On the origin of bleaching phenomena in red bed sediments of Triassic Buntsandstein deposits in Central Germany

The Lower Triassic Buntsandstein in Central Germany comprises one of the major clastic, lithified hydrocarbon reservoirs, it is a major groundwater aquifer and it is considered as a potential underground gas storage lithology. Thus, sandstones of the Buntsandstein from Thuringia and NE Hesse were used to analyse their geochemical composition combined with mineralogical data in order to investigate the origin of several bleaching phenomena in primary red beds, since these give a hint for mineral alteration, mineral formation and mineral reactivity in the course of fluid-rock-interactions. This is relevant for e.g. recent Carbon Capture and Storage (CCS) efforts. The origin of the observed bleaching phenomena is diverse and it is linked to certain stages of diagenesis and different episodes of fluid flow: (1) eodiagenetic bleaching coupled with palaeosoil formation and iron mobilisation, (2) mesodiagenetic bleaching as a result of hydrocarbon migration, (3) Tertiary bleaching due to CO₂ degassing from Miocene volcanism, (4) Tertiary telodiagenetic bleaching due to weathering under humid climate conditions, and (5) weathering processes related to recent telodiagenesis/pedogenesis. This study emphasizes the multiple nature of fluids, which can induce iron mobilisation and bleaching of red beds.     

Elucidating hydrological complexity and climate-influenced diagenesis during the early Carboniferous of South Wales

A revised age provided by conodonts from the Gilwern Oolite of the Clydach area of South Wales allows a clearer understanding of the palaeohydrology, palaeoclimatic history and diagenesis of previously correlated oolitic units. Earlier uncertainty over the apparent sub-regional differences in climate during the early Visean (Chadian—Arundian) lowstand is resolved. Previously a humid interval evidenced by prominent palaeo-epikarst capping the Gilwern Oolite along the northern outcrops of the South Wales synclinorium, was not recognized in what were regarded as correlative outcrops in the Chadian Gully Oolite in the southern part of the synclinorium. Conodont dating now shows that the Gilwern Oolite is much older (Courceyan) than the Chadian Gully Oolite, and during the prolonged exposure of the former there was an interval of weathering under a humid climate. This also explains the contrast between the diagenesis seen between the Gilwern and Gully oolites, which are no longer seen as correlatives.     

Distribution of diagenetic alterations within depositional facies and sequence stratigraphic framework of fluvial sandstones: Evidence from the Petrohan Terrigenous Group,Lower Triassic,NW Bulgaria

Sequence stratigraphy of fluvial deposits is a controversial topic because changes in relative sea level will eventually have indirect impact on the spatial and temporal distribution of depositional facies. Changes in the relative sea level may influence the accommodation space in fluvial plains, and hence have impact on types of fluvial system, frequency of avulsion, and style of vertical and lateral accretion. This study aims to investigate whether depositional facies and changes in the fluvial system of the Lower Triassic Petrohan Terrigenous Group sandstones (NW Bulgaria) in response to changes in the relative sea level have an impact on the spatial and temporal distribution of diagenetic alterations.     

Pyrite formation and the drowning of a palaeosol

Palaeosols may be modified in a variety of ways during burial diagenesis but significant alteration can take place during the earliest phases of burial caused by rising groundwaters. A calcrete palaeosol, the Heatherslade Geosol, from the Lower Carboniferous of South Wales, contains abundant pyrite which overprinted the original soil fabrics. The pyrite is interpreted as the product of anaerobic conditions caused by drowning during the early stages of a marine transgression. Unusual diamond-shaped forms of pyrite occur which possibly represent pseudomorphs after gypsum.     

