Stable isotopic signatures of superposed fluid events in granulite facies marbles of the Rauer Group, East Antarctica

The role of volatiles in the stabilization of the lower (granulite facies) crust is contentious. Opposing models invoke infiltration of CO₂-rich fluids or generally vapour-absent conditions during granulite facies metamorphism. Stable isotope and petrological studies of granulite facies metacarbonates can provide constraints on these models. In this study data are presented from metre-scale forsteritic marble boudins within Archaean intermediate to felsic orthogneisses from the Rauer Group, East Antarctica. Forsteritic marble layers and associated calcsilicates preserve a range of ¹³C- and ¹⁸O-depleted calcite isotope values (δ¹³C= -9.9 to -3.0% PDB, δ¹⁸O = 4.0 to 12.1% SMOW). A coupled trend of ¹³C and ¹⁸O depletion (～2%, ～5%, respectively) from core to rim across one marble layer is inconsistent with pervasive CO₂ infiltration during granulite facies metamorphism, but does indicate localized fluid-rock interaction. At another locality, more pervasive fluid infiltration has resulted in calcite having uniformly low, carbonatite-like δ¹⁸O and δ¹³C values. A favoured mechanism for the low δ¹⁸O and δ¹³C values of the marbles is infiltration by fluids that were derived from, or equilibrated with, a magmatic source. It is likely that this fluid-rock interaction occurred prior to high-grade metamorphism; other fluid-rock histories are not, however, ruled out by the available data. Coupled trends of ¹³C and ¹⁸O depletion are modified to even lower values by the superposed development of small-scale metasomatic reaction zones between marbles and internally folded mafic (?) interlayers. The timing of development of these layers is uncertain, but may be related to Archaean high-temperature (>1000d?C) granulite facies metamorphism.     

The biogenic origin of needle fibre calcite

Needle fibre calcite is one of the most ubiquitous habits of calcite in vadose environments (caves deposits, soil pores, etc.). Its origin, either through inorganic, indirect or direct biological processes, has long been debated. In this study, investigations at 11 sites in Europe, Africa and Central America support arguments for its biogenic origin. The wide range of needle morphologies is the result of a gradual evolution of the simplest type, a rod. This rod is the elementary brick which, by aggregation and welding, builds more complex needles. The absence of cross‐welded needles implies that they are welded in a mould, or under a longitudinal and unidirectional constraint, before being released inside the soil pores. The difference between the lengthening of the needles and the c axis can be explained by the existence of needles observed under a scanning electron microscope in organic sleeves, which can act as a mould during rod growth. Complex morphologies with epitaxial outgrowths on straight rods cannot have grown entirely inside organic microtubes; they must result from soil diagenesis after the release of straight rods in a soil‐free medium. Whisker crystals are interpreted as the result of growth and coalescence of euhedral crystals on a rod. Rhomb chains are considered to be the consequence of successive epitaxial growth steps on a needle during variations in growth conditions. Isotopic signatures for needle fibre calcite vary from ?16·63‰ to +1·10‰ and from ?8·63‰ to ?2·25‰ for δ¹³C and δ¹⁸O, respectively. The absence of high δ¹⁸O values for needle fibre calcite precludes a purely physicochemical origin (evaporative) for this particular habit of calcite. As epitaxial growth cannot precipitate in the same conditions as initial needles, needle fibre calcite stable isotopic signatures should be used with caution as a proxy for palaeoenvironmental reconstructions. In addition, it is suggested that the term needle fibre calcite should be kept for the original biogenic form. The other habit should be referred to as epitaxial forms of needle fibre calcite.     

Morphometry and distribution of isolated caves as a guide for phreatic and confined paleohydrological conditions

Isolated caves are a special cave type common in most karst terrains, formed by prolonged slow water flow where aggressivity is locally boosted. The morphometry and distribution of isolated caves are used here to reconstruct the paleohydrology of a karstic mountain range. Within a homogenous karstic rock sequence, two main types of isolated caves are distinguished, and each is associated with a special hydrogeologic setting: maze caves form by rising water in the confined zone of the aquifer, under the Mt. Scopus Group (Israel) confinement, while chamber caves are formed in phreatic conditions, apparently by lateral flow mixing with a vadose input from above.     

