Evolution of late Triassic rift basin evaporites (Passaic Formation): Newark Basin, Eastern North America

The Passaic Formation of the late Triassic Newark Supergroup is 2700 m thick and was deposited in series of wide, deep to shallow lacustrine environments in the Newark rift basin (eastern North America). The Passaic Formation can be divided into lower, middle, and upper sections based on depositional structures, composition and the distribution and morphology of its evaporites. Evaporites formed as a result of syndiagenetic cementation and/or displacive processes. Evaporitive minerals now include gypsum and anhydrite, although other mineral species, such as glauberite, may have originally existed. Most of the evaporites of the Passaic Formation occur within massive red mudstone and siltstone lithologies in the form of diffuse cements, void-fillings, euhedral crystals, crystal clusters and nodules. These evaporites grew displacively within the fine siliciclastic matrix as a result of changes in the hydrochemical regimes of the rift basin. A well-developed upward increase in the amount of evaporite material is present in the Passaic Formation. This resulted from: (1) long-term, progressive increase in aridity, and (2) significant increase in evaporation surface area of the basin during its tectonic evolution. A nonmarine source for the evaporites is evident from the isotopic data. Sulphate δ³⁴S ranges from 11%. to 3.3%. CDT, while δ¹⁸O ranges from + 15.1%. to + 20.9%. SMOW, indicating derivation from early diagenetic oxidation of organic sulphur and pyrite within the organic-rich, lacustrine deposits. The ⁸⁷Sr/⁸⁶Sr ratios in sulphate are radiogenic (average 0.71211), showing the interaction of basin waters with detrital components and that the Newark Basin was isolated from the world ocean. Most of the original evaporites show evidence of diagenetic change to polycrystalline and polymineralic pseudomorphs now filled with recrystallized coarse-grained anhydrite (1–3 mm size) and low-temperature albite. Homogenization temperatures of fluid inclusions within the coarse-grained anhydrite indicate crystallization temperatures for anhydrite in the range of 150° to 280°C. Such elevated temperatures resulted from circulation of hot water in the basin. Later exhumation of these rocks caused partial to total replacement of anhydrite by gypsum in the upper part of the section. The resulting increase in volume due to hydration of anhydrite at shallow depths also emplaced non-evaporative satin-spar veins (fibrous gypsum) along bedding planes and in fractures. While the local geology of the Newark rift basin controlled the distribution of facies, the sedimentological development of the Passaic Formation evaporites resulted from the world-wide climatic aridity that prevailed during the late Triassic. because the Newark Basin sequence was only covered with about 3 km of sedimentary overburden that correspond to about 100°C and hence suggests that evaporites have experienced alteration by hot fluids. 5 As the Triassic marks the greatest evaporite formation world-wide and profound sense of parched continentality throughout the world existed before the final break-up of the Pangea, the Passaic Formation evaporites are an example of the influence of these palaeoclimatic conditions at the eastern margin of North America.     

Unravelling the fluid flow evolution and precipitation mechanisms recorded in calcite veins in relation to Pangea rifting–Newark Basin,USA

Calcite veins hosted in the Triassic Stockton, Lockatong and Passaic formations of the Newark Basin are investigated to reconstruct the fluid evolution. To constrain the parameters of calcite precipitation, a microthermometry study was carried, which reveals precipitation of calcite from a low to moderate saline H₂O-NaCl fluid (0.4 to 13.2 wt% NaCl equiv.) under low to moderate hydrothermal (137 °C to 232 °C) conditions. This fluid composition is interpreted to reflect mixing between a deep basement-derived heated diluted fluid and relatively low to moderate saline diagenetic formation waters hosted in the different Triassic formations. Carbon and strontium isotope analysis on the vein calcites suggests that these elements are derived from the pre-Triassic basement and the sedimentary cover through fluid-rock interactions. The aforementioned geochemical findings are supported by Rare Earth Elements and Yttrium (REY) systematics and oxygen isotope data.The Late Triassic extensional activity and gravity-driven fluid flow mechanism facilitated the infiltration of meteoric waters to deeper lithostratigraphic units (i.e., Precambrian-Paleozoic basement-Triassic Stockton Formation) where they became heated. In response to the extensional tectonics, the deep-seated hydrothermal basement-derived diluted fluids migrated upward along the tectonic-related fractures and the major faults to upper shallow crustal levels. Here, the heated, diluted meteoric waters were mixed with low, moderately saline, and relatively cooler formation waters, leading to calcite precipitation. The pH increase is suggested to be a contributing factor in the precipitation of calcite.     

