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1.
Pedogenic calcretes commonly exhibit clotted micrite, circum-granular calcite (grain coats) and microspar/spar veins. The three calcite-types with different dimensions were analyzed for their magnesium content to determine the relationship between crystal elongation and magnesium incorporation. The results show a very low MgO content for grain coats and microspars and high values for clotted micrite indicating that the ideal kinetic model does not hold true and several variables govern the end composition of calcites. The magnesium concentrations of meteoric calcites are genetically linked to the evolutionary history of the soil and climate. Grain coats, which are elongated calcites, contain the least amount of Mg and is related to the initial stages of pedogenesis wherein the limiting factor is the Mg/Ca ratio of the parent fluid. Lower magnesium contents arise due to smaller quantities of Mg being released during incipient weathering. Micrite morphology and composition is controlled by the greater availability of Mg ions through weathering, higher pCO2 in soil due to increased time-dependent soil respiration, which causes a rise in calcite precipitation rates and clay authigenesis. This in turn exerts a physical control on morphology by occluding pore space and providing numerous nuclei for calcite precipitation. The wide variability in spar cements is inherently controlled by inhomogeneties in parent fluid compositions with lower-than-micrite values on account of slower precipitation rates.  相似文献   

2.
The Pleistocene Miami Limestone that crops out on the lower Florida Keys is overlain by thin (16 cm or less), discontinuous, Holocene calcareous crusts (caliche) that are usually laminated, composed dominantly of calcite micrite and may or may not incorporate part of the underlying limestone. Both allochems and sparry calcite cement in the former unit contain endolithic algae and fungi, borings and unicellular algae. Biogenic structures identical to those in the Miami Limestone also occur in the calcareous crusts but are somewhat less abundant in the latter unit versus the former unit. The calcareous crusts were formed in the vadose diagenetic environment. Some of the CaCO3 necessary for the micrite that comprises the bulk of the crusts was probably derived from solution of carbonate from a soil cover and some from wind blown salt spray. Most of the micrite, however, was formed by replacement of the uppermost portions of the Miami Limestone. Replacement involved micritisation of allochems and a previously unreported process, sparmicritisation, the degrading recrystallization of sparry calcite to micrite. Minor sparmicritisation was caused by micrite calcification of endolithic fungi or algae within sparry calcite cement or by micrite precipitation in empty borings within such cement. Most sparmicritisation took place by dissolution of sparry calcite and concomitant precipitation of micrite in the space occupied previously by the dissolved spar. Such sparmicritisation is interpreted to be caused by chemical reactions involving the crystals, pore water which is moving slowly but steadily and organic compounds released during bacterial decomposition of fungi, algae or both. It is recognized that sparmicritisation occurs in the marine diagenetic environment and is not, therefore, necessarily indicative of vadose diagenesis. Incomplete sparmicritisation is responsible for some of the clotted textures typically found within calcareous crusts and may explain such textures in many other carbonate rock types. A combination of sparmicritisation and micritisation has probably greatly influenced the porosity of many reefs and, in some cases, led to the formation of ‘micritic reefs’.  相似文献   

3.
Mineralogical, textural and geochemical investigations were made to determine the post-depositional evolution of Devonian and Early Carboniferous carbonates from Valle de Tena. The carbonate association is made up of low-Mg calcite, which occurs as micrite, spar cements, neomorphic patches and spar filling veinlets. Non-stoichiometric dolomite and ankerite occur as cements (dolomite also as replacements) in the Middle Devonian, post-dating calcite types. All these phases pre-date tectonic stylolites, indicating compaction after stabilization of the carbonate minerals. Strontium concentrations indicate that Early Devonian and Early Carboniferous micrites initially precipitated as aragonite; Middle and Late Devonian micrites precipitated as high-Mg calcites. Both precursors were diagenetically stabilized to low-Mg calcites through interaction with meteoric waters in phreatic environments. Trace elements in dolomite and ankerite indicate precipitation from Sr-enriched meteoric water. All studied carbonates, except Middle Devonian limestones, precipitated in reducing environments, which favoured incorporation of Fe and Mn. Late calcite generations precipitated from more saline waters than micrites. Light 18O values in micrites suggest alteration mainly in meteoric-phreatic environments. The dolomites and ankerites precipitated from more 18O-depleted fluids than the calcites, suggesting a greater contribution from meteoric waters. Variations in 13C of micrites represent primary secular trends, according to published 13C variations. The 13C oscillations within each succession probably relate to sea-level oscillations. Strontium isotopes also point to a meteoric origin of diagenetic fluids. Model calculations suggest that O and Sr isotopes equilibrated between calcites and fluid at relatively low water/rock ratios, whereas C isotopic signatures are inherited from limestones.  相似文献   