A comparison of the early diagenetic environment in intertidal sands and muds of the Manukau Harbour,New Zealand

The early diagenetic environment of intertidal sandy sediments (sands) and muddy sediments (muds) is described and compared from two cores taken from an unpolluted part of the Manukau Harbour, New Zealand. Extraction techniques characterized the form of the trace elements (Fe, Mn, S, C, Pb, Zn, Cu) at different depths in the sediment. Dissolved forms of Fe, Mn, and S were measured in interstitial water. Nonresidual metal concentrations, humic acid, FeS, and FeS₂ are an order of magnitude higher in the muds than in the sands because of dilution by unreactive sand particles. Muds contain a larger proportion of metals in the mobile fractions; exchangeable (Mn), carbonate (Mn, Fe, Zn), and easily-reducible oxide (Fe, Mn, Zn, Pb). This is due to greater surface area (for Mn adsorption); the favorable conditions for MnCO₃, FeCO₃, and FeS precipitation; and higher concentrations of easily reducible iron oxide and humic acid. Therefore, compared to the sands, muds are more important as reservoirs for toxic metals, both in terms of quantity and availability. At either site there was very little difference between the forms of Zn, Pb or Cu identified by sequential extraction as sediments changed from oxic to anoxic conditions. One reason for this is that the amounts and proportions of some of the important components that bind metals, viz., amorphous iron hydrous oxides, humic acids, and FeS₂, do not change much. Other components that do change with redox conditions, for example, manganese phases and FeS, are only minor components of the sediment. Redox conditions, then, have relatively little effect on trace-metal partitioning in the sediment matrix of these unpolluted sediments.     

Speleogenesis in aeolian calcarenite: A case study in western Victoria

Most studies of karst landscapes and their processes have been concerned with consolidated, often well-jointed limestones. There are particular problems involved in the study of karst procesess in softer, less-compact limestones such as chalk, coral reefs, and aeolian calcarenite. Previous studies in aeolian calcarenite indicated these problems and a scheme was developed of speleogenesis in aeolian calcarenite. A study of karst processes in aeolian calcarenite at Bats Ridge in western Victoria has developed this scheme further. The karst features and processes at Bats Ridge are an integral part of the landscape of a mid-Pleistocene calcarenite dune system. The resolution of problems of the rapid subaerial speleogenesis in the area is achieved by the synthesis of the known karst features of the ridge and the geology and geomorphology of the area. Karst development on this aeolianite ridge depends on lithological conditions as well as the availability of aggressive water capable of solution. The diagenesis of the calcarenite is occurring now and must have been occurring by the mid-Pleistocene. This simultaneous lithification of the carbonate dunes into aeolian calcarenite rock and the development of solutional karst features in the dunes is the characteristic feature of the speleogenesis in this area. It is the formation of a hardened kankar layer (cap rock) in the dunes of sufficient compressive and tensile strength to support cavities, which is the result of these interrelated factors, that has strongly determined the formation of the karst features.     

菌藻对碳酸盐颗粒的泥晶化作用研究─以滇西保山地区下石炭统研究为例

碳酸盐颗粒泥晶化由真菌类和藻类的穿孔所引起，颗粒泥晶化可划分为四个阶段６种类型，泥晶套和泥晶铸型分别代表泥晶化的成长、成熟阶段。丰富的泥晶化颗粒为浅滩标志；泥晶化的深度与沉积速度成反比；泥晶化均匀程度与颗粒翻转次数成正比；颗粒泥晶化类型组合与风暴沉积有关；暴露环境出现溶蚀孔洞或负鲕。菌藻的泥晶化作用可加速海水及成岩压实作用对颗粒的破碎和细化并产生内碎屑和灰泥；鲕粒泥晶化后转变为辐射鲕和假鲕。     

四川盆地东北部三叠系飞仙关组碳酸盐岩成岩作用和白云岩成因的研究现状和存在问题

四川盆地东北部三叠系飞仙关组是我国重要的天然气储集层，优质储层形成机制直接与碳酸盐岩成岩作用、尤其是白云岩化作用相关，但飞仙关组碳酸盐岩在锰含量、锶含量、阴极发光性等特征上反映其成岩过程与经典成岩理论相悖；碳酸盐岩的锶同位素组成和锰、锶含量的关系也表明与大气水有关的成岩过程和作为重要储集岩的结晶白云岩的形成机制无关，传统的白云岩化机制难以解释结晶白云岩的成因。具有海源色彩的高锶、低锰成岩流体在很大程度上控制了飞仙关组碳酸盐的成岩作用，其来源与成因值得进一步关注，控制其运移、封存和发生水—岩反应的时空机制有待回答。整个海相三叠纪时间段盆地尺度碳酸盐岩和蒸发岩的沉积地球化学研究、尤其是不同结构组分碳酸盐的锶同位素组成、锶和锰含量研究（包括碳酸盐岩中不同结构组分的阴极发光性研究），可为四川盆地东北部飞仙关组碳酸盐岩成岩作用（尤其是白云岩化作用和作为重要储集岩的结晶白云岩的成因研究），天青石矿床成因研究和四川盆地三叠系深层富钾、锶、硼、溴卤水的成因研究提供重要的线索。     