渤中凹陷CFD18-2油田高岭石胶结作用及其对储层物性的影响

为探究成岩作用过程中所形成的次生黏土矿物对储层物性的影响,借助偏光显微镜及扫描电镜的镜下分析,并结合储层物性等数据,对渤中凹陷附近沙垒田凸起东南部CFD18-2油田东三段高岭石的特征、类型、成因及其对储层物性的影响进行了研究。研究结果表明：1）研究区高岭石为有机酸溶蚀长石形成的自生高岭石,呈现典型的"手风琴状"及"蠕虫状",常充填于粒间孔、长石次生溶孔及碳酸盐胶结物溶孔中并形成良好的晶间孔隙。2）研究区主要发育两期高岭石,第一期主要充填于早期碳酸盐胶结物溶孔中,呈微小"蠕虫状";第二期充填于铁方解石与铁白云石胶结物溶孔中,部分高岭石具碱性溶蚀特征,且第二期高岭石与晚期伊利石共生。3）研究区东三段储层具备一定的渗流能力,使长石溶蚀形成的"副产物"被流体带走;但在破坏性成岩作用下,储层渗流能力会逐渐变差,最终使得"副产物"堆积于孔隙,降低储层物性。4）高岭石及同期硅质胶结物对储层物性的影响是一把"双刃剑",当高岭石及硅质的体积分数低于6.81%时,长石溶蚀有利于改善储层物性;当高岭石及硅质的体积分数高于6.81%时,则不利于储层物性的改善。     

Within‐colony variation in skeletal mineralogy of Adeonellopsis sp. (Cheilostomata: Bryozoa) from New Zealand

Three colonies of the erect, robust branching, cheilostome bryozoan Adeonellopsis sp. were collected from Doubtful Sound, New Zealand, to investigate within‐colony variation in carbonate mineralogy. One‐hundred‐and‐twenty‐one sections from 9 branches were found to contain mostly aragonite, with calcite ranging from 1.1 to 7.3 wt% (mean ± SD = 2.4 ± 1.2 wt%, n = 120). The magnesium (Mg) content in calcite ranged from 5.3 to 13.1 wt% magnesium carbonate (8.8 ± 1.0 wt% MgCO₃; n = 120). Calcite content decreased with increasing age proximally along the branch, indicating that secondary thickening is achieved with aragonite. In contrast, an oscillating trend in Mg content along branches suggests that seasonal or interannual environmental parameters may influence this geochemical parameter. Mineralogical variability highlights the need for multiple samples from the same colony to be measured when determining quantitative carbonate mineralogy in bryozoans. Bimineralic bryozoans such as Adeonellopsis sp. may have lower preservation potential than monomineralic bryozoans, and consequently may not survive diagenesis to become fossils. Bimineralic species may also be more vulnerable to dissolution pressure and possible ocean acidification than monomineralic calcitic taxa.     

Deciphering the depositional environment of the laminated Crato fossil beds (Early Cretaceous,Araripe Basin,North‐eastern Brazil)

The laminated limestones of the Early Cretaceous Crato Formation of the Araripe Basin (North‐eastern Brazil) are world‐famous for their exceptionally well‐preserved and taxonomically diverse fossil fauna and flora. Whereas the fossil biota has received considerable attention, only a few studies have focused on the sedimentary characteristics and palaeoenvironmental conditions which prevailed during formation of the Crato Fossil Lagerstätte. The Nova Olinda Member represents the lowermost and thickest unit (up to 10 m) of the Crato Formation and is characterized by a pronounced rhythmically bedded, pale to dark lamination. To obtain information on palaeoenvironmental conditions, sample slabs derived from three local stratigraphic sections within the Araripe Basin were studied using high‐resolution multiproxy techniques including detailed logging, petrography, μ‐XRF scanning and stable isotope geochemistry. Integration of lithological and petrographic evidence indicates that the bulk of the Nova Olinda limestone formed via authigenic precipitation of calcite from within the upper water column, most probably induced and/or mediated by phytoplankton and picoplankton activity. A significant contribution from a benthonic, carbonate‐secreting microbial mat community is not supported by these results. Deposition took place under anoxic and, at least during certain episodes, hypersaline bottom water conditions, as evidenced by the virtually undisturbed lamination pattern, the absence of a benthonic fauna and by the occurrence of halite pseudomorphs. Input of allochthonous, catchment‐derived siliciclastics to the basin during times of laminite formation was strongly reduced. The δ¹⁸O values of authigenic carbonate precipitates (between ?7·1 and ?5·1‰) point to a ¹⁸O‐poor meteoric water source and support a continental freshwater setting for the Nova Olinda Member. The δ¹³C values, which are comparatively rich in ¹³C (between ?0·1 and +1·9‰), are interpreted to reflect reduced throughflow of water in a restricted basin, promoting equilibration with atmospheric CO₂, probably in concert with stagnant conditions and low input of soil‐derived carbon. Integration of lithological and isotopic evidence indicates a shift from closed to semi‐closed conditions towards a more open lake system during the onset of laminite deposition in the Crato Formation.     

