辽河盆地西部凹陷沙河街组砂岩碳酸盐胶结物特征

碳酸盐胶结物中氧碳同位素组成研究是分析成岩过程中流体-岩石相互作用的重要技术方法.综合运用岩石学、矿物学和地球化学方法，对辽河盆地西部凹陷沙河街组砂岩中碳酸盐胶结物的化学组成和碳酸盐胶结物及成岩流体同位素组成特征进行系统分析.研究表明，研究区碳酸盐岩主要为方解石和白云石，胶结物主要类型为嵌晶式胶结、孔隙式胶结、斑块状胶结和星点状胶结.碳、氧稳定同位素组成能有效地反映成岩-成矿流体及其他物质的来源，碳酸盐胶结物与现今浅层地下水氧同位素组成差异巨大而与变质水同位素组成具有相似性，反映了盆地演化过程中活动热流体对成岩作用的影响.包裹体的氢、氧同位素组成可表征成矿溶液的演化特征，砂岩碳酸盐胶结物包裹体更富集氢的轻同位素和氧的重同位素，表明发生了明显的“氧-18漂移”.碳酸盐胶结的成矿溶液表现出“受热雨水”的同位素组成特征，反映了深源活动热流体对成岩作用的影响.      

Origin of dolomitization on the Barbwire Terrace, Canning Basin, Western Australia

A thick, areally extensive subsurface sequence of Upper Devonian carbonates occurs on the Barbwire Terrace in the Canning Basin of Western Australia. It is a platform sequence in which most of the shallow water lithologies have been thoroughly dolomitized. Slightly deeper water marls have remained as limestones. The major, regional dolomite type in the sequence is not restricted to peritidal lithologies and forms large thicknesses of dolomite (up to 600 m) with no primary calcite. A small volume of evaporitic, supratidal dolomite is present at one location. This dolomite is derived from highly saline fluids developed in an arid supratidal environment. Replacement dolomite of the regional dolomite type has a xenotopic form, with undulose extinction, and irregular crystal boundaries. In addition, saddle dolomite cements appear to have precipitated contemporaneously with the major phase of replacement dolomite. This suggests the regional dolomite type was precipitated at slightly elevated temperatures. Dolomitized stylolites and cements appear to indicate that dolomitization occurred after cementation and pressure solution. Geochemically, the synsedimentary supratidal and regional dolomite types are quite distinctive. Supratidal dolomites have δ18O values which are significantly higher (δ18O=?2 to +1‰ (PDB)) than the regional dolomite type (δ18O=?9 to ?2‰ (PDB)). Assuming the lowest δ18O values for the sabkha dolomite represent replacement in marine waters, the oxygen isotopic composition for Upper Devonian Canning Basin marine dolomite would be around δ18O=?2‰ (PDB). The petrographic and geochemical characteristics of the regional dolomite type support a burial diagenetic origin. However, sources of magnesium in current burial dolomitization models appear insufficient to account for the large volume of dolomite on the Barbwire Terrace. Therefore, it is suggested that dolomitization may have taken place in a near-surface environment with a major recrystallization event superimposed during burial diagenesis.     

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。     

A survey of multi-stage diagenesis and dolomitization of Jurassic limestones along a regional shelf-to-basin transect in the Ziz Valley,Central High Atlas Mountains,Morocco

