Thermal history of the evaporitic Haselgebirge mélange in the Northern Calcareous Alps (Austria)

In the central and eastern part of the Northern Calcareous Alps, Upper Permian evaporitic rocks form a tectonic mélange whose distribution is restricted largely to the topmost thrust unit (Juvavicum). Mudrock and dolostone samples associated with the evaporites in ten major outcrops (mostly mines) were examined in order to constrain the paleothermal conditions of the mélange. Measurements of illite "crystallinity" reveal a regionally variable pattern of metamorphic grade ranging from diagenesis to the high anchizone and possibly epizone. Most samples contained very little organic matter and vitrinite particles were rare. Samples containing vitrinite show consistent minimum reflectance values of ～1.3–1.7% R_o, whereas maximum reflectance values are more variable (up to 4.9%). The former data constrain the minimum burial temperatures to ～160–180°C. The observed variability in illite "crystallinity" and organic maturity both between and within individual outcrops is consistent with the mélange architecture of this unit and is in good agreement with the regional thermal pattern recognized in Middle to Upper Triassic carbonate formations within the Juvavicum by conodont color alteration studies. Mélange formation and heating of the evaporites is suggested to be linked to the Upper Jurassic closure of the Meliata-Hallstatt Ocean and subsequent thrusting of obducted terranes (Juvavicum) into the depositional realm of the Northern Calcareous Alps.     

Evinosponges in the Triassic Esino Limestone (Southern Alps): documentation of early lithification and late diagenetic overprint

A carbonate buildup of Middle Triassic age, the Esino Limestone, outcrops in the Southern Calcareous Alps of Lombardy (N Italy). Along its margin and within the open subtidal facies, the Esino Limestone contains calcite cement-filled cavities of cm to m size. These features, known as evinosponges, may form pervasive networks within the host rock. The filling consists of concentric, isopachous layers of fibrous low-Mg calcite crystals characterized by strong undulose extinction and bent cleavages. The cement crusts are non-luminescent under cathodoluminescence, but both cements and host rock are cross-cut by micro-fractures filled with bright-luminescent calcite, related to late void-filling sparite. Mixing of different carbonates is reflected in stable isotope data. On the hand specimen scale, the oxygen and carbon isotope compositions of cements and host rock show little variation. When compared on a regional scale, the values cover a broad range from δ¹⁸O(PDB)=?5‰ to ?12‰ and from δ¹³O =0‰ to +3‰. The linear covariant trends defined by the oxygen and carbon isotope data for different sampling regions reflect the admixture of late, isotopically depleted calcite with an isotopically enriched non-luminescent calcite of early diagenetic origin. The Esino Limestone fibrous cements, which were probably precipitated in the marine or marine-meteoric phreatic environment, were affected by late diagenetic processes that caused mineral deformation and isotopic depletion through recrystallization and the admixture of a later calcite. These later calcites precipitated from penetrative fluids possibly related to Late Triassic volcanic activity and/or to the Late Cretaceous/Early Palaeogene alpine orogeny.     

Silicification of sulphate evaporites and their carbonate replacements in Eocene marine sediments, Tunisia: two diagenetic trends

Samples of chert nodules, diagenetic carbonates and evaporites (gypsum/anhydrite) collected from the gypsiferous limestones of the Kef Eddour Member (Ypressian‐Priabonian) near Metlaoui and Sehib (Tunisia) show selective silicification with great variety in the silicified by‐products. Based on δ¹³C values, which support an organic origin for the carbon, carbonates replaced evaporites microbially through bacterial sulphate reduction. Observations and results suggest two scenarios for chert formation that are related to the rate and timing of diagenetic carbonate replacement of the evaporites (anhydrite/gypsum). In the absence of early diagenetic carbonate phases, silica with δ¹⁸O values from +25 to +28·6‰ [standard mean ocean water (SMOW)] replaced the outer parts of anhydrite nodules at pH < 9. In contrast, pore‐fluid pH values > 9 in the innermost parts of the anhydrite nodules prevented silica precipitation. The record of this chemical barrier is preserved in the microquartz rims and geode features that formed in the inner parts of the nodules after dissolution of the anhydrite nucleus. The microbial diagenetic replacement of evaporites (bacterial sulphate reduction) by carbonates (calcite, aragonite and dolomite) favoured silica replacement of carbonates rather than evaporites. Silica, with δ¹⁸O signature of +21 to +26‰ (SMOW), replaced carbonates on a volume‐for‐volume basis, yielding a more siliceous groundmass, and accounting for 90–95% of the nodules. The relatively higher δ¹⁸O values of quartz replacing anhydrite can be explained by a diagenetic fluid in equilibrium with mixed (meteoric/marine) to marine water. The lower δ¹⁸O values of the quartz that replaced the diagenetic carbonates are ascribed to flushing by meteoric water in a later diagenetic stage. The silica supply for chert formation could be derived from the reworked bio‐siliceous deposits (diatomites) to the west of the basin [vestiges of an opal‐CT precursor undetectable by X‐ray diffraction (XRD) were revealed by δ²⁹Si magic‐angle‐spinning nuclear magnetic resonance investigations], diagenesis of the extraformational and overlying clay‐rich beds (the host limestones are clay‐poor as shown by XRD measurements), and minor volcanogenic and hydrothermal contributions during early diagenetic stages.     