4.
The morphology and geochemistry of pedogenic carbonate found in vertic claystone palaeosols in the Devonian Catskill Formation in central Pennsylvania preserve a record of the physical and chemical environment of carbonate precipitation. The carbonate is characterized by three distinct petrographic generations. Pedogenic rhizoliths and nodules are the earliest precipitated generation, and typically consist of dull red-brown luminescent micrite. Clear, equant calcite spar cement fills voids in the centres of rhizoliths, as well as circumgranular cracks and septarian voids in nodules. Early spar cements are non-luminescent to dull luminescent, whereas later spar cements exhibit bright yellow-orange luminescence. Late stage pedogenic fractures are always occluded with very bright yellow-orange luminescent spar cements. The incorporation of progressively higher concentrations of Mn (up to 34000 ppm) into successively younger calcite spar cements, without concomitant increases in Fe, suggests carbonate precipitation from an evolving meteoric water in which Mn2+ became increasingly mobile over time. The increased mobility is possibly due to decreasing Eh, resulting from oxidation of organic matter after rapid soil burial on the floodplain. The amount of Fe2+ available for incorporation into calcite was limited because most iron was immobile, having been earlier oxidized and bound to the palaeosol clay matrix as a poorly crystallized ferric oxide or oxyhydroxide mineral. Carbon isotope compositions of pedogenic carbonate correlate with the inferred depth of carbonate precipitation. Rhizoliths preserved below the lowest stratigraphic occurrences of pedogenic slickensides are consistently depleted in 13C relative to nodules, which formed stratigraphically higher, within the zone of active soil shrink and swell processes. Nodular carbonate, precipitated in proximity to deep cracks in the soil, is enriched due to increased gas exchange with isotopically heavy atmospheric CO2. Accordingly, rhizolith compositions will most accurately estimate palaeoatmospheric levels of CO2; the use of nodule compositions may result in overestimation of PCO2 by as much as 30%.  相似文献   

5.
The influence of pH and concentration on boron coprecipitation by calcite were evaluated under near-equilibrium conditions at 25°C. Calcite was precipitated by adding a metastable polymorph (vaterite or aragonite) to a solution of known boron concentration. This method maintains a nearly constant solution composition during the slow conversion of the metastable polymorph to calcite.Boron uptake in calcite was found to be strongly pH-dependent, increasing two orders of magnitude from pH 8.5 to pH 10.5. Boron incorporation into calcites precipitated from vaterite-saturated solutions was five times greater than in calcites precipitated from aragonite-saturated solutions. Ostensibly, these results suggest that the calcite precipitation rates were not low enough to attain equilibrium partitioning of boron into calcite. However, scanning electron micrograph analyses showed that the prevalent crystal forms of calcite generated from aragonite and those generated from vaterite were distinctly different. The different quantities of boron incorporated into these calcites may reflect different crystal growth mechanisms, consistent with face-dependent, nonequilibrium partitioning of trace elements in calcite.At a constant pH of 9.0, boron uptake increased from less than 15 to over 290 mg/kg CaCO3 as the solution boron concentration was increased from 5 to 100 mg/kg. Our results agree with those of other investigators, despite differences in solution composition, and calcite precipitation techniques used. The agreement between the studies may be because the crystal growth morphology of the calcite was rhombohedral in both cases.  相似文献   