Petrographic and geochemical data from five localities in the Ziz Valley of Morocco indicate that Jurassic limestones have undergone early diagenesis that varied with location from shelf to basinal settings, burial diagenesis that was most pronounced in basinal settings, and late diagenesis caused by compression and uplift of the High Atlas Mountains.Marine cements occur at all five localities from shelf-to-basin center, although cement types vary from peloidal microcrystalline cements updip on the shelf-to-equant calcite in basinal settings. Presence of moldic grains and/or Mg-poor, Fe-poor blocky cements suggest that meteoric waters influenced early diagenesis at all shelf localities and on an upturned fault block in the basinal region, leaving only one locality unaffected by early meteoric processes. ⁸⁷Sr/⁸⁶Sr ratios of 0.70810–0.70895 (greater than ⁸⁷Sr/⁸⁶Sr of coeval limestones), Mg contents that decrease upward from 47.5 to 43.0 mol% MgCO₃, presence of dolomitized marine cements, and dolomite cements that postdate marine cements but predate meteoric-to-burial cements suggest that dolomitization and dolomite cementation at two shelf localities took place in mixed meteoric and marine waters early in diagenesis. However, poorer preservation of depositional fabrics, lower δ¹⁸O values, and larger and more anhedral crystals suggest that dolostones downdip underwent later modification during burial, whereas those updip did not.Compaction during diagenesis generated numerous concavo–convex and sutured intergranular contacts at updip shelf, downdip shelf, and basinal localities where earlier meteoric cementation was not extensive. Compaction was insignificant in more extensively cemented mid-shelf settings. High Sr (1200–3800 ppm) and Fe (1000–2300 ppm) contents in brachiopod grains suggest that LMC components underwent some modification during burial in basinal settings in Sr-rich reducing waters. Fe contents of late intergranular cements increase from 2000 ppm at the basin's edge to as much as 6000 ppm in the basin's center. Bedding-parallel stylolites occur at all localities.The most negative δ¹⁸O values of sparry dolomites near the Tizi n'Firest fault (−6.2‰ vs. PDB) imply diagenetic temperatures of 65–85°C assuming water δ¹⁸O values of 0.0–2.0‰ vs. SMOW. Those temperatures are much less than previous estimates of burial temperatures in the High Atlas basin. An isotopic gradient extrapolating to roughly 5‰/km in diagenetically modified dolostones likewise suggests a geothermal gradient less than gradients previously proposed for at least parts of the area.Comparison of morphologies of transverse stylolites, which are found at all localities, with morphologies of bedding parallel stylolites suggests that transverse stylolites formed due to compression during late diagenesis. Uplift accompanying that compression allowed influx of low-Mg waters that, along with other factors, caused calcitization of dolomites. The Fe concentration of calcite that fills late fractures increases from less than 2000 ppm at the basin center to values in excess of 3000 ppm at the basin edge, opposite trends in earlier cements and reflecting uplift of the High Atlas Mountains and resultant changes in patterns of groundwater flow.     

Controls of facies and sediment composition on the diagenetic pathway of shallow-water Heterozoan carbonates: the Oligocene of the Maltese Islands

Relatively few studies have so far addressed diagenetic processes in Heterozoan carbonates and the role that sediment composition and depositional facies exert over diagenetic pathways. This paper presents a study of Oligocene shallow-water, Heterozoan carbonates from the Maltese Islands. We investigate stratigraphic distribution, abundance and timing of diagenetic features and their relationship to sediment composition and depositional facies. The studied carbonate rocks comprise rud- to packstones of the Heterozoan association predominantly containing coralline red algae, bryozoans, echinoids and benthic foraminifers. XRD analyses show that all high-Mg calcite has been transformed to low-Mg calcite and that no aragonite is preserved. Diagenetic processes include dissolution of aragonitic biota, neomorphism of high-Mg calcitic biota to low-Mg calcite and cementation by fibrous, bladed, epitaxial and blocky cements. Stable isotopes on bulk rock integrated with petrographic data suggest that the study interval was not exposed to significant meteoric diagenesis. We interpret early cementation to have taken place in the marine and marine burial environment. The distribution and abundance of early diagenetic features, determining the diagenetic pathway, can be related to the primary sediment composition and depositional texture. Sorting and micrite content are important controls over the abundance of diagenetic features.     

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.     

