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1.
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The reaction rate and composition of calcite and aragonite overgrowths precipitated from seawater solutions of various salinities (i.e. S=5, 15, 25, 35, 44) were determined at 25°C and 10−2.5-atm. CO2 partial pressure using a constant disequilibrium seeded technique. The rate data were fitted to an empirical rate law of the form:
logR=n(ωc(or a)-1)+logk

where n is the empirical reaction order; and k is the rate constant. Calcite precipitation rates in seawater solutions do not vary appreciably as a result of salinity variations over the range investigated, while those for aragonite show an increase in going from the higher (i.e. S=35, 44) to the lower (i.e. S=5, 15, 25) salinity range. This study also confirms previously published findings that above a given saturation state (i.e. Ωc>/2.6) aragonite precipitates more rapidly than calcite at 25°C.

The incorporation of Sr2+ in aragonite and Mg2+ in calcite overgrowths are independent of the precipitation rate. The partition coefficient of Sr2+ in aragonite is approximately equal to unity and is unaffected by salinity variations between 5 and 44. However, the Mg2+ partition coefficient in calcite, increases with decreasing salinity of the parent seawater solutions, possibly as a result of variations in the sulfate content of the solutions and solids.

The experimental results were discussed in the context of a number of geological environments.  相似文献   


3.
The chemistry of orthophosphate uptake from synthetic seawater onto the surfaces of synthetic calcite, aragonite and low-magnesium biogenic calcite has been studied, in order to elucidate the kinetics of the process (generally believed to be the major control of dissolved reactive phosphate in carbonate-rich marine sediments). Our results differ from those obtained by others, who have studied orthophosphate uptake in low ionic strength solutions and at much higher supersaturations relative to apatite.In both ‘free drift’ and chemostat experiments, Mg and F have only a minor effect on the reaction rate. Even at constant solution composition the rate of orthophosphate uptake was found to decrease by 106 over a two week period. The data from the ‘free drift’ experiments can be fitted to the Elovich equation. This indicates that the kinetics observed for this reaction can be explained by an exponential decrease in available surface reaction sites and/or a linear increase in the activation energy associated with chemisorption as the reaction proceeds.  相似文献   

4.
The morphology and composition of abiogenic (synthetic) aragonites precipitated experimentally from seawater and the aragonite accreted by scleractinian corals were characterized at the micron and nano scale. The synthetic aragonites precipitated from supersaturated seawater solutions as spherulites, typically 20-100 μm in diameter, with aggregates of sub-micron granular materials occupying their centers and elongate (fibrous) needles radiating out to the edge. Using Sr isotope spikes, the formation of the central granular material was shown to be associated with high fluid pH and saturation state whereas needle growth occurred at lower pH and saturation state. The granular aggregates have significantly higher Mg/Ca and Ba/Ca ratios than the surrounding fibers.Two types of crystals are identified in the coral skeleton: aggregates of sub-micron granular material and bundles of elongate (fibrous) crystals that radiate out from the aggregates. The granular materials are found in “centers of calcification” and in fine bands that transect the fiber bundles. They have significantly higher Mg/Ca and Ba/Ca ratios than the surrounding fibers.The observed relationship between seawater saturation state and crystal morphology and composition in the synthetic aragonites was used as a framework to interpret observations of the coral skeleton. We propose that coral skeletal growth can be viewed as a cyclical process driven by changes in the saturation state of the coral’s calcifying fluids. When saturation state is high, granular crystals precipitate at the tips of the existing skeletal elements forming the centers of calcification. As the saturation state decreases, aragonitic fibres grow in bundles that radiate out from the centers of calcification.  相似文献   

5.
The coprecipitation of Sr, Mg, Na and K with anhydrite during the dehydration of gypsum was studied in laboratory experiments. The partition coefficients of Mg and Sr between anhydrite and solution decrease with increasing temperature. The partition coefficients of the alkali-ions do not depend upon temperature, but are affected by the brine composition.The mechanism of the phase transformation gypsum → anhydrite occurs via dissolution and precipitation, when the coprecipitated-ions are repartitioned between the new phase and the solution. The partition coefficients established in this study are applicable also for primary anhydrite.During the dehydration of gypsum at elevated temperatures metastable bassanite may form as an intermediate stage. The amount of cations coprecipitated with bassanite is much larger than the amount coprecipitated with anhydrite or gypsum. This phenomenon may have an influence on the partitioning of cations during the dehydration of gypsum, particularly on Sr.The partition coefficients of seawater cations between anhydrite and the brine are similar to those between gypsum and the brine. For this reason the coprecipitated-ions are not expected to be good indicators to distinguish between primary and secondary calcium sulfate minerals.The temperature effect on the coprecipitation of Mg and Sr with anhydrite makes these ions possible indicators for the temperature at which the phase transformation occurred. This temperature corresponds to the depth of burial of the gypsum at the stage of dehydration.The coprecipitation of seawater cations with anhydrite in the natural environment was studied in two systems: A small Pleistocene evaporite lens from the Sinai Peninsula and the Triassic anhydrite of the Mohilla Formation, Israel. The coprecipitated-ion composition of these samples was used to derive the conditions under which the anhydrite was formed.  相似文献   