Diagenetisch gebildeter Magnesit und Dolomit in den Grödener Schichten des Dobratsch im Gailtal,Kärnten — österreich

Dolomite, magnesite, calcite and aragonite are described from sandstones and conglomerates of the Grödener Schichten of the Dobratsch in the Gailtal Alps, Carinthia — Austria. The carbonates occur as early and late diagenetic cements, as recrystallized matrix of more or less laminated carbonate layers (up to 0.5 m thick), as concretions, as fillings of early diagenetic shrinkage cracks and late diagenetic fissures and as crystals in open cavities and clefts. The formation of dolomite and magnesite may have been caused by pore solutions highly enriched in magnesium, which are likely to have formed by evaporation in a hypersaline environment. Magnesite and dolomite most probably have been formed diagenetically from aragonite and/or calcite during progressive evaporation cycles. Because of magnesite is a common constituent in Permo-Scythian sediments of the Eastern Alps, its presence is of importance for the evaluation of the environment. Additionally the wide-spread occurrence of magnesite within these post variscian sediments has important implications regarding the paleogeographical reconstruction and the evaluation of diagenetic processes.     

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.     

Diagenesis of a mixed siliciclastic/evaporitic sequence of the Middle Muschelkalk (Middle Triassic), the Catalan Coastal Range, NE Spain

The Middle Muschelkalk (Middle Triassic) of the Catalan Coastal Range (north-east Spain) comprises sandstone, mudstone, anhydrite and minor carbonate layers. Interbedded sandstones and mudstones which are dominant in the north-eastern parts of the basin are terminal alluvial fan deposits. South-westward in the basin, the rocks become dominated by interbedded evaporites and mudstones deposited in sabkha/mudflat environments. The diagenetic and pore water evolution patterns of the Middle Muschelkalk suggest a strong facies control. During eodiagenesis, formation of microdolomite, anhydrite, baryte, magnesite, K-feldspar and mixed-layer chlorite/smectite was favoured within and adjacent to the sabkha/mudflat facies, whereas calcite, haematite, mixed-layer illite/smectite and quartz formed mainly in the alluvial facies. Low δ¹⁸O_SMOW values for microdolomite (+23.7 to +28.4%) and K-feldspar overgrowths (+17.3 to +17.7%) suggest either low-temperature, isotopic disequilibrium or precipitation from low-¹⁸O porewaters. Low-¹⁸O waters might have developed, at least in part, during low-temperature alteration of volcanic rock fragments. During mesodiagenesis, precipitation of quartz overgrowths and coarse dolomite occurred in the alluvial sandstones, whereas recrystallization of microdolomite was dominant in the sabkha/mudflat facies. The isotopic compositions of these mesogenetic phases reflect increasing temperature during burial. Upon uplift and erosion, telogenetic calcite and trace haematite precipitated in fractures and replaced dolomite. The isotopic composition of the calcite (δ¹⁸O_SMOW=+21.5 to +25.6%o; δ¹³C= 7.7 to - 5.6%o) and presence of haematite indicate infiltration of meteoric waters.     