Closed-system marine burial diagenesis: isotopic data from the Austin Chalk and its components

ABSTRACT
The carbon and oxygen isotopic composition of the Austin Chalk was examined in cores representing a range of depths from surface to 3000 m in order to document the effects of burial diagenesis on carbon and oxygen isotopic composition. Low magnesium calcite oysters were separated (from 500 um wide areas) and analysed to estimate the starting composition of Cretaceous marine sediment. These gave an average value of -2·5%δ¹⁸O; + 2·0%δ¹³C (PDB). The compositions of micrite, intergranular cement, and fracture cement were analysed, and their deviation from this original marine composition was evaluated to document the progression of chalk diagenesis. Interestingly, micrite exhibits only minor variation in composition from marine values despite present burial depth ranges in excess of 3000 m. The average deviation from δ18O marine is less than 1·5. Furthermore, intergranular cement and particularly fracture cements, which occur only in the deepest cores and which clearly post-date micrite lithification, are generally indistinguishable from micrite in composition. Isotopic compositions exhibit no correlation with depth of burial despite abundant petrographic evidence of deep burial diagenesis. This uniformity in composition is interpreted as reflecting a closed, rock-dominated diagenetic system in which the compositions of precipitated carbonate cements were controlled by the composition of dissolving carbonates during lithification. As such, the composition of burial cement is not representative of the rock-water temperatures during precipitation.
Thus, in the context of isotopic analyses from other carbonate systems, unless the degree of openness of the diagenetic system is known, oxygen isotopic signatures of cements cannot directly be converted to the rock-water temperatures at which they were precipitated unless the composition of the ambient porefluid is also known.     

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).     

Diagenesis of Barremian-Aptian platform carbonates (the Urgonian Limestone Formation of SE France): near-surface and shallow-burial diagenesis

The diagenesis of carbonate platform sediments is controlled by the original facies and mineralogy, climate, sea-level changes and burial history; these controls are clearly seen in the diagenesis of the Urgonian platform carbonates of SE France. Early diagenesis in the Urgonian platform included the precipitation of marine cements, dissolution of rudist shells and minor karstification. Diagenetic features produced during this phase were controlled by several falls in relative sea-level during the Barremian to mid-Aptian punctuating platform sedimentation, the original mineralogy of the sediment and the prevailing semi-arid/arid climate in the region at this time. Following a relative sea-level rise and further sedimentation, progressive burial of the platform led to minor compaction, followed by precipitation of coarse, equant, zoned to non-luminescent, calcite cement. This cement was cut by later stylolites, suggesting a relatively shallow-burial origin. Stable isotope (mean values - 7.94%δ¹⁸O and 0.36%δ¹³C) and trace element (mean values of Fe 334 ppm, Mn 92 ppm and Sr 213 ppm) data suggest that these cements precipitated from meteoric fluids at temperatures slightly elevated relative to depositional temperatures. A variable thickness of replacive dolomite which occurs preferentially within the shelf-margin facies of the lower part of the Urgonian post-dates mechanical fracturing and chemical compaction, but pre-dates the main phase of stylolitization. It is probable that the dolomitizing fluid was sourced by the early compaction-driven release of connate fluids held within the underlying muddy units. The burial history of these rocks suggests that calcite cementation and dolomitization took place at relatively shallow burial depths (1–1.5 km). The overall diagenetic history of the Urgonian Limestone Formation is a reflection of the pre-conditioning of the platform limestones by climate, sea level, tectonics and the shallow burial depths experienced by the platform during the later Mesozoic.     

Calcite cementation during bacterial manganese, iron and sulphate reduction in Jurassic shallow marine carbonates

Faunally restricted argillaceous wackestones from the Middle Jurassic of eastern England contain evidence of early diagenetic skeletal aragonite dissolution and stabilization of the carbonate matrix, closely followed by precipitation of zoned calcite cements, and precipitation of pyrite. Distinctive cathodoluminescence and trace element trends through the authigenic calcites, their negative δ¹³C compositions and the location of pyrite in the paragenetic sequence indicate that calcite precipitation took place during sequential bacterial Mn, Fe and sulphate reduction. Calcite δ¹⁸O values are compatible with cementation from essentially marine pore fluids, although compositions vary owing to minor contamination with ¹⁸O-depleted ‘late’cements. Mg and Sr concentrations in the calcites are lower than those in recent marine calcite cements. This may be a result of kinetic factors associated with the shallow burial cementation microenvironments. Bicarbonate for sustained precipitation of the authigenic calcites was derived largely from aragonite remobilization, augmented by that produced through anaerobic organic matter oxidation in the metal and sulphate reduction environments. Aragonite dissolution is thought to have been induced by acidity generated during aerobic bacterial oxidation of organic matter. Distinction of post-oxic metal reduction and anoxic sulphate reduction diagenetic environments in modern carbonate sediments is uncommon outside pelagic settings, and early bacterially mediated diagenesis in modern platform carbonates is associated with extensive carbonate dissolution. High detrital Fe contents of the Jurassic sediments, and their restricted depositional environment, were probably the critical factors promoting early cementation. These precipitates constitute a unique example of calcite authigenesis in shallow water limestones during bacterial Mn and Fe reduction.     