6.
7.
Deep-sea corals have been shown to be useful archives of rapid changes in ocean chemistry during the last glacial cycle. Their aragonitic skeleton can be absolutely dated by U-Th data, freeing radiocarbon to be used as a water-mass proxy. For certain species of deep-sea corals, the growth rate allows time resolution that is comparable to ice cores. An additional proxy is needed to exploit this opportunity and turn radiocarbon data into rates of ocean overturning in the past.Neodymium isotopes in seawater can serve as a quasi-conservative water-mass tracer and initial results indicate that deep-sea corals may be reliable archives of seawater Nd isotopes. Here we present a systematic study exploring Nd isotopes as a water-mass proxy in deep-sea coral aragonite. We investigated five different genera of modern deep-sea corals (Caryophyllia, Desmophyllum, Enallopsamia, Flabellum, Lophelia), from global locations covering a large potential range of Nd isotopic compositions. Comparison with ambient seawater measurements yields excellent agreement and suggests that deep-sea corals are reliable archives for seawater Nd isotopes.A parallel study of Nd concentrations in these corals yields distribution coefficients for Nd between seawater and coral aragonite of 1-10, omitting one particular genus (Enallopsamia). The corals and seawater did however not come from exactly the same location, and further investigations are needed to reach robust conclusions on the incorporation of Nd into deep-sea coral aragonite.Lastly, we studied the viability of extracting the Nd isotope signal from fossil deep-sea corals by carrying out stepwise cleaning experiments. Our results show that physical removal of the ferromanganese coating and chemical pre-cleaning have the highest impact on Nd concentrations, but that oxidative/reductive cleaning is also needed to acquire a seawater Nd isotope signal.  相似文献   

8.
The main objectives of this study were to investigate conditions for stable and metastable liquid immiscibility in dry borosilicate synthetic systems and to evaluate effects of temperature and bulk melt composition on two-liquid element partitioning and boron speciation. To distinguish between the stable immiscibility and quench heterogeneity, we used high-temperature centrifuge phase separation. For the case of stable liquid immiscibility, silica-rich (LS) and borate-rich (LB) conjugate liquids formed two distinct layers separated by a sharp meniscus. The liquids were quenched into glasses, which were analysed by electron microprobe. Some of the glasses were also studied by Raman spectroscopy. We used several synthetic mixtures along the danburite-anorthite (CaB2Si2O8-CaAl2Si2O8) and danburite-reedmergnerite (CaB2Si2O8-NaBSi3O8) joins. In addition, we studied four complex, six-component, Mg-bearing compositions with variable Na2O and Al2O3 contents. The experiments show that the width of the LS-LB miscibility gap decreases more rapidly with the B-Al substitution (in the danburite-anorthite join) than with the Ca-Na substitution, implying that interactions between network-forming elements have a greater effect on borate-silicate unmixing than the nature of network-modifying cations. Ca and Mg partition strongly to the depolymerised borate-rich liquid with LB-LS partition coefficients of ∼40 and higher. On the other hand, two-liquid partition coefficients of Na and Al in most cases are close to 1 and show complex variations with temperature and bulk melt composition. Raman spectra of LB glasses quenched at different temperatures suggest that the proportion of trigonal boron in bulk boron content decreases with decreasing temperature. The change in boron speciation appears to affect Al and Na two-liquid partitioning in such a way that at low temperatures, the latter element becomes more compatible with LS.  相似文献   