塔中地区热化学硫酸盐还原作用对深埋白云岩储层的改造

塔里木盆地塔中地区深埋碳酸盐岩储层显示出极强的非均质性。如灰岩地层孔隙度极低,而含酸性气藏的白云岩储层最大孔隙度高达27%。然而,造成这些现象的原因仍然不清楚。通过岩芯、薄片、扫描电镜观察,结合流体包裹体均一温度、盐度分析,方解石、白云石的碳氧同位素测定,试图解决这一问题。前人研究认为,塔中地区碳酸盐岩优质储层分布主要受控于原始沉积条件（如高能的礁滩相）和表生溶蚀,热液活动和断裂活动也起到重要作用。然而,多期流体活动和成岩作用导致大量同生期和表生期形成的溶蚀孔洞被破坏。在某些井区（如ZG9井和TZ75井）,埋藏溶蚀作用可能对优质储层形成起到重要作用。在寒武系和奥陶系岩芯中发现了大量硬石膏、重晶石、黄铁矿、沥青、方解石等,方解石交代硫酸盐,方解石具有较高的均一温度及较低的碳同位素值说明其形成与热化学硫酸盐还原作用（TSR）有关。在发生TSR的白云岩井段,储层物性较好,说明TSR可能对深埋储层的改善具有促进作用。这些认识有助于指导深层寒武系碳酸盐岩储层的进一步勘探。     

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.     

Late Jurassic tectonics and sedimentation: breccias in the Unken syncline,central Northern Calcareous Alps

This study analyses and discusses well preserved examples of Late Jurassic structures in the Northern Calcareous Alps, located at the Loferer Alm, about 35 km southwest of Salzburg. A detailed sedimentary and structural study of the area was carried out for a better understanding of the local Late Jurassic evolution. The Grubhörndl and Schwarzenbergklamm breccias are chaotic, coarse-grained and locally sourced breccias with mountain-sized and hotel-sized clasts, respectively. Both breccias belong to one single body of breccias, the Grubhörndl breccia representing its more proximal and the Schwarzenbergklamm breccia its more distal part, respectively. Breccia deposition occurred during the time of deposition of the Ruhpolding Radiolarite since the Schwarzenbergklamm breccia is underlain and overlain by these radiolarites. Formation of the breccias was related to a major, presumably north-south trending normal fault scarp. It was accompanied and post-dated by west-directed gravitational sliding of the Upper Triassic limestone (“Oberrhätkalk”), which was extended by about 6% on top of a glide plane in underlying marls. The breccia and slide-related structures are sealed and blanketed by Upper Jurassic and Lower Cretaceous sediments. The normal fault scarp, along which the breccia formed, was probably part of a pull-apart basin associated with strike slip movements. On a regional scale, however, we consider this Late Jurassic strike-slip activity in the western part of the Northern Calcareous Alps to be synchronous with gravitational emplacement of “exotic” slides and breccias (Hallstatt mélange), triggered by Late Jurassic shortening in the eastern part of the Northern Calcareous Alps. Hence, two competing processes affected one and the same continental margin.     

Origin and diagenetic evolution of Ca–Mg–Fe carbonates in some coalfields of Japan

Carbonate concretions, lenses and bands in the Pleistocene, Palaeogene and Upper Triassic coalfields of Japan consist of various carbonate minerals with varied chemical compositions. Authigenic carbonates in freshwater sediments are siderite > calcite > ankerite > dolomite >> ferroan magnesite; in brackish water to marine sediments in the coal measures, calcite > dolomite > ankerite > siderite >> ferroan magnesite; and in the overlying marine deposits, calcite > dolomite >> siderite. Most carbonates were formed progressively during burial within a range of depths between the sediment-water interface and approximately 3 km. The mineral species and the chemical composition of the carbonates are controlled primarily by the initial sedimentary facies of the host sediments and secondarily by the diagenetic evolution of pore water during burial. Based on the regular sequence and burial depth of precipitation of authigenic carbonates in a specific sedimentary facies, three diagenetic stages of carbonates are proposed. Carbonates formed during Stage I (< 500 m) strongly reflect the initial sedimentary facies, e.g. low Ca-Mg siderite in freshwater sediments which are initially rich in iron derived from lateritic soil on the nearby landmass, and Mg calcite and dolomite in brackish-marine sediments whose pore waters abound in Ca²⁺ and Mg²⁺ originating in seawater and calcareous shells. Carbonates formed during Stage II (500–2000 m) include high Ca-Mg siderite, ankerite, Fe dolomite and Fe–Mg calcite in freshwater sediments. The assemblage of Stage II carbonates in brackish-marine sediments in the coal measures is similar to that in freshwater sediments. This suggests similar diagenetic environments owing to an effective migration and mixing of pore water due to the compaction of host sediments. Carbonates formed during Stage III (> 2000 m) are Fe calcite and extremely high Ca-Mg siderite; the latter is exclusively in marine mudstones. The supply of Ca is partly from the alteration of silicates in the sediments at elevated burial temperatures. After uplift, calcite with low Mg content precipitates from percolating groundwater and fills extensional cracks.     