6.
A 3 km long lateral facies transition from Oligo-Miocene skeletal grainstones into packstones and mudstones displays systematic variation in carbonate skeletal fragment alteration and secondary carbonate mineral composition. Within the skeletal grainstone end-member all aragonitic grains have dissolved, all Mg-calcite skeletal fragments have altered to calcite, and calcite has been precipitated as both void-filling spar and as syntaxial overgrowths on echinoid fragments. Within the transitional grainstone-packstone lithologies some skeletal fragments show preservation of their original mineralogy, while calcite, ferroan calcite spar and dolomite have precipitated in void spaces. Within the packstone-mudstone end-member of the transition, aragonitic grains have been preserved and Mg-calcite skeletal fragments have retained most of their magnesium. Thin, originally porous grainstone layers within the pack-stone-mudstones contain sideroplesite and ferroan calcite spar in void spaces, and iron has been incorporated in skeletal fragments which were originally Mg-calcite. In these grains iron has been incorporated at the expense of magnesium until the grains approach the composition of the surrounding ferroan calcite cement. The lateral variation in diagenetic alteration across this facies transition is a function of differing groundwater movement and composition, controlled ultimately by the composition, porosity and permeability of the host lithologies.  相似文献   

7.
High-magnesium calcite overgrowths were precipitated on Iceland spar calcite crystals buried in Bahamian sediments. Their composition was within the range of carbonate cements in this area. The precipitation rate of the overgrowths was slower and the magnesium content higher than predicted from laboratory experiments, possibly due to adsorption of organic compounds.  相似文献   

8.
Recent work has established that marine teleost (bony) fish represent a prolific source of mud grade, mainly high‐Mg calcite, carbonate sediment by means of primary precipitation within the intestine. Previously documented crystalline products display a diverse array of morphologies, many unique in shallow tropical marine settings, and have a wide range of magnesium contents (from 18 to 39 mol% MgCO3). This study utilizes scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, X‐ray diffraction and liquid ion chromatography to provide a more extensive and expansive morphological, mineralogical and chemical characterization of the crystalline forms produced by a wider range of piscine functional groups (covering 21 different fish species common in The Bahamas). Several crystal morphologies not previously described in fish‐derived carbonates are documented, and chemical composition is found to be more variable than previously reported: in addition to high‐Mg calcites with >18 mol% MgCO3, high‐Mg calcites with lower MgCO3 contents and low‐Mg calcites are identified. From the expanded species range, MgCO3 content in fish‐derived carbonates ranges from ca 0˙5 to > 40 mol%, and particle length is in the range 0˙1 to >50 μm (typically <2 μm for individual crystals). Amorphous Mg‐carbonates (with detectable CaCO3 of <2 mol%) are also found to varying extent in the precipitates of many species. Dominant mineralogy and MgCO3 content varies with producing species and crystal morphology (itself a species‐dependent variable). Given the very small grain size and often high MgCO3 contents of these carbonates, interesting questions arise about their preservation potential. Thus, the extent to which carbonates produced by different species may follow different post‐excretion preservation pathways is considered.  相似文献   

9.
Geochemistry of soil, soil water, and soil gas was characterized in representative soil profiles of three Michigan watersheds. Because of differences in source regions, parent materials in the Upper Peninsula of Michigan (the Tahquamenon watershed) contain only silicates, while those in the Lower Peninsula (the Cheboygan and the Huron watersheds) have significant mixtures of silicate and carbonate minerals. These differences in soil mineralogy and climate conditions permit us to examine controls on carbonate and silicate mineral weathering rates and to better define the importance of silicate versus carbonate dissolution in the early stage of soil-water cation acquisition.Soil waters of the Tahquamenon watershed are the most dilute; solutes reflect amphibole and plagioclase dissolution along with significant contributions from atmospheric precipitation sources. Soil waters in the Cheboygan and the Huron watersheds begin their evolution as relatively dilute solutions dominated by silicate weathering in shallow carbonate-free soil horizons. Here, silicate dissolution is rapid and reaction rates dominantly are controlled by mineral abundances. In the deeper soil horizons, silicate dissolution slows down and soil-water chemistry is dominated by calcite and dolomite weathering, where solutions reach equilibrium with carbonate minerals within the soil profile. Thus, carbonate weathering intensities are dominantly controlled by annual precipitation, temperature and soil pCO2. Results of a conceptual model support these field observations, implying that dolomite and calcite are dissolving at a similar rate, and further dissolution of more soluble dolomite after calcite equilibrium produces higher dissolved inorganic carbon concentrations and a Mg2+/Ca2+ ratio of 0.4.Mass balance calculations show that overall, silicate minerals and atmospheric inputs generally contribute <10% of Ca2+ and Mg2+ in natural waters. Dolomite dissolution appears to be a major process, rivaling calcite dissolution as a control on divalent cation and inorganic carbon contents of soil waters. Furthermore, the fraction of Mg2+ derived from silicate mineral weathering is much smaller than most of the values previously estimated from riverine chemistry.  相似文献   

