Micro-XANES mapping of sulphur and its association with magnesium and phosphorus in the shell of the brachiopod, Terebratulina retusa

Biominerals are natural composite materials comprising organic and inorganic components. Detailed knowledge of the nature and distribution of both components is a crucial requirement in order to advance our understanding of biomineral formation, their material properties and preservation potential as well as the interpretation of environmental data. Detailed chemical data are essential for our understanding of the nature and distribution of such components. Micro-XANES mapping at the sulphur K-edge reveals that, in the brachiopod Terebratulina retusa, the sulphate concentration is higher in the outer (primary) layer than in the calcite fibres of the secondary layer. This is co-incident with a higher magnesium concentration. In contrast, the sheaths surrounding the calcite fibres contain sulphur as thiol, confirming the presence of protein while, the sulphur within the fibres themselves, occurs as sulphate. Micro-XANES analysis of the insoluble organic extract from T. retusa indicates the presence of organic sulphate while Micro-Raman spectroscopy confirms that structurally substituted sulphate (SSS) is also present although semi-quantitative Raman spectroscopy carried out in this spectral region (wavenumbers 900–1200) indicates that the sulphate present is at the threshold of detection by Raman spectroscopy. The distribution of phosphorus in the shell of T. retusa correlates well with that of protein indicating the presence of phosphorylated proteins in the periostracum, the sheaths surrounding the calcite fibres and the interface between the primary and secondary layer.     

An Atomic Force Microscopy study of the growth of calcite in the presence of sodium sulfate

In situ atomic force microscopy (AFM) has been used to compare the growth of pure calcite and the growth of calcite in the presence of sulfate ions from aqueous solutions at a constant value of supersaturation (S.I. = 0.89) with respect to calcite. The effect of sulfate ions on calcite growth rates is determined and a potential incorporation of sulfate ions is identified in the calcite during growth. Solutions supersaturated with respect to calcite with solution concentration ratio of one and a constant pH of 10.2, were prepared and sulfate was added as Na₂SO₄ aqueous solution. The solution composition was readjusted in order to keep the supersaturation and pH constant. PHREEQC was used to determine relevant solution concentrations. In situ AFM experiments of calcite growth were performed using a fluid cell and flowing solutions passed over a freshly cleaved calcite surface. Growth rates were determined from the closure of the rhombohedral etch pits induced by initial dissolution with pure water. The spreading rate of 2-dimensional nuclei was also measured. At low concentrations of sulfate (≤ 0.5 mM), no effect on the growth rate of the calcite was observed. At higher concentrations (2 to 3 mM) of sulfate, the growth rate increased, possibly because a higher concentration of calcium and carbonate was necessary to maintain the supersaturation constant. At much higher concentrations of additional sulfate (up to 60 mM) the growth rate of the calcite was substantially decreased, despite the fact that a further increase of calcium and carbonate was required. The morphology of 2-dimensional growth nuclei became increasingly elongated with increasing sulfate content. Measurements of step height showed that newly grown steps were approximately 1 Å higher when grown in high sulfate concentrations, compared to steps grown in sulfate-free solutions. At sulfate concentrations above 5 mM the growth mechanism changes from layer growth to surface roughening. These observations suggest that the new growth has incorporated sulfate into the calcite surface.     

Formation of ‘Beach Rock’ at Siesta Key, Florida and its influence on barrier island development

Seaward-dipping strata of carbonate-cemented shell debris located along the coast of Siesta Key on the Gulf Coast of the Florida peninsula have long been interpreted to be beachrock equivalent in age to the Pleistocene Anastasia Formation (Stage 5e) of the east coast of Florida. Detailed examination of thin sections along with radiometric dating and isotopic analyses demonstrates clearly that this is a Holocene deposit that is not beachrock but was lithified in a meteoric environment. Whole rock dates, dates from shells only, and from cement only demonstrate that these beach deposits were in place by at least 1800 yr BP and might have been there as long ago as 4300 yr BP. This means that some type of barrier island was in place at that time. Previous investigations have depicted Siesta Key as having a maximum age of 3000 yr with these deposits being located about 2 km landward of the beach deposits. This suggests that the beach deposits might have been the site of the original position of Siesta Key. These data also indicate that sea level must have been near its present position at the time that these foreshore beach deposits were deposited; sometime between 1800 and 4300 yr ago. This scenario indicates that sea level along this coastal reach probably reached its present level at least about 2000 yr ago.     

深层搅拌法在超软弱港口地基上的工程应用

某港口堆场地基上部5．0m系吹填而成，地表下18m范围均属软土，经真空预压初级加固后地基承载力仅在80—90kPa，局部区域上部淤泥土层土性指标较差，含水量大于50％，地基承载力不足60kPa。为了使地基达到230kPa的承载要求，设计采用深层搅拌法加固超软弱地基。通过现场成桩工艺试验和检测表明，桩身水泥土强度在90d龄期时大于1．80MPa，单桩承载力标准值大于150kN，以φ600桩径、桩长13．5m、置换率为0．308和φ500桩径、桩长13．5m、置换率为0．267两种方案布置的复合地基承载力标准值均超过了230kPa的设计要求。试验结果表明，深层搅拌法在港口超软弱地基土应用只要施工工艺适当，完全可以使地基承载力提高2—3．5倍以土，从而节省大量的工程投资。     

Carbon and oxygen isotopic composition of car- bonate cements of different phases in terrigenous siliciclastic reservoirs and significance for their origin： A case study from sandstones of the Triassic Yanchang Formation, southwestern Ordos Basin, China