Diagenetic mineral development within the Upper Jurassic Haynesville-Bossier Shale,USA

Despite recent advances, diagenetic processes in fine-grained sediments are still relatively poorly understood. Key questions still to be resolved include the types of diagenetic minerals present in mudstones and the extent of element mobility in these low permeability systems. This study utilizes data from the Haynesville-Bossier Shale, USA, to analyze lithologies, discriminate authigenic phases and identify mobile elements during diagenesis. It has implications for understanding how authigenic minerals develop and the sources of those authigenic minerals in fine-grained sediments. On the basis of grain-size and mineralogy five lithologies are designated: (i) silica-rich argillaceous mudstones; (ii) argillaceous siliceous mudstones; (iii) mixed siliceous mudstones; (iv) mixed mudstones; and (v) authigenically-dominated mudstones. The diagenetic development of the Haynesville-Bossier Shale can be divided into early and late diagenesis. Ferroan and non-ferroan dolomite, framboidal pyrite and bioclast pore-filling kaolinite and calcite grain replacements and cements all formed during early diagenesis. Late diagenetic mineral phases include illite formed by the illitization of smectite, replacive and displacive chlorite, calcite-replacive albite, quartz-replacive calcite and replacive and/or displacive quartz. The presence of extensive late diagenetic mineral precipitates indicates that there was a degree of element mobility on at least the local scale. Aluminium present in albite is most likely to have resulted from the illitization of smectite. Quartz overgrowths probably resulted from illitization and the pressure dissolution at quartz silt grain boundaries. Externally, hydrothermal fluids resulting from regional-scale igneous activity appear to have played a role in the formation of chlorite and possibly albite. The work indicates that extensive mineral development and element mobility occurred during late diagenesis.     

Analcime in lake and lake-margin sediments of the Carboniferous Rocky Brook Formation, Western Newfoundland, Canada

In the Deer Lake Basin of western Newfoundland, Canada, analcime has been found within fine-grained, siliciclastic and carbonate, lake and lake-margin sediments of the Carboniferous Rocky Brook Formation. Analcime is the only zeolite observed in these unmetamorphosed and non-volcanogenic rocks. Microscopic analcime occurs as vug-filling, limpid, isotropic to anisotropic crystals. Microprobe analyses show this type of analcime to be lower in silica than most analcime in sedimentary rocks. A second textural type of finer-grained submicroscopic analcime can be detected from X-ray diffraction spectra of Rocky Brook Formation mudstones, where it is associated with phyllosilicates (illite, interstratified chlorite/smectite, smectite, chlorite), other silicates (quartz, feldspar) and carbonates (dolomite, calcite). Results of this study suggest that the analcime in the Rocky Brook Formation formed either by direct lakewater/porewater precipitation or by reaction of these waters with one or more clay mineral types or plagioclase.     

Contact metamorphic mineral assemblages,late Triassic Newark group,New Jersey

Essentially isochemical thermal metamorphism of soda-rich Stockton, Lockatong and Brunswick formations of the Newark Group by diabase sills produced unusually varied and unique mineral assemblages, most of which are predominantly Na. feldspar and biotite. Within a meter of a sill Stockton arkose was altered to quartzo-feldspathic hornfels with common diopside and sphene. Within 50 m of a sill Lockatong calcitic and dolomitic mudstone formed calc-silicate hornfels with differing combinations of diopside-hedenbergite, andradite and grossular, prehnite, datolite, idocrase and wollastonite. Within a meter of a sill metamorphosed Lockatong calcareous feldspathic argillite contains sanidine-anorthoclase, aegirine, aegirine-augite, riebeckite and scapolite. Lockatong analcime-dolomite argillite was altered to unique feldspathoidal assemblages containing cancrinite, natrolite-thomsonite and rarely sodalite within 134 m, and nepheline within 30 m of the Byram Sill. Reddish-brown Brunswick mudstone produced spotted pelitic hornfels within a few 10's of meters of a sill.Response to thermal metamorphism varied directly with diminishing grain size. In both sandstone and mudstone Na. feldspar increases and K. feldspar decreases toward intrusions; quartz is rare or absent in highest-grade hornfels. Development of biotite was retarded by detrital clay minerals and hematite pigment, as well as by low temperature. Minor differences in composition among carbonate-rich and analcime-rich Lockatong deposits led to a diversity of closely associated assemblages. Aqueous solutions and relatively low temperature, probably in part during retrogressive metamorphism, produced hydrous minerals. Datolite, tourmaline, scapolite and fluorite suggest minor additions of volatiles, but the widespread feldspathoids were made from soda-rich sedimentary rocks without significant additions from an igneous source.     