Shallow-marine carbonate cementation in Holocene segments of the calcifying green alga Halimeda

Early-diagenetic cementation of tropical carbonates results from the combination of numerous physico-chemical and biological processes. In the marine phreatic environment it represents an essential mechanism for the development and stabilization of carbonate platforms. However, diagenetic cements that developed early in the marine phreatic environment are likely to become obliterated during later stages of meteoric or burial diagenesis. When lithified sediment samples are studied, this complicates the recognition of processes involved in early cementation, and their geological implications. In this contribution, a petrographic microfacies analysis of Holocene Halimeda segments collected on a coral island in the Spermonde Archipelago, Indonesia, is presented. Through electron microscopical analyses of polished samples, this study shows that segments are characterized by intragranular cementation of fibrous aragonite, equant High-Mg calcite (3.9 to 7.2 Mol% Mg), bladed Low-Mg calcite (0.4 to 1.0 Mol% Mg) and mini-micritic Low-Mg calcite (3.2 to 3.3 Mol% Mg). The co-existence and consecutive development of fibrous aragonite and equant High-Mg calcite results initially from the flow of oversaturated seawater along the aragonite template of the Halimeda skeleton, followed by an adjustment of cement mineralogy towards High-Mg calcite as a result of reduced permeability and fluid flow rates in the pores. Growth of bladed Low-Mg calcite cements on top of etched substrates of equant High-Mg calcite is explained by shifts in pore water pH and alkalinity through microbial sulphate reduction. Microbial activity appears to be the main trigger for the precipitation of mini-micritic Low-Mg calcite as well, based on the presumable detection of an extracellular polymeric matrix during an early stage of mini-micrite Low-Mg calcite cement precipitation. Radiocarbon analyses of five Halimeda segments furthermore indicate that virtually complete intragranular cementation in the marine phreatic environment with thermodynamically/kinetically controlled aragonite and High-Mg calcite takes place in about 100 years. Collectively, this study shows that early-diagenetic cements are highly diverse and provides new quantitative constraints on the rate of diagenetic cementation in tropical carbonate factories.     

非热液成因的鞍形白云石:来自加拿大萨斯喀彻温省东南部奥陶系Yeoman组的岩石学和地球化学证据

加拿大萨斯喀彻温省东南部上奥陶统Yeoman组碳酸盐岩中发育有少量的鞍形白云石胶结物。这些鞍形白云石仅局限于Yeoman组上部厚约20~30 m的白云岩带中,上覆及下伏碳酸盐岩地层中均明显缺失这类鞍形白云石,表明其形成于一个相对封闭的体系中。此类奥陶系鞍形白云石胶结物以具有与宿主交代白云岩相似的碳同位素δ13C值（-0.2‰~0.9‰PDB）及锶同位素比值（0.708 2~0.709 0）为特征,表明前期的白云石围岩通过压溶作用形成的碳和锶是鞍形白云石胶结物的主要来源。另外,测得的鞍形白云石胶结物均一温度范围为99~105℃,可以由该区域的正常埋藏温度解释。基于上述资料和观察,我们认为萨斯喀彻温省东南部上奥陶统Yeoman组鞍形白云石胶结物与早期交代白云石的自调节白云石化作用（埋藏过程中相对封闭的体系中通过化学压实作用形成）有关,而与加西盆地其它地方已经证实的热液活动无关。因此,鞍形白云石的分布未必指示热液活动或热流体,也并不是所有的鞍形白云石都与热流体有关。     