9.
Surface seawater samples from Kamaran Strait of Yemen were collected for physical and chemical parameter determinations. This work reports the results of air and surface seawater temperature, salinity, pH, and total alkalinity measurements. The air temperature ranged from 29.9°C to 36.5°C with an average value of 31.5?±?1.5°C, whereas the seawater surface temperature ranged from 34.0°C to 36.0°C with a mean value of 34.5?±?0.5°C. The salinity was observed to be high, ranging from 38.03 to 38.81 with an average value of 38.45?±?0.22. The pH ranged from 7.74 to 8.27 with a mean value of 8.11?±?0.10. The total alkalinity was found to range from 2.3860 to 2.5000 meq L?1 with an average value of 2.4288?±?0.0351 meq L?1. The result of the study showed that there was a negative correlation between the pH and surface seawater temperature and salinity. The surface seawater of the Kamaran Strait was found to be several fold supersaturated with respect to calcium carbonate. The measured percent degree of saturation ranged from 454% to 668% with respect to calcite and from 246% to 361% with respect to aragonite. The lowest value of supersaturation with respect to both calcite and aragonite were found in front of as-Salif port, where human and developmental activities are intensively increased. The visual inspection of coral reefs distribution and their intensity were obviously observed in areas of high value of supersaturation with respect to both minerals, high transparency of seawater column, and low human activities. Further studies are needed to investigate the occurrence, distribution, and mineralogy of corals and the effects of physical and chemical parameters upon their growth in the region.  相似文献   

10.
《Geodinamica Acta》2013,26(4):275-287
The Narcao and Cixerri basins in Southwestern Sardinia are east-west trending basins of Oligocene age. Recent geological mapping, combined with structural and stratigraphical analyses, support the proposed hypothesis that these basins were very open growth synclines confined within a structural high, delimited by northwest trending dextral strike slip faults. Previously the basins have been interpreted as fault-bounded grabens. The newer revised interpretation is consistent with the existence of NNW trending dextral strike-slip dynamic, related to a north-south shortening which has generated reverse faulting and tight folds in the underlying, pre-synclinal evolution, Eocene succession. This deformation, along with an interfering sub-orthogonal thrust and fold system which affects the Mesozoic sequence, was traditionally linked to the Pyrenean Orogenesis. The Oligocene–Aquitanian shortening, which resulted in the growth synclines and strike-slip faulting, is consistent with the structural development recognized in north-central Sardinia; there structures related to the collision between continental margins that resulted in the Northern Apennines are well documented. Therefore, the Oligocene tectonics of Southwestern Sardinia also must be related to the collision event between the Southern Europe margin (i.e. a crustal sector corresponding to the future Corsica-Sardinia block) and the Adria Plate, which generated the Northern Apennines. Conversely, the previous E-W shortening- related structures must be related to Pyrenean tectonics.  相似文献   

11.
The relationship between molluscan shell growth rate and skeletal δ18O and δ13C was investigated in a detailed field study for the scallop, Pecten maximus. Seasonal variation in shell growth rate was found to be a governing factor influencing shell δ18O and δ13C. At low shell growth rates, shell δ18O were more positive (of the order +0.4‰) and δ13C more negative (up to −2‰) as compared with predicted values for precipitation of inorganic calcite in isotopic equilibrium with seawater. The deviations in δ18O were hypothesized as reflecting possible differences in solution carbonate chemistry at the site of mineralization in the extrapallial fluid as compared with that of the external seawater medium. The deviations in shell δ13C were consistent with incorporation of isotopically depleted respiratory 13C (i.e., a metabolic effect). A trend toward more depleted shell δ18O and δ13C values occurred at higher shell growth rates, with negative δ18O values as compared with predicted equilibrium at shell growth rates above 0.13 mm per day. These simultaneous negative deviations in skeletal δ18O and δ13C were interpreted as resulting from a kinetic effect. The implications for environmental reconstruction from molluscan isotopic records are discussed in light of a model of isotopic behavior based on the findings of the study.  相似文献   