Authigenic albite in carbonate rocks – a tracer for deep-burial brine migration?

Euhedral, post-depositional albite from the Eastern and Western Alps, the western Carpathians and some Greek islands was examined petrographically and geochemically to gain insights into the nature of feldspar reactions in carbonate rocks. This study focuses on coarsely crystalline, homogeneously nucleated albite in order to avoid problems related to the presence of inseparable detrital material in fine-grained albite varieties. All albite samples show a very restricted compositional variability and are typically ≥ 99 mol% Ab component. Unit-cell parameters determined by Rietveld analysis are slightly more variable than previously accepted, but confirm high Al–Si ordering characteristic of low albite. The oxygen isotopic composition of albite ranges from + 19·4‰ to + 28·3‰ VSMOW. There is no direct relationship between the δ¹⁸O value and the inferred temperature of albite formation, nor is there one with stoichiometry. The coarse crystal size (up to several millimetres in diameter), petrographic evidence showing albite cross-cutting stylolites, greater abundance of albite in carbonate rocks subject to high-grade diagenetic or weak metamorphic overprinting and available fluid inclusion data suggest that albite precipitation is favoured at higher temperatures in carbonates than in sandstones. Pore fluids were invariably brines, as suggested by the inferred high positive δ¹⁸O_fluid values, the common association of albite-bearing carbonates and evaporites and reports of saline fluid inclusions in albite. The presence of authigenic albite may thus be a useful tracer of palaeobrine–carbonate reactions, particularly in deep-burial and incipient metamorphic settings.     

渤海湾盆地北塘凹陷古近系沙河街组三段白云岩中方沸石的特征及成因

渤海湾盆地北塘凹陷古近系沙河街组三段白云岩中有多种矿物,X射线衍射(XRD)分析识别出的主要矿物有白云石、方沸石、石英、长石、黏土矿物、黄铁矿及方解石等,其中方沸石平均含量达38.8%。根据钻井岩心、岩石薄片、扫描电镜、电子探针和地球化学分析等资料,对沙三段白云岩中方沸石的矿物特征进行详细描述并探究其成因。结果表明,沙三段白云岩中的方沸石有2种分布样式,分别是纹层型和充填型,其中前者多与白云石互层、呈纹层状,偶见似结核状;后者形成较晚,方沸石以填隙物形式充填在裂缝、孔隙之中。这2种方沸石的存在形式、晶体形态、伴生矿物各不相同,其中纹层型方沸石多与白云石共生,晶体粒径小于0.04,mm,为泥晶结构;充填型方沸石多与黄铁矿、有机质共生,晶体粒径大于0.04,mm,为粉晶结构。根据主、微量元素及碳、氧同位素分析结果,计算出古盐度平均为28.8‰,Sr/Ba值平均为2.93,表明渤海湾盆地北塘凹陷沙河街组三段沉积时期为碱—咸溶液沉积环境,具备形成方沸石的条件。电子探针测试的Si/Al值表明,这2类方沸石母质来源不同,纹层型方沸石母质为黏土矿物,而充填型方沸石母质与热液有关。与国内含方沸石白云岩的盆地进行对比,并从岩石学特征、形成温度等方面进行分析,认为研究区方沸石有2种成因,其中纹层型方沸石是同生成岩阶段的产物,而充填型方沸石则受到热液流体的影响。     

