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

Maggie Cusack  Yannicke Dauphin  Jean-Pierre Cuif  Murielle Salom  Andy Freer  Huabing Yin 《Chemical Geology》2008,253(3-4):172-179

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.  相似文献   

An Atomic Force Microscopy study of the growth of calcite in the presence of sodium sulfate   总被引：1，自引：0，他引：1  

Aikaterini I. Vavouraki  Christine V. Putnis  Andrew Putnis  Petros G. Koutsoukos   《Chemical Geology》2008,253(3-4):243-251

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.  相似文献   

Microbial release of potassium from K-bearing minerals by thermophilic fungus Aspergillus fumigatus     

Bin Lian  Bin Wang  Mu Pan  H. Henry Teng 《Geochimica et cosmochimica acta》2008,72(1):87-98

A strain of thermophilic fungus Aspergillus fumigatus was cultured with K-bearing minerals to determine if microbe-mineral interactions enhance the release of mineralic potassium. Experiments were carried out in two settings, one with the mineral grains and the fungal cells in direct contact, and the other employing a membrane (pore size 0.22 μm) to separate the two. Measurements over a period of 30 days showed that, irrespective of the experimental setup, the concentration of free K in the culture was drastically higher than those in any of the control experiments where no living organism was present. Moreover, the occurrence of mineral-cell physical contact enhanced potassium release by an additional factor of 3 to 4 in comparison to the separation experiments. For contact experiments, Electron Probe Microanalysis revealed the formation of mycelium-mineral aggregates, and Atomic Force Microscopy imaging further indicated the possible ingestion of mineral particles by the fungus cells. Contrasting to what was observed and expected in control experiments, the potassium solubilization rate showed a positive dependence upon pH when fungi and minerals were mixed directly, and exhibited no correlations with solution acidity if cell-rock contact was restrained. These results appear to suggest that A. fumigatus promoted potassium release by means of at least three likely routes, one through the complexation of soluble organic ligands, another appealing to the immobile biopolymers such as the insoluble components of secretion, and the third related to the mechanical forces in association with the direct physical contact between cells and mineral particles.  相似文献   

Variations in the Rate of Anaerobic Succinate Accumulation within the Central and Marginal Regions of an Euryoxic Bivalve Mantle     

Ed  Greenfield Miles A.  Crenshaw 《Marine Ecology》1981,2(4):353-362

Abstract. Anaerobic metabolism in the central and marginal portions of the mantle of Mercenaria mercenaria was compared. Anaerobic succinate accumulation was more rapid in the central region. This difference may be due to higher phosphoenolpyruvate carboxykinase activity in the central region. Thus, the central region is more specialized for anaerobic metabolism and the marginal region more for net shell growth. The original rate of succinate accumulation in the mantle is similar in isolated mantles and intact clams, suggesting that mantle succinate production does not require translocation of precursors from other tissues. However, in intact clams, the rate of succinate accumulation in the central region of the mantle slows after four hours. The reduced rate is probably caused by reducing the metabolic rate. Succinate accumulation and shell dissolution are slower in freshly collected clams than in clams that had been stored anaerobically. The difference may be due to induction of PEPCK synthesis during storage. Shell derived calcium did not accumulate in the mantle and, therefore did not alter the intracellular calcium concentration in the mantle.  相似文献   

The Levant Slumps and the Phoenician Structures: collapse features along the continental margin of the southeastern Mediterranean Sea     

Yossi Mart  William Ryan 《Marine Geophysical Researches》2007,28(4):297-307

Two distinct series of slumps deform the upper part of the sedimentary sequence along the continental margin of the Levant. One series is found along the base of the continental slope, where it overlies the disrupted eastern edge of the Messinian evaporites. The second series of slumps transects the continental margin from the shelf break to the Levant Basin. It seemed that the two series were triggered by two unrelated, though contemporaneous, processes. The shore-parallel slumps were initiated by basinwards flow of the Messinian salt, that carried along the overlying Plio-Quaternary sediments. Seawater that percolated along the detachment faults dissolved the underlying salt to form distinctly disrupted structures. The slope-normal slumps are located on top of large canyons that cut into the pre-Messinian sedimentary rocks. A layer of salt is found in the canyons, and the Plio-Quaternary sediments were deposited on that layer. The slumps are bounded by large, NW-trending faults where post-Messinian faulted offset was measured. We presume that the flow of the salt in the canyons also drives the slope-normal slumps. Thus thin-skinned halokynetic processes generated the composite post-Tortonian structural patterns of the Levant margin. The Phoenician Structures are a prime example of the collapse of a distal continental margin due to the dissolution of a massive salt layer.  相似文献   

琉球群岛东部海区表层沉积物中浮游有孔虫分布及指示意义     

吴永华  程振波  石学法  李小艳  石丰登  鞠小华 《海洋地质与第四纪地质》2007,27(6):1-7

对琉球群岛东部海区123个表层沉积物样品中浮游有孔虫因子分析结果表明,浮游有孔虫组合在溶跃面以上表现为Globigerinoides ruber-Globigerinata glutinata组合,溶跃面以下为Globorotalia inflata-Neoglobo-quadrina pachyderma (dex.)组合,局部受黑潮影响区域黑潮标志种Pulleniatina obliquiloculata含量相对丰富,为Neogloboquadrina dutertrei-P.obliquiloculata组合;表层沉积物中浮游有孔虫的丰度及组合分布特征对于碳酸盐溶跃面深度及碳酸盐补偿深度有一定的指示意义。另外,碳酸盐保存特征研究表明,该区域现代碳酸盐溶跃面深度约为3100 m,碳酸盐补偿深度约为4300 m。  相似文献   