10.
Secondary carbonate formations, such as travertine and calcareous tufa deposits, are important archives for quaternary continental climate studies and archaeology. The extremely complex growth mechanisms result in some serious problems for precise mass spectrometric uranium-series dating. Often, detrital and organic particles contaminate the carbonate and large pore volumes yield a great potential for open system behavior. We utilized microscopic, mineralogical and geochemical methods prior to sample selection to determine the abundance of primary calcite, i.e. micrite and spar. Furthermore, the state of alteration was characterized by cathodoluminescence and trace-element analysis. We conclude that travertine and calcareous tufa are appropriate for precise U-series age determination if a) micrite and/or spar are the dominant phases; b) cathodoluminescence of both phases is weak or absent; c) Fe and Al levels are low; and d) Sr concentrations are close to the average of the studied site. We mapped and sampled solely areas of major micrite/spar abundance having minor alteration for accurate U-series dating. When this new method was applied, travertines located in eastern Germany (sites Bad Langensalza, Burgtonna and Weimar-Ehringsdorf) gave single 230Th/238U-ages consistent with the lithological growth sequence and greatly improved compared to previously published chronologies. In addition, we determined 230Th/U isochron ages on bulk samples that confirm our single ages. In contrast to primary calcite, pore cements are homogeneously distributed throughout the travertine fabric and reflect early diagenetic processes and/or weathering.  相似文献   

11.
Large pisoliths from the Laguna Pastos Grandes playa in the Bolivian Altiplano have a wide diversity of cortical fabrics and variable mineralogical composition. The cortical laminae are composed of radial calcite bundles, spar calcite, micrite, amorphous silica, mixed micrite-amorphous silica, quartz, gypsum and halite. Diatoms are common in the outer parts of some radial calcite laminae and amorphous silica laminae, but cyanobacterial filaments are rare. Although the organization of the cortical laminae is highly variable, some repetitive sequences of different laminae are present. Cavities in and between pisoliths contain micrite, detrital grains, calcite bundles and peloids morphologically similar to those found in marine reefs. The pisoliths grow in shallow ephemeral pools fed by hot springs. Radial bundles of calcite precipitate rapidly by degassing and photosynthetic removal of CO2 following spring snowmelt. Conditions for micrite precipitation are unclear, but there is evidence to suggest formation in partially stagnant waters, some of elevated salinity. Amorphous silica laminae precipitate mainly by evaporative concentration; quartz may precipitate from warm silica-rich spring waters that remain below amorphous silica saturation. The evaporite minerals form during desiccation of the pools or from spray. The peloids in cavities are probably primary precipitates. Different types of laminae may form simultaneously in different pools because of the highly variable conditions across the playa. Lateral migration of spring locations through time has created a complex carbonate-silica pavement. Large spherical pisoliths form in outflow channels near spring orifices and across discharge aprons where waters are several decimetres deep. With mineral precipitation, channels are filled and become shallow, producing discoid pisoliths and crusts. In shallow waters and on distal aprons only small pisolith gravels form. As spring pools fill with deposits, their locations shift laterally; new pisoliths form elsewhere or precipitation may recommence on older abandoned pisoliths.  相似文献   