Authigenic quartz and albite in Devonian limestones: origin and significance

Euhedral quartz and albite crystals are common in Devonian (Givetian-Frasnian) shallow-marine shelf carbonates from the Belgian Ardennes. Several features such as morphology, the presence of carbonate inclusions, inversion temperatures and occurrence in the insoluble residues of stylolitic surfaces indicate that these crystals have developed authigenically. Oxygen isotope ratios point to an intermediate deep burial realm of origin at temperatures of 60–90°C. The predominance of illite and the almost total absence of smectite clay minerals is interpreted as an indication that illitization produced the silica needed for authigenesis. The mineral composition of inclusions indicates that the carbonate host rock must have consisted of low-Mg calcite already at the time of authigenesis. These inclusions represent an earlier diagenetic stage than the present carbonate rock, since they were protected from further diagenetic alteration by the surrounding quartz. The calcite inclusions display a higher Sr/Ca and Mg/Ca ratio than the carbonate host-rock. Because neomorphic diagenesis of the carbonate continued after silicate authigenesis, the contents of Mg and Sr in the calcite of the host carbonate are even lower. The authigenic feldspar mineralogy seems to be determined by the composition of the host-sediment.     

含钠长石翡翠成因探讨

为详细探讨含钠长石翡翠的成因机制,笔者选取了若干来自缅甸的含钠长石翡翠,对其进行了详细的岩相学、矿物化学等方面的研究。含钠长石翡翠样品属于豆青种,主要由硬玉、钠长石、方沸石和少量的多硅白云母、钡铝硅酸盐等矿物组成。其中的硬玉发育清晰的环带结构,成分从核部至边缘发生规律性的成分变化。翡翠同时受到两期后期流体活动的改造,第一期以钠长石为代表,第二期以方沸石为代表,流体的改造作用使硬玉呈现碎裂状、碎斑状结构和交代穿孔等结构。结果表明,含钠长石翡翠样品表现出从成岩流体中直接结晶的特点,该流体富集Na、Al、Si、K、Ba以及少量的Ca、Fe、Mg等元素,微量元素则相对富集LREE、HFSE和sr等元素。结合前人的研究结果以及该玉石中的矿物反应关系,笔者推测缅甸翡翠形成的压力和温度范围分别在6-14kbar和300℃-450℃。     

Analcimic zones in the tertiary of anatolia and their geological positions

The Anatolian Tertiary and especially the Neogene have some geological series with analcime as the principal rock-forming mineral. Sedimentation basins receiving material in suspension and in solution permit the authigenesis of analcime dolomite, calcite and opal(C-T). Analcimes formed by hydrothermal alteration on the ocean floor, after the pillow lava and diabasic dyke complexes of ophiolites, can form a source of detrital analcime when they are on the continental medium. Continental alteration of the pillow lavas and diabasic dykes permits the formation of solutions suitable in composition for analcime authigenesis. Analcimes formed in these environments are particularly related to the silica content of these media.Principal clay minerals formed with analcimic formations are smectites and (14_s—14_c) mixed layers. Illite, chlorite and corrensite are also present in smaller quantities.     

Depositional environments and diagenesis in Lake Parakeelya: a Cambrian alkaline playa from the Officer Basin, South Australia

Laminated and desiccated siliceous dolostones, dolomitic mudstones and dolomitic sandstones in the Cambrian Parakeelya Alkali Member of the Observatory Hill Formation accumulated in an alkaline playa. Four facies are recognized (from lake centre to lake edge): lake, saline mudflat, dry mudflat and sandflat facies. The facies occur in cycles. Cycles of tens of metres thickness record the gradual expansion and contraction of the playa. Superimposed smaller cycles of tens of centimetres thickness record minor oscillations in the position of the strandline in a shallow lake. The dominance of saline mudflat, dry mudflat and sandflat facies indicates that the lake was rimmed by broad flat areas with negligible relief. The high δ¹⁸O values of primary and penecontemporaneous diagenetic carbonates of +24 to +28‰ (SMOW) indicate strong evaporation of ground and surface waters within the lake system. Calcite pseudomorphs of the sodium carbonate minerals trona and shortite have δ¹⁸O values between + 19 and + 22.5‰, and contain fluid inclusions with variable salinites and homogenization temperatures up to around 110°C. This suggests that the euhedral alkaline evaporites were dissolved by heated waters; calcite pseudomorphs then precipitated from a mixed solution formed by the interaction of these incoming fluids with the relatively saline interstitial brines. The sodium bicarbonate solutions formed by dissolution of the evaporites would have been dispersed by the basinal brines so that despite the closed drainage, further groundwater concentration did not take place.     