Factors Controlling Sulfide Geochemistry in Sub-tropical Estuarine and Bay Sediments

The primary factors that control the concentration of total reduced (inorganic) sulfide in coastal sediments are believed to be the availability of reactive iron, dissolved sulfate and metabolizable organic carbon. We selected nine sites in shallow (<3 m), close to sub-tropical, estuaries and bays along the central Texas coast that represented a range in sediment grain size (a proxy for reactive iron), salinity (a proxy for dissolved sulfate), and total organic carbon (a proxy for metabolizable organic carbon). Based on these parameters a prediction was made of which factor was likely to control total reduced sulfide at each site and what the relative total reduced sulfide concentration was likely to be. To test the prediction, the sediments were analyzed for total reduced sulfide, acid volatile sulfide, and citrate dithionate-extractable, HCl-extractable and total Fe in the solid phase. Using solid-state gold–mercury amalgam microelectrodes and voltammetry, we determined pore water depth profiles of Fe(II) and ΣH₂S and presence or absence of FeS_(aq). At five of the nine sites the calculated degree of sufildization of citrate dithionite-reactive-iron was close to or greater than 1 indicating that rapidly reactive iron was probably the limiting factor for iron sulfide mineral formation. At one site (salinity = 0.9) dissolved Fe(II) was high, ΣH₂S was undetectable and the total reduced sulfide concentration was low indicating sulfate limitation. At the last three sites a low degree of sulfidization and modest total reduced (inorganic) sulfide concentrations appeared to be the result of a limited supply of metabolizable organic carbon. Fe(II)–S(-II) clusters (FeS_(aq)) were undetectable in 10 out of 12 bay sediment profiles where ΣH₂S was close to or below detection limits, but was observed in all other porewater profiles. Acid volatile sulfide, but not total reduced sulfide, was well correlated with total organic carbon and ranged from being undetectable in some cores to representing a major portion of total reduced sulfide in other cores. Although predicted controls on total reduced sulfide were good for very low salinity water or sandy sediments, they were only right about half the time for the other sediments. The likely reasons for the wrong predictions are the poor correlation of total organic carbon with grain size and differing fractions of metabolizable organic carbon in different sedimentary environments. Differences in sediment accumulation rates may also play a role, but these are difficult to determine in this region where hurricanes often resuspend and move sediments. This study demonstrates the need to examine more complex and often difficult to determine parameters in anoxic “normal marine” sediments if we are to understand what controls the concentration and distribution of sulfides.     

Hydrogeochemical models locating sulfate-methane transition zone in marine sediments overlying black shales: A new tool to locate biogenic methane?

Precise hydrogeochemical modeling of early diagenesis is a key in the reconstruction of sedimentary basin models. This determines the mineralogical evolution of the sediment and consequently the porosity of the rock. During early diagenesis also part of the initial organic matter is converted into biogenic gas: CH₄ CO₂, and H₂S. These processes are part of complex reaction chains during sedimentation, and biogeochemical reactions leave different signals that can be observed today. In this work, we reproduce the early diagenetic processes as integrated signals over geological times in sediments of the Demerara Rise by applying chemical thermodynamics using the PHREEQC (version 2) computer code. The investigated sediments are characterized by the presence of black shales in 410–490 mbsf and by a diagenetic barite layer above in 300–350 mbsf at depth of sulfate-methane transition (SMT). We determine the parameters that influence the location of diagenetic barite peaks in sediments overlying black shales by means of a novel modeling approach. Crucial parameters are the amount of bacterial organic matter mineralization, sedimentation rates and bottom water sulfate concentrations. All parameters are intertwining and influence the sulfate-methane cycle. They affect the location of the SMT visualized by diagenetic barite peaks. However, our model approach opens a wide field in exploring early diagenetic reactions, processes and products (such as biogenic methane) over geological times mirrored by diagenetic minerals and pore water concentration profiles that can be detected in present-day sediments.