12.
A laterally extensive calcrete profile has been identified in the Late Asbian (Lower Carboniferous) shallow marine shelf limestones of the Llangollen area, North Wales. The upper surface of the profile is defined by a laterally discontinuous palaeokarstic surface and by laminated calcareous crusts which developed within the underlying limestone. The profile contains a unique series of early pore-filling vadose cements which only occur down to 1 m below the palaeokarstic surface. Cathodoluminescence reveals that these cements pre-date the late pore-filling meteoric phreatic cements which occur throughout local Asbian lithologies. A spar cement stratigraphy has been established for the calcrete profile. Subaerial vadose cements comprise two generations of non-luminescent cement, followed by a brightly luminescent generation which occasionally shows an acicular habit. This needle-fibre calcite represents the final stage of vadose cementation. Precipitation of vadose cements was contemporary with subaerial alteration and micritization of the limestone. Textures, visible only with cathodoluminescence, provide evidence of recurrent periods of fabric dissolution. The most extensive phase of dissolution occurred immediately after the precipitation of the non-luminescent subaerial vadose cements. Several different textures have been recorded, each reflecting the morphology of a partially dissolved substrate. Dissolution textures are generally confined to the walls of the larger pores and to early brecciation fractures. These probably acted as fluid pathways in the calcrete during early subaerial diagenesis. Much of the non-marine micrite in the calcrete profile appears as needle-fibre calcite under cathodoluminescence. This acicular calcite was probably formed in response to localized supersaturation of meteoric pore fluids caused by periods of near-surface evaporation. Since needle-fibre luminescence is strongly variable, these ambient conditions are not believed to have directly controlled the activator ion concentrations of cementing pore waters. Needle-fibre calcite is considered to be a cement precipitate which has almost completely recrystallized to micrite, probably during the late stages of subaerial diagenesis. Two generations of subaerial micrite which define a ‘micrite stratigraphy’, have been distinguished under cathodoluminescence. Reconstructing the diagenetic history of this ancient calcrete profile has revealed that subaerial alteration was multistaged, with many diagenetic processes acting simultaneously during a single phase of emergence.  相似文献   

13.
Stoichiometric solubility constants of calcite in initially supersaturated solutions of various magnesium to calcium concentration ratios but identical ionic strength were determined at 25°C and one atmosphere total pressure.The thermodynamic solubility constant of calcite is used with ion pairing equations to interpret the data reported in this study. Results indicate that even though magnesian calcites, rather than pure calcite, precipitate from seawater solutions containing magnesium ions, the incorporation of MgCO3 in the calcite crystal lattice does not extensively alter the equilibrium calcium carbonate activity product.The equilibrium activity of the ionic species in solution and the composition of magnesian calcite overgrowths precipitated from solutions of similar composition are used to calculate the solubility of magnesian calcites. The values for magnesian calcite solubilities obtained by this approach are lower than those obtained from the dissolution kinetics of biogenic carbonates.  相似文献   

14.
为了研究洞穴母岩对洞穴系统及次生沉积物产生的影响,以重庆丰都雪玉洞母岩为研究对象,对其沉积地质特征进行了详细的研究,同时还探讨母岩的沉积地质特征与洞穴发育及次生沉积物特征之间的关联。结果表明,雪玉洞的母岩层位为下三叠统飞仙关组第二段,其沉积相为颗粒滩。母岩的岩性为砂屑灰岩、鲕粒灰岩、砾屑灰岩, 夹少量微晶灰岩。母岩和洞穴次生沉积物的主要矿物成分是低镁方解石（LMC, low magnesium calcite）。母岩较低的Mg/Ca导致洞穴滴水的Mg/Ca也较低,这使得组成次生沉积物的低镁方解石晶体快速侧向生长,并导致方解石晶体纯净、粗大且自形程度高。雪玉洞母岩顶底板岩层沉积期稳定的滩间海沉积环境有助于形成高强度的厚层微晶灰岩从而为洞穴系统的发育提供有效的支撑。这表明洞穴母岩的沉积地质特征会在物质基础的层面对洞穴系统的发育以及洞穴次生沉积物的特征产生显著影响。   相似文献   