The eroded Late Jurassic Kurbnesh carbonate platform in the Mirdita Ophiolite Zone of Albania and its bearing on the Jurassic orogeny of the Neotethys realm

Several Late Jurassic (Kimmeridgian?-Tithonian) to Early Cretaceous (Late Berriasian-Valanginian) shallow-water carbonate clasts of different facies are contained in mass-flow deposits in a pelagic sequence in the Kurbnesh area of central Albania. These clasts are used to reconstruct shallow-water carbonate platforms, which formed on top of the radiolaritic-ophiolitic wildflysch (ophiolitic mélange) of the Mirdita Zone. Stratigraphic interpretation of the platform carbonates was compiled on basis of calcareous algae, benthic foraminifera, and calpionellids. From biostratigraphic data and microfacies analysis, the Neocomian clasts can be directly correlated with autochthonous platform carbonates of the western part of the Munella carbonate platform, which at least reaches up to the Late Aptian. A Late Jurassic precursor platform (Kurbnesh carbonate platform; nomen novum) was completely eroded until the Valanginian and is only documented by the clasts described here. It was deposited on top of the Mirdita Ophiolite Zone nappe stack, which formed during the Middle to Late Jurassic Kimmeridian orogeny. Thrusting and imbrications as well as the formation of the syntectonic wildflysch (mélange) therefore occurred much earlier than previously assumed. Our results constrain the Kimmeridian orogeny, which was controlled by the closure of the Neotethys Ocean, and show excellent correlation with the Eastalpine-Dinaric- Hellenic orogenic system.     

Bimodal stable isotope signatures of Zildat Ophiolitic Mélange, Indus Suture Zone, Himalaya: implications for emplacement of an ophiolitic mélange in a convergent setup

Zildat Ophiolitic Mélange (ZOM) of the Indus Suture Zone, Himalaya, represents tectonic blocks of the fragmented oceanic metasediments and ophiolite remnants. The ZOM is sandwiched between the Zildat fault adjacent to a gneissic dome known as Tso Morari Crystalline (TMC) and thin sliver of an ophiolite called as the Nidar Ophiolitic Complex. The ZOM contain chaotic low-density lithologies of metamorphosed oceanic sediments and hydrated mantle rocks, in which carbonates are present as mega-clasts ranging from 100 meters to few centimeters in size. In this work, calcite microstructures, fluid inclusion petrography and stable isotope analyses of carbonates were carried out to envisage the emplacement history of the ZOM. Calcite microstructure varies with decreasing temperature and increasing intensity of deformation. Intense shearing is seen at the marginal part of the mélange near Zildat fault. These observations are consistent with the mélange as a tectonically dismembered block, formed at a plate boundary in convergent setup. The δ¹⁸O and δ¹³C isotope values of carbonates show bimodal nature from deeper (interior) to the shallower (marginal, near the Zildat fault) part of the mélange. Carbonate blocks from deeper part of the mélange reflect marine isotopic signature with limited fluid–rock interaction, which later on provide a mixing zone of oceanic metasediments and/or hydrated ultramafic rocks. Carbonates at shallower depths of the mélange show dominance of syn-deformation hydrous fluids, and this has later been modified by metamorphism of the adjacent TMC gneisses. Above observations reveal that the mélange was emplaced over the subducting Indian plate and later on synchronously deformed with the TMC gneissic dome.     

江汉盆地白垩系渔洋组砂岩的成岩作用及其热力学分析

江汉盆地白垩系渔洋组砂岩存在五种类型的成岩作用。其中,与油气运移有关并对储层孔隙演化产生重要影响的是硬石膏的胶结与交代作用和后期方解石再次胶结作用。为了更好的研究成岩作用发生的控制因素以及成岩环境的变化,我们通过细致的热力学推导,绘制出包含方解石、白云石和硬石膏等矿物相在内的五组分相图。通过相图分析可以看出,pH 值在成岩作用过程中有着重要的作用。方解石和白云石的胶结及交代作用代表了偏中性或碱性的成岩环境;而硬石膏的胶结及交代作用则表明成岩环境由中性或碱性向酸性转变,例如酸性的油气前锋流体的注入。另外,成岩环境中阳离子(Ca~(2 )、Mg~(2 ))和阴离子(CO_3~(2-)、SO_4~(2-))的浓度对方解石、白云石和硬石膏的胶结、溶解及交代作用也有重要影响。     