Replacement of evaporites within the Permian Park City Formation, Bighorn Basin, Wyoming, USA

The Permian Park City Formation consists of cyclically bedded subtidal to supratidal carbonates, cherts and siltstones. Early diagenesis of Park City Formation carbonates occurred under the influence of waters ranging from evaporative brines to dilute meteoric solutions and resulted in evaporite emplacement (syndepositional nodules and cements), as well as dolomitization, silicification and leaching of carbonate grains. Major differences are seen, however, in the diagenetic patterns of subsurface and surface sections of Park City Formation rocks. Subsurface samples are characterized by extensively preserved evaporite crystals and nodules, and preserve evidence of significant silicification (chert, chalcedony and megaquartz) and minor calcitization of evaporites. In outcrop sections, the evaporites are more poorly preserved, and have been replaced by silica and calcite and also leached. The resultant mouldic porosity is filled with widespread, very coarse, blocky calcite spar. These replacements appear to be multistage phenomena. Field and petrographic evidence indicates that silicification involved direct replacement of evaporites and occurred during the early stages of burial prior to hydrocarbon migration. Siliceous sponge spicules provided a major source of silica, and the fluids involved in replacement were probably a mixture of marine and meteoric waters. A second period of replacement and minor calcitization is inferred to have occurred during deep burial (under the influence of thermochemical sulphate reduction), although the presence of hydrocarbons probably retarded most other diagenetic reactions during this time interval. The major period of evaporite diagenesis, however, occurred during late stage uplift. The late stage replacement and pore-filling calcites have δ¹³C values ranging from 0·5 to -25·3%, and δ¹⁸O values of -16·1 to -24·3₀ (PDB), reflecting extensive modification by meteoric water. Vigorous groundwater flow, associated with mid-Tertiary block faulting, led to migration of meteoric fluids through the porous carbonates to depths of several kilometres. These waters reacted with the in situ hydrocarbon-rich pore fluids and evaporite minerals, and precipitated calcite cements. The Tosi Chert appears to have been an even more open system to fluid migration during its burial and has undergone a much more complex diagenetic history, as evidenced by multiple episodes of silicification, calcitization (ferroan and non-ferroan), and hydrocarbon emplacement. The multistage replacement processes described here do not appear to be restricted to the Permian of Wyoming. Similarly complex patterns of alteration have been noted in the Permian of west Texas, New Mexico, Greenland and other areas, as well as in strata of other ages. Thus, multistage evaporite dissolution and replacement may well be the norm rather than the exception in the geological record.     

Diagenesis in tertiary sandstones from Kettleman North Dome. California—II. Interstitial solutions: Distribution of aqueous species at 100°C and chemical relation to the diagenetic mineralogy

Interstitial brines from the Temblor and the McAdams sandstones at Kettleman are essentially NaCaCl solutions with subsidiary SO₄ and the total salinities are roughly 30,000 and 10,000 ppm, respectively. Activities of H⁺ and all other aqueous species have been calculated for 100°C (the in situ temperatures of the brines) from chemical analyses of the brines and 100-degree dissociation constants alone. The brine alkalinities measured at surface temperature appear to be too low when comparing them against alkalinities calculated from the measured pHs of the brines. Consequently, alkalinities calculated for 25°C were substituted for the measured ones in the calculation of the distribution of aqueous species at 100°C.Although the brines are nearly neutral (pH 6·3–d7·9) at surface temperature, their pHs calculated for 100°C range from 8·1 to 8·7 (± 0·35). These pHs and the 100-degree activities of the other aqueous species permit graphic representation of the brines on activity diagrams. Most brines fall at or near the boundaries between the stability fields of quartz, albite, microcline, mica, montmorillonite and anhydrite. Because these minerals are present as authigenic phases in the sandstones, the calculations suggest that the minerals are in stable equilibrium with the brines. By contrast, the calculations suggest that the brines are supersaturated by about three orders of magnitude with respect to calcite, also present in the sandstones. One possible explanation for this is kinetic inhibition of calcite crystallization by Mg²⁺ and SO₄^2? ions in the brines. Phosphatic pellets, glauconite and probably dolomite, pyrite and some kaolinite are early authigenic minerals preserved in the sandstones and they are not now in equilibrium with the brines, which are supersaturated with respect to dolomite and pyrite. The chemical relationship between the brines and the diagenetic minerals laumontite and sphene, also present in the Temblor Formation, cannot be assessed reliably until the thermodynamic properties of laumontite and of aqueous titanium complexes are well known.     