Early carbonate cements in the Yanchang Formation sandstones are composed mainly of calcite with relatively heavier carbon isotope （their δ^18O values range from -0.3‰- -0.1‰） and lighter oxygen isotope （their δ^18O values range from -22.1‰- -19.5‰）. Generally, they are closely related to the direct precipitation of oversaturated calcium carbonate from alkaline lake water. This kind of cementation plays an important role in enhancing the anti-compaction ability of sandstones, preserving intragranular volume and providing the mass basis for later disso- lution caused by acidic fluid flow to produce secondary porosity. Ferriferous calcites are characterized by relatively light carbon isotope with δ^13C values ranging from -8.02‰ to -3.23‰, and lighter oxygen isotope with δ^18O values ranging from -22.9‰ to -19.7‰, which is obviously related to the decarboxylation of organic matter during the late period of early diagenesis to the early period of late diagenesis. As the mid-late diagenetic products, ferriferous cal- cites in the study area are considered as the characteristic authigenic minerals for indicating large-scaled hydrocarbon influx and migration within the clastic reservoir. The late ankerite is relatively heavy in carbon isotope with δ^13C values ranging from -1.92‰ to -0.84‰, and shows a wide range of variations in oxygen isotopic composition, with δ^18O values ranging from -20.5‰ to -12.6‰. They are believed to have nothing to do with decarboxylation, but the previously formed marine carbonate rock fragments may serve as the chief carbon source for their precipitation, and the alkaline diagenetic environment at the mid-late stage would promote this process.     

西藏扎布耶盐田盐渍土的改性配比试验

根据盐渍土的物理化学性质,采用掺入不同比例石灰或水泥的方法进行改性处理。经击实、抗剪和抗压强度试验结果表明,盐渍土掺入石灰或水泥改性后,混合料的最大干密度、最优含水率、强度指标等均有增加,特别是内聚力迅速增长。研究表明,盐渍土混合料的性状得到了明显改善,改性后的混合料可用于修建盐田埝堤类相关工程。     

硅质碎屑砂岩中胶结物来源的新认识

分析了浅埋藏砂岩的成岩环境,并从岩石学、矿物学、同位素及质量平衡估算方面论证硅质碎屑砂岩中的胶结物主要来源于砂岩浅埋藏期间的地下水,进而分析浅埋藏带内地下水的流动机制及早期胶结作用对晚期成岩作用的影响。     

硫铅酸盐“S”型瞬凝水泥干法护壁堵漏技术研究

介绍了硫铝酸盐“Ｓ”型瞬凝水泥干法者漏时使用的配方,阐述了输送工具和扫孔钻具的设计以及灌注工艺技术。     

Microfabrics of calcite ultramylonites as records of coaxial and non-coaxial deformation kinematics: Examples from the Rocher de l'Yret shear zone (Western Alps)

Microfabrics were analysed in calcite mylonites from the rim of the Pelvoux massif (Western Alps, France). WNW-directed emplacement of the internal Penninic units onto the Dauphinois domain produced intense deformation of an Eocene-age nummulitic limestone under lower anchizone metamorphic conditions (slightly below 300 °C). Two types of microfabrics developed primarily by dislocation creep accompanied by dynamic recrystallisation in the absence of twinning. Coaxial kinematics are inferred for samples exhibiting grain shape fabrics and textures with orthorhombic symmetry. Their texture (crystallographic preferred orientation, CPO) is characterised by two c-axis maxima, symmetrically oriented at 15° from the normal to the macroscopic foliation. Non-coaxial deformation is evident in samples with monoclinic shape fabrics and textures characterised by a single oblique c-axis maximum tilted with the sense of shear by about 15°. From the analysis of suitably oriented slip systems for the main texture components under given kinematics it is inferred that the orthorhombic textures, which developed in coaxial kinematics, favour activity of <10–11> and <02–21> slip along the f and r planes, respectively, with minor contributions of basal-<a> slip. In contrast, the monoclinic textures, which developed during simple shear, are most suited for duplex <a> slip along the basal plane. The transition between the dominating slip systems for the orthorhombic and monoclinic microfabrics is interpreted to be due to the effects of dynamic recrystallisation upon texture development. Since oblique c-axis maxima documented in the literature are most often rotated not with but against the shear sense, calcite textures alone should not be used as unequivocal shear sense indicators, but need to be complemented by microstructural criteria such as shape preferred orientations, grain size estimates and amount of twinning.     

Diagenesis and fracturing of Paleocene–Eocene carbonate turbidite systems in the Ionian Basin: The example of the Kelçyra area (Albania)

The Kelçyra area is emplaced in a foreland fold-and-thrust belt (FFTB), characterized by a westward thrusting with the Triassic evaporites as the major décollement level. Several secondary features related with this evolution, like backthrusting, folding, duplex structures, evaporite diapirism are present. During the FFTB evolution, the study area has been subjected to several fracturing events with associated stages of fluid migration. During the pre-deformational stage, complex textures such as crack-and-seal features most likely reflect expulsion of overpressured fluids. These fluids were dominantly host-rock buffered. Within the post-deformational stage, a meteoric fluid caused cementation and development of a karst network during a period of emergence after the thrust emplacement. Subsequently, Mg calcite reprecipitated in the more stable carbonate phase calcite and dolomite, which filled part of the karts network. The latter is finally dedolomitized and locally partially dissolved by a second meteoric fluid flow, which greatly increased the secondary porosity.