12.
Understanding past climate change is critical to the interpretation of earth history. Even though relative temperature change has been readily assessed in the marine record, it has been more difficult in the terrestrial record due to restricted taxonomic distribution and isotopic fractionation. This problem could be overcome by the use of multiple paleoproxies. Therefore, the δ18O isotopic composition of five paleoproxies (rodent tooth enamel, δ18OPhosphate = +17.7 ± 2.0‰ n = 74 (VSMOW); fish scale ganoine δ18OPhosphate = +19.7 ± 0.7‰ n = 20 (VSMOW); gastropod shell δ18OCalcite = −1.7 ± 1.3‰ n = 50 (VPDB); charophyte gyrogonite δ18OCalcite = −2.4 ± 0.5‰ n = 20 (VPDB); fish otolith δ18OAragonite = δ18O = −3.6 ± 0.6‰ n = 20 (VPDB)) from the Late Eocene (Priabonian) Osborne Member (Headon Hill Formation, Solent Group, Hampshire Basin, UK) were determined. Because diagenetic alteration was shown to be minimal the phosphate oxygen component of rodent tooth enamel (as opposed to enamel carbonate oxygen) was used to calculate an initial δ18OLocal water value of 0.0 ± 3.4‰. However, a skewed distribution, most likely as a result of the ingestion of evaporating water, necessitated the calculation of a corrected δ18OLocal water value of −1.3 ± 1.7‰ (n = 62). This δ18OLocal water value corresponds to an approximate mean annual temperature of 18 ± 1°C. Four other mean paleotemperatures can also be calculated by combining the δ18OLocal water value with four independent freshwater paleoproxies. The calculated paleotemperature using the fish scale thermometry equations most likely represents the mean temperature (21 ± 2°C) of the entire length of the growing season. This should be concordant with the paleotemperature calculated using the Lymnaea shell thermometry equation (23 ± 2°C). The lack of concordance is interpreted to be the result of diagenetic alteration of the originally aragonitic Lymnaea shell to calcite. The mean paleotemperature calculated using the charophyte gyrogonite thermometry equation (21 ± 2°C), on the other hand, most likely represents the mean temperature of a single month toward the end of the growing season. The fish otolith mean paleotemperature (28 ± 2°C) most likely represents the mean temperature of the warmest months of the growing season. An approximate mean annual temperature of 18 ± 1°C, in addition to a mean growing season paleotemperature of 21 ± 2°C (using fish scale only) with a warmest month temperature of 28 ± 2°C, and high associated standard deviations suggest that a subtropical to warm temperate seasonal climate existed during the deposition of the Late Eocene Osborne Member.  相似文献   

13.
Shell aragonite from ammonites collected in the Upper Cretaceous of West Greenland was investigated by means of macroscopic/microscopic visual evaluation, analyses of calcite/aragonite ratios, carbon and oxygen isotopic compositions and Sr and Mg concentrations of shell carbonate and of amino acid compositions of organic matrices. The results are: (1) Material visually classified as well preserved may have suffered diagenetic modifications of mineralogical and chemical composition. (2) Of the chemical and mineralogical parameters studied, amino acid composition, calcite/aragonite ratios and magnesium concentrations were found to be most sensitive to post-depositional modifications, while oxygen isotope composition and strontium concentrations showed detectable diagenetic modifications only after more pronounced alterations. (3) Based on the Mg/Ca ratios and calcite concentrations of the shell aragonite, a diagenetic classification has been proposed grouping the material into well preserved, moderately preserved and poorly preserved. (4) The chemical and mineralogical composition of the best preserved material suggests that the Upper Cretaceous ammonites had a shell composition similar to that of modern Nautilus and other aragonite-shelled molluscs.  相似文献   

14.
A quasi-harmonic model has been used to simulate the thermodynamic behaviour of the CaCO3 polymorphs, by equilibrating their crystal structures as a function of temperature so as to balance the sum of inner static and thermal pressures against the applied external pressure. The vibrational frequencies and elastic properties needed have been computed using interatomic potentials based on two-body Born-type functions, with O-C-O angular terms to account for covalency inside the CO3 molecular ion. A good agreement with experimental data is generally shown by simulated heat capacity and entropy, while the thermal expansion coefficient seems to be more difficult to reproduce. The results obtained for aragonite are less satisfactory than those of calcite, but they are improved by using a potential specifically optimized on properties of that phase itself.  相似文献   