Nature of the connection between the Northern and Southern Zechstein Basins across the Mid North Sea High     

M.K. Jenyon  P.M. Cresswell  J.C.M. Taylor 《Marine and Petroleum Geology》1984,1(4):355-363

The seismic expression of a salt-filled channel which cuts across the Mid North Sea High in Quadrant 37 is described, with features interpreted as being produced by salt-edge dissolution forming both eastern and western margins of the channel. The apparent half-graben nature of the channel is shown to be only superficial, and due to complex faulting associated with, but not defining, its western margin. The shallower faulting here is a Mesozoic to early Tertiary growth fault related to local dissolution of Zechstein salt. The dissolution effect appears in turn to have been localized by the presence of a deeper fault that was already downthrown to the east in Zechstein times, when it seems to have limited the eastward progradation of Zechstein shelf carbonates and anhydrites, and had probably ceased to move significantly before the onset of the Late Cimmerian erosional phase. The origin of this arcuate fault is tentatively ascribed to subsidence around a granite batholith. Zechstein salt originally spread some distance to the east and west of the channel; it was dissolved from the edges inwards, mainly before the Late Cretaceous, giving rise to a thicker Mesozoic sequence on parts of the flanks of the channel than in the middle. Besides providing an interesting structural case history, the features described have implications regarding Zechstein sedimentation, reservoir potential, the tectonic history of the North Sea, and the nature of the Mid North Sea High itself.  相似文献   

天然气溶解过程中组分分馏模型及其应用   总被引：1，自引：0，他引：1  

程付启  金强  林会喜  刘文汇 《高校地质学报》2008,14(1):120-125

天然气不同组分在水中溶解度的差异,导致溶解相与残留游离相天然气组分组成不同,即发生组分的溶解分馏效应。溶解分馏效应在天然气水溶运移、溶解散失等过程中均有发生。揭示天然气组分的溶解分馏规律、建立定量分馏模型,有助于天然气气源对比和成藏过程示踪。以Henry定律为依据,对不同组分溶解特征分析,提出了溶解度分数的概念,并建立了溶解分馏模型。根据该模型和各组分的溶解度分数和天然气溶解量,可计算各组分的溶解分馏量,恢复天然气初始组成特征。计算表明,威远震旦系气藏初期的天然气组成为:CH4为72.70%,C2H6为0.09%,CO2为22.41%,N2为4.07%,干燥系数(C1/C1-5)为99.876%。溶解作用使天然气中CO2含量显著降低,烃类气体含量增加,而天然气干燥系数降低。结果有助于天然气成因判识和气源对比等。  相似文献   

Kinetics of redox cycling of iron coupled with fulvic acid     

Yiwei Deng  Werner Stumm 《Aquatic Sciences - Research Across Boundaries》1993,55(2):103-111

The kinetics of conversion of iron(III) (hydr)oxides to ferrous iron mediated by fulvic acid have been investigated in order to improve the understanding of the redox cycling of iron at the oxic-anoxic boundary in natural waters. Under the conditions similar to natural waters, fulvic acid is able to reduce the iron(III) (hydr)oxide. The kinetics of the reaction depend on the reactivity of iron(III) (hydr)oxides and the reducing power of the fulvic acid. The rate of reaction is 60 nm/h obtained under following conditions: total concentration of Fe(III) 1.0 × 10^–4 M, pH 7.5, fulvic acid 5 mg/L. The rate is considered as a net result of reduction and oxidation in the > Fe^III-OH/Fe(II) wheel coupled with fulvic acid. In a real natural water system, reductants other than fulvic acid may be of importance. The results obtained in the laboratory, however, provide evidence that the Fe(OH)₃(s)/Fe(II) redox couple is able to act as an electron-transfer mediator for the oxidation of natural organic substances, such as fulvic acid by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.  相似文献   

Brønsted reactions on oxide mineral surfaces and the temperature-dependence of their dissolution rates     

William H. Casey  Marcus A. Cheney 《Aquatic Sciences - Research Across Boundaries》1993,55(4):304-313

The pH-dependence of oxide dissolution rates is controlled by Brønsted acid-base reactions at the mineral surface. These reactions are rapid but depend explicitly on temperature, as do the subsequent slow rates of bond hydrolysis. The net result is that dissolution rates vary in a complicated fashion with temperature and solution pH. The enthalpy changes of acid-base reactions on oxide materials are sufficiently similar, however, that general statements can be made about their contribution. The enthalpy changes from proton adsorption to a hydroxyl functional group (SOH), or to a deprotonated functional group (SO ^–), are generally exothermic. The enthalpy changes become increasingly endothermic, however, as charge accumulates on the mineral surface and the charged species interact electrostatically. The result is that mineral dissolution rates are least sensitive to temperature, as measured with an Arrhenius-like rate law, at pH conditions near the Point of Zero Net Proton Charge.  相似文献