Rock composition and origin of the Duwi Formation calcareous rocks, Upper Egypt

Upper Cretaceous phosphorite beds of the Duwi Formation, Upper Egypt, are intercalated with limestone, sandy limestone, marl, calcareous shales, and calcareous sandstone. Calcareous intercalations were subjected to field and detailed petrographic, mineralogical and geochemical investigations in order to constrain their rock composition and origin. Mineralogically, dolomite, calcite, quartz, francolite and feldspars are the non-clay minerals. Smectite, kaolinite and illite represent the clay minerals. Major and trace elements can be classified as the detrital and carbonate fractions based on their sources. The detrital fraction includes the elements that are derived from detrital sources, mainly clay minerals and quartz, such as Si, Al, Fe, Ti, K, Ba, V, Ni, Co, Cr, Zn, Cu, Zr, and Mo. The carbonate fraction includes the elements that are derived from carbonates, maily calcite and dolomite, such as Ca, Mg and Sr. Dolomite occurs as being dense, uniform, mosaic, very fine-to-fine, non-ferroan, and non-stoichiometrical, suggesting its early diagenetic formation in a near-shore oxidizing shallow marine environment. The close association and positive correlation between dolomite and smectite indicates the role of clay minerals in the formation of dolomite as a source of Mg^2＋ -rich solutions. Calcareous rocks were deposited in marine, oxidizing and weakly alkaline conditions, marking a semi-arid climatic period. The calcareous/argillaceous alternations are due to oscillations in clay/carbonate ratio.     

Magnesite diagenesis in redbeds: a case study from the Permian of the Northern Calcareous Alps (Tyrol, Austria)

The Upper Permian Gröden Formation of the Northern Calcareous Alps (Austria) is composed of alluvial fan and playa lake sediments that were deposited in intramontane basins. A conspicuous feature of these redbeds is the abundance of magnesite in the form of nodules and discrete layers in mudstones as well as intergranular cement in sandstones. Sedimentological observations indicate that the bulk of these carbonates formed during early diagenesis and were probably syndepositional. Petrographically, most magnesites consist of micrite or, less commonly, microspar. An early non-ferroan magnesite is post-dated by later stage ferroan magnesites. Nodules consisting of recrystallized, sparry magnesite were observed only at one location. The general absence of relics of a non-magnesite precursor mineral and the occurrence of shrinkage features suggest that the fine grained magnesites formed by transformation of a hydrated magnesium carbonate mineral, e.g. hydromagnesite. Carbon, oxygen, sulphur and strontium isotope ratios in conjunction with sedimentological criteria support a model of (hydro)magnesite precipitation in an inland playa lake system, which was fed by run-off from the surrounding hinterland. The scarcity of evaporites and the dominance of magnesite over calcite and dolomite suggest that the playa lake brines were low in sulphate and had high Mg/Ca ratios. The source for the high magnesium concentrations is thought to be the weathering of Devonian dolostones and associated massive magnesite deposits in the catchment area.     

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。     

Hydrogeochemical factors effecting the scaling problem in Balçova geothermal field,İzmir, Turkey

Reservoir fluid compositions have been assessed from analytical data on water samples collected from thermal and cold waters in Balçova geothermal field. The results of mineral equilibrium modelling indicate that the waters, with some exceptions, are systematically supersaturated with respect to calcite, aragonite, dolomite, chalcedony and quartz, but undersaturated with respect to amorphous silica, celestite, anhydrite and gypsum and undersaturated or supersaturated with respect to barite, low-albite, K-feldspar, gibbsite and Fe(OH)₃(a). Calculation of mineral saturation states and geochemical analyses of scale and field observations show that carbonate minerals (calcite, aragonite and dolomite) are most likely to be precipitated as a scale type. Besides carbonates, scale formation risk of amorphous silica, Fe(OH)₃(a), anhydrite, barite and celestite minerals should be taken into account in some wells and surface equipment. Most of the waters, with some exceptions, have carbonate scaling risk at all temperatures, whereas the other scaling risks only exist over a limited temperature range. While silica, Fe(OH)₃(a) and barite show a scaling tendency at low temperatures, anhydrite and celestite scaling occurs at higher temperatures.     

