降造成温度升高和碳酸盐沉淀,并与上覆载荷的增加同步发生,结果是孔隙的封堵、岩石的致密化和储层质量的变差。     

Dissolution experiment and transformation condition analysis of Paleogene aragonite in the Jiyang Depression,China

In general, aragonite exists as a metastable carbonate mineral under near-surface conditions, and is commonly transformed into calcite under the subsurface and during diagenesis. It is thus seldom found in sedimentary rocks, but aragonite is common in the Paleogene lacustrine shales in the Jiyang Depression in eastern China. Dissolution experiments were conducted on the Paleogene aragonite-enriched and calcite-enriched shales at different temperatures, pressures and acetic acid concentrations, and in different types of solution. The results show that aragonite is insoluble in the in situ formation water but dissolved more readily under acetic acid conditions than calcite with the degree of dissolution increasing with increasing temperature, pressure and acetic acid concentrations. During the shallow burial diagenesis of the Paleogene sediment sequence in the Jiyang Depression, aragonite was relatively stable and was not dissolved by the connate pore water in the shales. Increasing burial (temperature) and maturity of the organic matter produced large amounts of organic acids that accelerated the dissolution of aragonite. In the late stage, as the organic matter became over-matured, the pore water changed from acidic to alkaline, and calcite precipitated from the carbonate-rich solution. Therefore, the conditions provided by organic acids enabled the conversion of aragonite to calcite during sedimentary diagenesis in the Paleogene lacustrine shales in the Jiyang Depression. This transformation corresponded to the thermal evolution of the organic matter within the shale sequence.