Testing the preservation potential of early diagenetic dolomites as geochemical archives

Early marine diagenetic dolomite is a rather thermodynamically-stable carbonate phase and has potential to act as an archive of marine porewater properties. However, the variety of early to late diagenetic dolomite phases that can coexist within a single sample can result in extensive complexity. Here, the archive potential of early marine dolomites exposed to extreme post-depositional processes is tested using various types of analyses, including: petrography, fluid inclusion data, stable δ¹³C and δ¹⁸O isotopes, ⁸⁷Sr/⁸⁶Sr ratios, and U-Pb age dating of various dolomite phases. In this example, a Triassic carbonate platform was dissected and overprinted (diagenetic temperatures of 50 to 430°C) in a strike-slip zone in Southern Spain. Eight episodes of dolomitization, a dolostone cataclasite and late stage meteoric/vadose cementation were recognized. The following processes were found to be diagenetically relevant: (i) protolith deposition and fabric-preservation, and marine dolomitization of precursor aragonite and calcite during the Middle–Late Triassic; (ii) intermediate burial and formation of zebra saddle dolomite and precipitation of various dolomite cements in a Proto-Atlantic opening stress regime (T ca 250°C) during the Early–Middle Jurassic; (iii) dolomite cement precipitation during early Alpine tectonism, rapid burial to ca 15 km, and high-grade anchizone overprint during Alpine tectonic evolution in the Early Eocene to Early Miocene; (iv) brecciation of dolostones to cataclasite during the onset of the Carboneras Fault Zone activity during the Middle Miocene; and (v) late-stage regression and subsequent meteoric overprint. Data shown here document that, under favourable conditions, early diagenetic marine dolomites and their archive data may resist petrographic and geochemical resetting over time intervals of 10⁸ or more years. Evidence for this preservation includes preserved Late Triassic seawater δ¹³C_DIC values and primary fluid inclusion data. Data also indicate that oversimplified statements based on bulk data from other petrographically-complex dolomite archives must be considered with caution.     

Late Pleistocene mixing zone dolomitization, southeastern Barbados, West Indies

ABSTRACT Field, geochemical, and petrographic data for late Pleistocene dolomites from southeastern Barbados suggest that the dolomite precipitated in the zone of mixing between a coastal meteoric phreatic lens and normal marine waters. The dolomite is localized in packstones and wackestones from the algalAmphistegina fore-reef calcarenite facies. Stable isotopic evidence suggests that meteoric water dominated the diagenetic fluids responsible for dolomitization. Carbon isotopes in pure dolomite phases average about -15%₀ PDB. This light carbon is attributed to the influence of soil gas CO₂, and precludes substantial mixing with seawater. A narrow range of oxygen isotopic compositions coupled with a wide range of carbon compositions attest to the meteoric diagenetic overprint. Dolomitization likely occurred with as little as a five per cent admixture of seawater. Strontium compositions of the dolomites indicate probable replacement dolomitization of original unstable mineralogy. The dolomite is characterized by low sodium values. Low concentrations of divalent manganese and iron suggest oxidizing conditions at the time of dolomitization. A sequence of petrographic features suggests a progression of diagenetic fluids from more marine to more meteoric. Early marine diagenesis was followed by replacement dolomitization of skeletal grains and matrix. Limpid, euhedral dolomite cements precipitated in primary intra- and interparticle porosity subsequent to replacement dolomitization. As waters became progressively less saline, dolomite cements alternated with thin bands of syntaxial calcite cement. The final diagenetic phase precipitated was a blocky calcite spar cement, representing diagenesis in a fresh-water lens. This sequence of diagenetic features arose as the result of a single fall in eustatic sea-level following deposition. A stratigraphic-eustatic-diagenetic model constrains both the timing and rate of dolomitization in southeastern Barbados. Dolomitization initiated as sea-level began to fall immediately following the oxygen isotope stage 7–3 high stand, some 216 000 yr bp . Due to the rapidity of late Pleistocene glacio-eustasy, dolomitization (locally complete) is constrained to have occurred within about 5000 yr.     