15.
Diagenesis in shallow cores from the Lower Cretaceous Edwards Limestone was investigated in thin sections and with the scanning electron microscope (SEM). The SEM is a particularly useful tool in the study of diagenesis in porous fine-grained carbonate rocks because of its good resolution and depth of field.The Edwards Group was deposited in shallow-marine environments and underwent normal early diagenesis. Dolomite and evaporite minerals such as gypsum formed penecontemporaneously in some tidal-flat sediments. Slightly later, when the carbonate sediments were flushed by fresh water, carbonate mud recrystallized to micrite and aragonite allochems altered to calcite or were leached. Some cementation by calcite occurred in a fresh-water phreatic environment.The Edwards Limestone was divided into two zones by Miocene faulting along the Balcones Fault Zone. On the upthrown side of the fault a circulating fresh-water aquifer developed, whereas relatively stagnant brackish water remained present on the down-thrown side. Differences in the chemistry of the interstitial fluids in these zones resulted in different types of diagenesis. The presence of fresh water caused extensive oxidation, solution along fractures, recrystallization of micrite to coarse microspar and pseudospar, precipitation of equant sparry-calcite crystals in a variety of shapes and sizes, and extensive dedolomitization. The dedolomitization is thought to have been caused by the high Ca/Mg ratio of the circulating fresh water in a shallow subsurface environment.In the brackish-water zone, textures and fabrics related to deposition or early diagenesis, such as primary porosity, unoxidized organic material, framboidal pyrite, and evaporite minerals have been preserved. Some precipitation of authigenic dolomite, celestite, and kaolinite occurred in the brackish-water zone. In contrast to the fresh-water zone, precipitation of coarse calcite spar, dedolomitization, and recrystallization of micrite to microspar occurred only rarely in the brackish-water zone.  相似文献   

16.
An evaluation of the response of an Andosol and a Cambisol to acid deposition and weathering rates was studied by using a controlled laboratory leaching experiment. Both soils where derived from mafic parent material, a Histic Andosol from Western Iceland and a Cambisol from North East Scotland. De-ionized water and water acidified with H2SO4 (pH 3) was leached through reconstructed soil columns to simulate 34 years of precipitation.Acidic input increased cation leaching and weathering rates in both soil types and reduced pH levels. The Andosol proved generally to have higher weathering rates, leaching potential, ion exchange and acid-buffering capacity as well as maintaining a relatively steady pH despite intense acidic input. This was due to differences in parent material and mineral composition. The Andosol was developed from basaltic volcanic tephra, which had higher dissolution rates due to its amorphous mineral structures. The Cambisol was developed from gabbro with more stable mineral structures.  相似文献   

17.
Microbialites (benthic microbial carbonate deposits) were discovered in a hypersaline alkaline lake on Eleuthera Island (Bahamas). From the edge towards the centre of the lake, four main zones of precipitation could be distinguished: (1) millimetre‐sized clumps of Mg‐calcite on a thin microbial mat; (2) thicker and continuous carbonate crusts with columnar morphologies; (3) isolated patches of carbonate crust separated by a dark non‐calcified gelatinous mat; and (4) a dark microbial mat without precipitation. In thin section, the precipitate displayed a micropeloidal structure characterized by micritic micropeloids (strong autofluorescence) surrounded by microspar and spar cement (no fluorescence). Observations using scanning electron microscopy (SEM) equipped with a cryotransfer system indicate that micrite nucleation is initiated within a polymer biofilm that embeds microbial communities. These extracellular polymeric substances (EPS) are progressively replaced with high‐Mg calcite. Discontinuous EPS calcification generates a micropeloidal structure of the micrite, possibly resulting from the presence of clusters of coccoid or remnants of filamentous bacteria. At high magnification, the microstructure of the initial precipitate consists of 200–500 nm spheres. No precipitation is observed in or on the sheaths of cyanobacteria, and only a negligible amount of precipitation is directly associated with the well‐organized and active filamentous cyanobacteria (in deeper layers of the mat), indicating that carbonate precipitation is not associated with CO2 uptake during photosynthesis. Instead, the precipitation occurs at the uppermost layer of the mat, which is composed of EPS, empty filamentous bacteria and coccoids (Gloeocapsa spp.). Two‐dimensional mapping of sulphate reduction shows high activity in close association with the carbonate precipitate at the top of the microbial mat. In combination, these findings suggest that net precipitation of calcium carbonate results from a temporal and spatial decoupling of the various microbial metabolic processes responsible for CaCO3 precipitation and dissolution. Theoretically, partial degradation of EPS by aerobic heterotrophs or UV fuels sulphate‐reducing activity, which increases alkalinity in microdomains, inducing CaCO3 precipitation. This degradation could also be responsible for EPS decarboxylation, which eliminates Ca2+‐binding capacity of the EPS and releases Ca2+ ions that were originally bound by carboxyl groups. At the end of these processes, the EPS biofilm is calcified and exhibits a micritic micropeloidal structure. The EPS‐free precipitate subsequently serves as a substrate for physico‐chemical precipitation of spar cement from the alkaline water of the lake. The micropeloidal structure has an intimate mixture of micrite and microspar comparable to microstructures of some fossil microbialites.  相似文献   