Marine cements in mid-Tertiary cool-water shelf limestones of New Zealand and southern Australia

Large areas of southern Australia and New Zealand are covered by mid‐Tertiary limestones formed in cool‐water, shelf environments. The generally destructive character of sea‐floor diagenesis in such settings precludes ubiquitous inorganic precipitation of carbonates, yet these limestones include occasional units with marine cements: (1) within rare in situ biomounds; (2) within some stacked, cross‐bedded sand bodies; (3) at the top of metre‐scale, subtidal, carbonate cycles; and (4) most commonly, associated with certain unconformities. The marine cements are dominated by isopachous rinds of fibrous to bladed spar, interstitial homogeneous micrite and interstitial micropeloidal micrite, often precipitated sequentially in that order. Internal sedimentation of microbioclastic micrite may occur at any stage. The paradox of marine‐cemented limestone units in an overall destructive cool‐water diagenetic regime may be explained by the precipitation of cement as intermediate Mg‐calcite from marine waters undersaturated with respect to aragonite. In some of the marine‐cemented limestones, aragonite biomoulds may include marine cement/sediment internally, suggesting that dissolution of aragonite can at times be wholly marine and not always involve meteoric influences. We suggest that marine cementation occurred preferentially, but not exclusively, during periods of relatively lowered sea level, probably glacio‐eustatically driven in the mid‐Tertiary. At times of reduced sea level, there was a relative increase in both the temperature and the carbonate saturation state of the shelf waters, and the locus of carbonate sedimentation shifted towards formerly deeper shelf sites, which now experienced increased swell wave and/or tidal energy levels, fostering sediment abrasion and reworking, reduced sedimentation rates and freer exchange of sediment pore‐waters. Energy levels were probably also enhanced by increased upwelling of cold, deep waters onto the Southern Ocean margins of the Australasian carbonate platforms, where water‐mass mixing, warming and loss of CO₂ locally maintained critical levels of carbonate saturation for sea‐floor cement precipitation and promoted the phosphate‐glauconite mineralization associated with some of the marine‐cemented limestone units.     

Chemo‐mechanics of cemented granular solids subjected to precipitation and dissolution of mineral species

This paper studies the chemo‐mechanics of cemented granular solids in the context of continuum thermodynamics for fluid‐saturated porous media. For this purpose, an existing constitutive model formulated in the frame of the Breakage Mechanics theory is augmented to cope with reactive processes. Chemical state variables accounting for the reactions between the solid constituents and the solutes in the pore fluid are introduced to enrich the interactions among the microstructural units simulated by the model (i.e., grains and cement bonds). Two different reactive processes are studied (i.e., grain dissolution and cement precipitation), using the chemical variables to describe the progression of the reactions and track changes in the size of grains and bonds. Finally, a homogenization strategy is used to derive the energy potentials of the solid mixture, adopting probability density functions that depend on both mechanical and chemical indices. It is shown that the connection between the statistics of the micro‐scale attributes and the continuum properties of the solid enables the mathematical capture of numerous mechanical effects of lithification and chemical deterioration, such as changes in stiffness, expansion/contraction of the elastic domain, and development of inelastic strains during reaction. In particular, the model offers an interpretation of the plastic strains generated by aggressive environments, which are here interpreted as an outcome of chemically driven debonding and comminution. As a result, the model explains widely observed macroscopic signatures of geomaterial degradation by reconciling the energetics of the deformation/reaction processes with the evolving geometry of the microstructural attributes. Copyright © 2015 John Wiley & Sons, Ltd.     

An Evaluation of Phase Behaviors of the Oil-Gas-Water System in the Displacement of Crude Oil with CO2

CO₂ dissolution into an aqueous phase and water evaporation into a gaseous phase takes place during CO₂ injection into an oil reservoir. This study aims to evaluate the phase behaviors of the oil-gas-water system in the displacement of crude oil by CO₂. The composition of the JL oilfield in the northeast of China is taken as an example. The flash calculation of the oil-gas-water system was performed, based on the method presented by Li and Nghiem. The research re...     

海底玄武岩中次生组分HCl溶解实验研究

次生组分沉淀是海底岩石中普遍存在的现象,次生组分去除是减少次生组分干扰、获取海底岩石高质量数据的关键。选择西太平洋麦哲伦海山区MK海山相对新鲜的玄武岩作为研究对象,经研磨、均一化后将粉末样品分为49份,其中48份分别以0.25,0.50,1.00,1.50,2.00,2.50 mol/L六种浓度的足量HCl溶解0.5,1,2,4,8,16,32和64 h后,选取溶解残渣测定主要氧化物和特征微量元素质量分数,确定HCl溶解法在去除次生组分的同时不会对海底新鲜玄武岩中原生组分造成影响的HCl浓度-时间组合。结果表明,在HCl浓度为1.00～2.50 mol/L,溶解时间为0.5～2 h的12种HCl浓度-时间组合均可保证海底玄武岩中原生组分的安全,并可有效去除次生组分。综合海底蚀变玄武岩次生组分去除实验研究,推荐使用1.00～2.00 mol/L HCl,溶解时间在0.5～1 h的实验方案。