Diagenetic controls on the isotopic composition of carbonate‐associated sulphate in the Permian Capitan Reef Complex,West Texas

Late Palaeozoic‐age strata from the Capitan Reef in west Texas show facies‐dependent heterogeneity in the sulphur isotopic composition of carbonate‐associated sulphate, which is trace sulphate incorporated into carbonate minerals that is often used to reconstruct the sulphur isotopic composition of ancient seawater. However, diagenetic pore fluid processes may influence the sulphur isotopic composition of carbonate‐associated sulphate. These processes variously modify the sulphur isotopic composition of incorporated sulphate from syndepositional seawater in shelf crest, outer shelf, shelf margin and slope depositional settings. This study used a new multicollector inductively‐coupled plasma mass spectrometry technique to determine the sulphur isotopic composition of samples of individual depositional and diagenetic textures. Carbonate rocks representing peritidal facies in the Yates and Tansill formations preserve the sulphur isotopic composition of Guadalupian seawater sulphate despite alteration of the carbon and oxygen isotopic compositions by meteoric and dolomitizing diagenetic processes. However, sulphur isotopic data indicate that limestones deposited in reef and slope facies in the Capitan and Bell Canyon formations largely incorporate sulphate from anoxic marine‐phreatic pore fluids isotopically modified from seawater by microbial sulphate reduction, despite generally preserving the carbon and oxygen isotopic compositions of Permian seawater. Some early and all late meteoric calcite cements have carbonate‐associated sulphate with a sulphur isotopic composition distinct from that of Permian seawater. Detailed petrographic and sedimentary context for carbonate‐associated sulphate analyses will allow for improved reconstructions of ancient seawater composition and diagenetic conditions in ancient carbonate platforms. The results of this study indicate that carbonate rocks that diagenetically stabilize in high‐energy environments without pore fluid sulphate gradients can provide a robust archive of ancient seawater's sulphur isotopic composition.     

Die Verteilung des Strontiums in oberjurassischen Karbonatgesteinen der Nördlichen Kalkalpen

Several publications on the environmental control of strontium in carbonate rocks have stimulated this investigation. Samples from three lithologically different units of the marine Upper Jurassic in the Northeastern Alps are analysed for strontium (x-ray fluorescence, atomic absorption, microprobe). Reported data on Sr in Recent carbonate secreting organisms, Recent and fossil carbonate sediments, on partition between calcite, aragonite and seawater have been used for comparison with those of the Upper Jurassic carbonate rocks. Reef sediments predominantly consisting of aragonite and high magnesium calcite lost extreme portions of their original Sr during diagenesis. Some layers (Oberalmer Schichten, St. Koloman) of probable bathypelagic origin are still comparable in strontium with primary marine calcite (about 0,1 % Sr).The pattern of the Sr distribution in the investigated Upper Jurassic limestones is mainly due to different courses of diagenetic change from different primary carbonates into low magnesium calcite. The change in Sr concentrations of diagenetic solutions is a function of the type of the supporting carbonate in an closed or open system of carbonates with porous solutions and is a function of seawater- or freshwater influence on the latter. A small strontium portion of these rocks occurs in apatite crystals with abnormal sulfur contents which could be identified as fragments of fish teeth.

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Wir danken Herrn Dr. A. Schkbidbb, (Göttingen) für zahlreiche Mikrosondenuntersuchungen und Herrn A. FENMNGER (Graz) für die quantitative Bestimmung der Tonrückstände in den Kalken. Für einen Teil der analytischen Arbeiten wurde ein Röntgenspektrometer der Deutschen Forschungsgemeinschaft benutzt.     

Origin of deformed halite hopper crystals, pseudomorphic anhydrite cubes and polyhalite in Alpine evaporites (Austria, Germany)

The Alpine Haselgebirge Formation represents an Upper Permian to Lower Triassic evaporitic rift succession of the Northern Calcareous Alps (Eastern Alps). Although the rocksalt body deposits are highly tectonised, consisting mainly of protocataclasites and mylonites of halite and mudrock, the early diagenetic history can be established from non-tectonised mudrock bodies: Cm-sized euhedral halite hopper crystals formed as displacive cubes within mud just during shallow burial. The crystals were deformed by subsequent compaction. Later, migrating fluids led to the replacement of halite by anhydrite retaining the shapes of deformed halite cubes. Polyhalite formed from subsequent enhanced fluid migration. Mudrock provided water by dewatering, while potassium and magnesium were dissolved from primary salt minerals. When these fluids interacted with sulphates, polyhalite precipitated. ⁴⁰Ar/³⁹Ar analyses date the polyhalite from within the retaining shapes of deformed halite hopper-shaped cubes from two localities to ca. 235–232 Ma (Middle Triassic). At this time, ca. 20–25 Ma after sedimentation, polyhalite crystallised at shallow levels.