Lower Rotliegend fluvio-lacustrine sequences in the Saar-Nahe Basin

The Rotliegend beds of the middle of the Kusel Group to the middle of the Lebach Group in the Saar-Nahe Basin are characterized by sedimentary sequences which developed in streams, deltas, and lakes. The stream sequences consisting of cross-stratified sandstone units are attributed to braided fluvial environment. The lake-delta sequences usually show gradual transition from lacustrine mudstones to delta-front cross-stratified sandstones and to floodbasin, crevasse and overbank sandstones and mudstones. Loaded high-intensity flows occasionally result in deformation- and erosion-structures. Low-energy lacustrine sedimentation is evident from paper-shales and massive mudstones. The mudstones alternate with cross-laminated sandstones where influenced by terrigenous influx.     

古代碳酸盐岩台地自生泥质组分成因及意义

台地泥质组分沉积记录了源—汇过程和环境演化等沉积学领域信息,可作为古气候和古环境重建的重要载体。然而,利用沉积物中的泥质组分进行古气候和古环境恢复时仍存在相当大的复杂性和局限性。鉴于此,笔者以上寺剖面中二叠统茅口组为例,通过研究该层位富泥质组分灰岩—泥灰岩韵律的宏微观形貌学和矿物学特征,发现其泥质组分主要由成岩黏土矿物海泡石构成,其次为少量滑石和蒙脱石。基于前人认识,进一步运用电子探针和激光原位元素地球化学分析手段,综合认为海泡石中镁元素来源于继承海水的孔隙水以及亚稳定矿物的转化释放,硅元素可能来源于上扬子台地的同沉积期断裂热液。此外,滑石主要形成于海泡石埋藏过程中的成岩转化,蒙脱石可能也具有类似成因,但不排除有少量蒙脱石来源于火山物质的海底改造。结合区域资料,华南中二叠统浅水碳酸盐台地上广泛发育自生成因（早期成岩作用和埋藏成岩作用）泥质组分。因此,在利用泥质组分来恢复古环境的时候,需要谨慎识别其成因,这将有利于提高沉积旋回识别和环境解释的准确性;另一方面,对自生成因泥质组分进行专门研究,在成岩过程以及成岩地球化学信号识别上也具有参考价值。     

Discrete clay diagenesis in a very low-permeable sequence constrained by an isotopic (K–Ar and Rb–Sr) study

Multimethod analyses of several size fractions of clays were used to reconstruct the diagenetic history of the shallow buried claystones within the Paris Basin. A systematic decrease occurred in K-Ar dates relative to the decrease in size of the clay fractions, signifying higher amounts of newly formed clay material in the finer fractions. We suggest that the authigenic clay minerals occurring in the fine fractions had an Al-montmorillonite composition. By assuming that the isotopic K-Ar and Rb-Sr dates obtained on a bentonite layer in the sedimentary sequence stand for pure, authigenic clay minerals, one may interpret all K-Ar dates as mixtures of one authigenic and two detrital end-members. The results imply that a period of low sea level favoured diagenetic smectite-type clay formation about 10-15 million years after deposition of the sediments. Signatures of limited-scale chemical and isotopic homogenisation mean that the rock volumes affected by the diagenetic modifications had to be quite limited. The study of clay minerals extracted from some stylolites further suggests that any overpressure related to the origin of stylolites had no effect on clay authigenesis.     

Syngenetic and diagenetic features of evaporite-lutite successions of the Ipubi Formation,Araripe Basin,Santana do Cariri,NE Brazil

The Ipubi Formation in the Araripe Basin (Northeast Brazil) has evaporite-lutite successions rich in gypsum, a mineral of great regional economic relevance, a highlighted stratigraphic mark, and also a natural boundary for underlying successions potentially analogous to “Pre-Salt” hydrocarbon reservoirs of the Brazilian coastal basins. In this study, syngenetic and diagenetic aspects of the Ipubi Formation at Santana do Cariri (Ceará State) were investigated by means of facies analysis, petrography, and mineralogical/chemical analyses of evaporites and shales.The results show that the contact relationship between evaporites and marly shales, without signs of subaerial exposure and laterally adjacent, was associated with shallow, calm and somewhat anoxic waterbodies, locally salt-supersaturated (brines) but under seasonal variations of water levels. This scenario could have shared place with hydrothermal phenomena in a playa lake depositional system. Regarding diagenesis, although there is evidence supporting pseudomorphic replacement of gypsum by anhydrite, the burial of the Ipubi Formation would have been limited due to the frequent occurrence of gypsum without any trace of chemical replacement.     