18.
The seeded precipitation (crystal growth) of aragonite and calcite from sea water, magnesium-depleted sea water, and magnesium-free sea water has been studied by means of the steady-state disequilibrium initial rate method. Dissolved magnesium at sea water levels appears to have no effect on the rate of crystal growth of aragonite, but a strong retarding effect on that of calcite. By contrast, at levels less than about 5 per cent of the sea water level, Mg has little or no effect on calcite growth. Extended crystal growth on pure calcite seeds in sea water of normal Mg content resulted in the crystallization of magnesium calcite overgrowths, containing 7–10 mole % MgCO3 in solid solution. This suggests that the rate inhibition by Mg is due to its incorporation within the calcite crystal structure during growth, which causes the resulting magnesian calcite to be considerably more soluble than pure calcite. The standard free energy of formation of 8.5 mole% Mg calcite calculated on this assumption is in good agreement with independent estimates of magnesian calcite stability.From the work of Katz (Geochim. Cosmochim. Acta37, 1563–1586, 1973), Plummer and Mackenzie (Amer. J. Sci. 273, 515–522, 1974), and the present paper, it can be predicted that the most stable calcite in Ca-Mg exchange equilibrium with sea water contains between 2 and 7 mole%MgCO3 in solid solution. Likewise, calcites containing more than 8.5 mole% MgCO3 are less stable, and those containing less than 8.5 mole% MgCO3 are more stable than aragonite plus Ca and Mg in sea water.  相似文献   

19.
ABSTRACT
The carbon and oxygen isotopic composition of the Austin Chalk was examined in cores representing a range of depths from surface to 3000 m in order to document the effects of burial diagenesis on carbon and oxygen isotopic composition. Low magnesium calcite oysters were separated (from 500 um wide areas) and analysed to estimate the starting composition of Cretaceous marine sediment. These gave an average value of -2·5%δ18O; + 2·0%δ13C (PDB). The compositions of micrite, intergranular cement, and fracture cement were analysed, and their deviation from this original marine composition was evaluated to document the progression of chalk diagenesis. Interestingly, micrite exhibits only minor variation in composition from marine values despite present burial depth ranges in excess of 3000 m. The average deviation from δ18O marine is less than 1·5. Furthermore, intergranular cement and particularly fracture cements, which occur only in the deepest cores and which clearly post-date micrite lithification, are generally indistinguishable from micrite in composition. Isotopic compositions exhibit no correlation with depth of burial despite abundant petrographic evidence of deep burial diagenesis. This uniformity in composition is interpreted as reflecting a closed, rock-dominated diagenetic system in which the compositions of precipitated carbonate cements were controlled by the composition of dissolving carbonates during lithification. As such, the composition of burial cement is not representative of the rock-water temperatures during precipitation.
Thus, in the context of isotopic analyses from other carbonate systems, unless the degree of openness of the diagenetic system is known, oxygen isotopic signatures of cements cannot directly be converted to the rock-water temperatures at which they were precipitated unless the composition of the ambient porefluid is also known.  相似文献   

20.
准噶尔盆地西北缘石炭—二叠系火山岩裂缝十分发育, 普遍充填方解石矿物。通过对钻井岩心裂缝类型划分、 方解石脉原生流体包裹体均一温度测试、 方解石地球化学数据测试与分析, 揭示了方解石脉成因。结果表明, 石炭—二叠系火山岩中的裂缝主要包括风化裂缝、 构造裂缝、 成岩裂缝和溶蚀裂缝。裂缝中方解石的原生流体包裹体均一温度分布为40℃～150℃, 变化范围较大, 具有低温、 高温及混合流体特征。方解石的碳、 氧同位素表明, 方解石的形成与大气淡水和埋藏流体有关, 锶同位素和锰元素进一步证实, 埋藏流体为深部热液流体或埋藏流体溶蚀了火山物质。准噶尔盆地西北缘石炭—二叠系火山岩受逆冲推覆构造和风化淋滤作用双重影响, 构造裂缝和风化裂缝彼此连通并沟通了深部热液与大气淡水。在火山岩裂缝中形成了兼具大气淡水与深部热液流体特征的方解石充填物。  相似文献   

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