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.     

Changes in carbon and oxygen isotope composition during limestone diagenesis

The calcite fossils of the Derbyhaven Beds, Isle of Man, have δ¹³C values (+ 1·8 PDB) similar to modern, shallow-water marine skeletons, but the δ¹⁸O values (?6·1 PDB) are much lighter than modern skeletons. The light oxygen values indicate either re-equilibration with isotopically light water before cementation started, or Carboniferous sea water with δ¹⁸O of ?6‰. Aragonite dissolution was followed by precipitation of zoned calcite cement. In this cement, up to six intracrystalline zones, recognized in stained thin sections, show isotopic variation. Carbon varies from + 3-8 to + 1-2‰. and oxygen from ? 2-6 to ? 12-4‰. with decreasing age of the cement. This trend is attributed to increasing temperature and to isotopic evolution of the pore waters during burial. The zoned calcite is sequentially followed by dolomite and kaolinite cements which continue the trend towards light isotopic values. This trend is continued with younger, fault-controlled dolomite, and is terminated by vein-filling calcite and dolomite. The younger calcite, interpreted as a near-surface precipitate from meteoric waters, is unrelated to the older sequence of carbonates and has distinctly different carbon isotope ratios: δ¹³C ? 6-8‰.     

Early diagenetic carbonate precipitation and pore fluid migration in the Kimmeridge Clay of Dorset, England

In the argillaceous sequence of Kimmeridge Clay a carbonate rich bed is composed of ferroan dolomite cement with varying amounts of excess CaCO³, and Fe²⁺ substitution in the Mg²⁺ sites. The isotopic and chemical compositions change symmetrically about the centre of the band proving that it grew by vertical accretion during diagenesis. Textural and isotopic evidence shows that growth centred on a horizon rich in primary carbonate which became dolomitized and assimilated during production of diagenetic carbonate. This accounts for the lateral extent of the concretion. Early central diagenetic carbonate was produced from organic matter by bacterial fermentation (δ¹³C =+0.59‰) and later marginal carbonate by abiotic breakdown, (δ¹³C tending towards — 2.73‰). δ¹⁸O values range from — 1.56 to — 4.46‰ because the dolomite precipitated during progressive burial. As burial increased, magnesium, whose dominant source was trapped seawater, became depleted while the relative availability of Fe²⁺, whose source was dominantly reduced detrital oxides, increased. Dolomitization and the source of diagenetic components for dolomite formation are discussed. Diffusion and pore fluid migration transported ions to the site of precipitation. Early cementation of the band served to influence pore fluid migration, but thereafter pore fluid migration controlled carbonate precipitation.     

贵州紫云二叠纪生物礁的胶结作用

应用岩石学和地球化学方法研究了中国西南地区发育最好的紫云二叠纪生物礁组合的胶结作用,识别出七种胶结物类型,详细描述了它们的岩石学及地球化学特征,探讨了礁组合的胶结作用史。     

Dolomite characteristics and diagenetic model of the Calcari Grigi Group (Asiago Plateau,Southern Alps – Italy): an example of multiphase dolomitization