Fluid–rock reactions in an evaporitic mélange, Permian Haselgebirge, Austrian Alps

Tectonically isolated blocks of carbonate rocks present within the anhydritic Haselgebirge mélange of the Northern Calcareous Alps record a complex history of deformation and associated deep-burial diagenetic to very low-grade metamorphic reactions. Fluids were hot (up to ≈ 250 °C) and reducing brines charged with carbon dioxide. Individual carbonate outcrops within the mélange record different regimes of brine–rock reactions, ranging from pervasive dolomite recrystallization to dedolomitization. Early diagenetic features in these carbonates were almost entirely obliterated. Matrix dolomite alteration was related to thermochemical sulphate reduction (TSR) recognized by the replacement of anhydrite by calcite + pyrite ± native sulphur. Pyrite associated with TSR is coarsely crystalline and characterized by a small sulphur isotope fractionation relative to the precursor Permian anhydrite. Carbonates associated with TSR show low Fe/Mn ratios reflecting rapid reaction of ferrous iron during sulphide precipitation. As a result, TSR-related dolomite and calcite typically show bright Mn(II)-activated cathodoluminescence in contrast to the dull cathodoluminescence of many (ferroan) carbonate cements in other deep-burial settings. In addition to carbonates and sulphides, silicates formed closely related to TSR, including quartz, K-feldspar, albite and K-mica. ⁴⁰Ar/³⁹Ar analysis of authigenic K-feldspar yielded mostly disturbed step-heating spectra which suggest variable cooling through the argon retention interval for microcline during the Late Jurassic. This timing coincides with the recently recognized subduction and closure of the Meliata-Hallstatt ocean to the south of the Northern Calcareous Alps and strongly suggests that the observed deep-burial fluid–rock reactions were related to Jurassic deformation and mélange formation of these Permian evaporites.     

Carbonate dissolution in Mesozoic sand- and claystones as a response to CO2 exposure at 70 °C and 20 MPa

The response to CO₂ exposure of a variety of carbonate cemented rocks has been investigated using pressurised batch experiments conducted under simulated reservoir conditions, 70 °C and 20 MPa, and with a durations of up to14 months. Calcite, dolomite, ankerite and siderite cement were present in the unreacted reservoir rocks and caprocks. Core plugs of the reservoir rocks were used in order to investigate the alterations in situ. Crushing of the caprock samples was necessary to maximise reactions within the relatively short duration of the laboratory experiments. Synthetic brines were constructed for each batch experiment to match the specific formation water composition known from the reservoir and caprock formations in each well. Chemical matched synthetic brines proved crucial in order to avoid reactions due to non-equilibra of the fluids with the rock samples, for example observations of the dissolution of anhydrite, which were not associated with the CO₂ injection, but rather caused by mismatched brines.Carbonate dissolution as a response to CO₂ injection was confirmed in all batch experiments by both petrographical observations and geochemical changes in the brines. Increased Ca and Mg concentrations after 1 month reaction with CO₂ and crushed caprocks are ascribed to calcite and dolomite dissolution, respectively, though not verified petrographically. Ankerite and possible siderite dissolution in the sandstone plugs are observed petrographically after 7 months reaction with CO₂; and are accompanied by increased Fe and Mn contents in the reacted fluids. Clear evidence for calcite dissolution in sandstone plugs is observed petrographically after 14 months of reaction with CO₂, and is associated with increased amounts of Ca (and Mg) in the reacted fluid. Dolomite in sandstones shows only minor dissolution features, which are not clearly supported by increased Mg content in the reacted fluid.Silicate dissolution cannot be demonstrated, either by chemical changes in the fluids, as Si and Al concentrations remain below the analytical detection limits, nor by petrographical changes, as partly dissolved feldspar grains and authigenic analcime are present in the sediments prior to the experiments. It is noteworthy, that authigenic K-feldspar and authigenic albite in sandstones show no signs of dissolution and consequently seem to be stable under the experimental conditions.