A multidisciplinary study, conducted over the carbonate platform deposits of the Liassic Calcari Grigi Group (Southern Alps), highlighted how the use of outcrop analogues can contribute to better define the distribution of dolomitic bodies related to fault networks, to characterize the petrophysical properties of the dolomitic sequence and unravel a complex diagenetic history. This study was carried out in the Asiago Plateau (southernmost part of the eastern Southern Alps, northern Italy) which provides excellent outcrops of the Jurassic Calcari Grigi Group. The dolomitization of the Jurassic sequence is variable in terms of stratigraphic extension and geographic distribution. In the studied localities the dolomitization is generally limited to the Mount Zugna Formation and is characterized by an undulatory front, with ‘sub‐vertical dolomitic chimneys’ along the major faults. Within this unit, and often associated with faults, stacked high‐porosity and permeability bed‐parallel dolomitic bodies are developed that show excellent petrophysical properties. The dolomitic intervals are characterized by pervasive unimodal and patchy polymodal dolomite crystals. Thin section, cathodoluminescence, isotopic and fluid inclusion analyses were used to constrain the paragenetic evolution of the sequence which is similar in all the studied localities. The first dolomitization stage is marked by zoned dolomite crystals with a dull luminescent core. The porosity is thought to have increased after this stage, with dark blue luminescent dolomite accompanied by the corrosion of older crystals. The appearance of saddle dolomite marks the onset of the porosity reduction stage, ending with the infilling of vugs and the remaining open pores with calcite cement. The diagenetic evolution locally stopped at the saddle dolomite stage with the complete occlusion of the remaining pores. Paragenetic and fluid‐inclusion data suggest an evolutionary trend of increasing temperatures and decreasing salinity toward brackish fluids responsible for dolomite and calcite precipitation. The integration of the available data seem to indicate that the diagenetic evolution of the study area is related to: (i) the interplay between evolving fluids (from marine to brackish); (ii) the burial of the sequence (increasing temperature); and (iii) the evolution of the hydrogeological system (fault and fracture network, fluid mixing). This complex paragenetic evolution is strongly linked to the evolution of the porosity framework that evolved from a good, widespread network in the early stages of the burial history to a confined system in the later stages due to reduction of porosity by the deposition of late calcite and dolomite cements.     

Diagenetic alterations in temperate shelf carbonates from southeastern Australia

Temperate shelf carbonates form in cool marine waters and have skeletal and mineralogical compositions which are different from their tropical counterparts. They commonly lack non-skeletal grains and are often composed of low- and high-magnesium calcite with subordinate aragonite. Many of the aragonitic components found in tropical carbonates, such as corals, ooids, blue-green algae and lime mud, are absent.

Temperate shelf carbonates undergo diagenesis in marine waters with lower carbonate saturation than do tropical carbonates, and are exposed to cool climates with moderate to low rainfall. Marine cementation is rare because of low carbonate saturations in the surrounding waters. However, aragonite and high-magnesium calcite cements have been reported forming under specialized conditions associated with biogenic precipitation, submarine methane and sulphate-reducing bacteria, and more commonly in the intertidal environment where evaporation has increased carbonate concentrations.

In Pleistocene and Tertiary temperate shelf carbonates from southeastern Australia, evidence of marine diagenesis is rare to absent. Diagenetic stabilization of aragonite and high-magnesium calcite has taken from 80,000 y to 1 My, or longer, during subaerial exposure. This is slower than rates reported from tropical climates. A general lack of aragonite in some facies within these temperate carbonates leads to a lack of secondary porosity and only sparse low-magnesium calcite cement, even after prolonged fresh-water diagenesis. However, with lengthy exposure and under the right climatic conditions, karstic solution and calcrete precipitation can occur.

In sequences containing siliciclastic clays, pyrite and glauconite, abundant iron is present in interstitial waters leading to the precipitation of ferroan calcite cements in the phreatic and shallow burial environments, and to the substitution of iron for magnesium in stabilizing high-magnesium calcite skeletal material.

A unique void-filling, micritic internal sediment occurs in discrete layers in many of the Tertiary temperate shelf carbonate sequences in southeastern Australia. This internal sediment is localized as a pore-filling material above permeability barriers such as fine-grained sediments or volcanics, and above paleo-water tables which formed during periods of subaerial exposure. It is a feature of the vadose zone and lithifies to form a dense micritic low-magnesium calcite cement with characteristic pink/brown coloration, often associated with erosion surfaces and nodule beds.

Dolomite is uncommon in the southeastern Australian temperate shelf carbonates. It forms associated with preferential fluid pathways or mixing zones. Ferroan dolomite forms in siliciclastic clay-rich carbonates in the shallow burial environment. The ubiquitous fine, evaporite-related dolomite so common in tropical carbonates is absent.