15.
Detailed knowledge of the extent of post-genetic modifications affecting shallow submarine hydrocarbons fueled from the deep subsurface is fundamental for evaluating source and reservoir properties. We investigated gases from a submarine high-flux seepage site in the anoxic Eastern Black Sea in order to elucidate molecular and isotopic alterations of low-molecular-weight hydrocarbons (LMWHC) associated with upward migration through the sediment and precipitation of shallow gas hydrates. For this, near-surface sediment pressure cores and free gas venting from the seafloor were collected using autoclave technology at the Batumi seep area at 845 m water depth within the gas hydrate stability zone.Vent gas, gas from pressure core degassing, and from hydrate dissociation were strongly dominated by methane (> 99.85 mol.% of ∑[C1–C4, CO2]). Molecular ratios of LMWHC (C1/[C2 + C3] > 1000) and stable isotopic compositions of methane (δ13C = ? 53.5‰ V-PDB; D/H around ? 175‰ SMOW) indicated predominant microbial methane formation. C1/C2+ ratios and stable isotopic compositions of LMWHC distinguished three gas types prevailing in the seepage area. Vent gas discharged into bottom waters was depleted in methane by > 0.03 mol.% (∑[C1–C4, CO2]) relative to the other gas types and the virtual lack of 14C–CH4 indicated a negligible input of methane from degradation of fresh organic matter. Of all gas types analyzed, vent gas was least affected by molecular fractionation, thus, its origin from the deep subsurface rather than from decomposing hydrates in near-surface sediments is likely.As a result of the anaerobic oxidation of methane, LMWHC in pressure cores in top sediments included smaller methane fractions [0.03 mol.% ∑(C1–C4, CO2)] than gas released from pressure cores of more deeply buried sediments, where the fraction of methane was maximal due to its preferential incorporation in hydrate lattices. No indications for stable carbon isotopic fractionations of methane during hydrate crystallization from vent gas were found. Enrichments of 14C–CH4 (1.4 pMC) in short cores relative to lower abundances (max. 0.6 pMC) in gas from long cores and gas hydrates substantiates recent methanogenesis utilizing modern organic matter deposited in top sediments of this high-flux hydrocarbon seep area.  相似文献   

16.
Collalti  Dino  Strobl  Eric 《Natural Hazards》2022,110(3):2059-2086
Natural Hazards - This study investigates economic damage risk due to extreme rainfall during tropical storms in Jamaica. To this end, remote sensing precipitation data are linked to regional...  相似文献   

17.
The solubilities of synthetic, natural and biogenic aragonite and calcite, in natural seawater of 35%. salinity at 25°C and 1 atm pressure, were measured using a closed system technique. Equilibration times ranged up to several months. The apparent solubility constant determined for calcite of 4.39(±0.20) × 10?7 mol2 kg?2 is in good agreement with other recent solubility measurements and is constant after 5 days equilibration. When we measured aragonite solubility we observed that it decreased with increasing time of equilibration. The value of 6.65(±0.12) × 10?7 mol2 kg?2, determined for equilibration times in excess of 2 months, is significantly less than that found in other recent measurements, which employed equilibration times of only a few hours to days. No statistically significant difference was found among the synthetic, natural and biogenic material. Solid to solution ratio, contamination of aragonite with up to 10 wt% calcite and recycling of the aragonite made no statistically significant difference in solubility when long equilibration times were used.Measured apparent solubility constants of aragonite and calcite are respectively 22( ± 3)% and 20( ± 2)% less than apparent solubility constants calculated from thermodynamic equilibrium constants and seawater total activity coefficients. These large differences in measured and calculated apparent solubility constants may be the result of the formation of surface layers of lower solubility than the bulk solid.  相似文献   

18.
云南兰坪富锶文石的振动光谱特征   总被引:3,自引:0,他引:3       下载免费PDF全文
为进一步研究富锶文石的晶体结构、颜色成因和矿物成因,采用振动光谱、EMPA和SEM对富锶文石进行了测试和分析。红外光谱、拉曼光谱测试分析表明,由于富锶文石存在着锶与钙的类质同像现象,其红外光谱和拉曼光谱中CO3^2-的v1、v2、v3、v4种振动模式波数介于文石和碳酸锶矿之间,与文石、碳酸锶矿等文石型碳酸盐振动光谱特征一致,并且文石的v4存在分裂峰。EMPA面扫描发现Ca^2 、Sr^2 的分布与富锶文石内部环带的分布存在一致性。由于CuO含量较少,分布规律不明显。SEM分析发现在环带之间存在空隙,各环带中富锶文石结晶程度和晶体表面特征不一,不同颜色和形态的环带反复生长。生长过程中,流体成分中各种元素的含量、温度和压力的变化造成不同颜色环带的形成,反映了该富锶文石是经过不同时期沉积形成的。  相似文献   

19.
A semi-empirical treatment of isothermal element partitioning caused by flow rate-dependent calcite growth from hydrothermal solutions yields element/Ca ratios that are qualitatively similar to those observed in calcite bands of the Pb-Zn banded ores from the Harz Mountains, Germany. The comparison of the calculations with the analytical results suggests that flow rates varied between episodes of calcite precipitation as well as during formation of individual bands. Based on a flow rate-dependent element partition coefficient, changing element/Ca ratios in precipitates from a hydrotherm are therefore not necessarily indicative of changing compositions of the fluid. The variations in element/Ca ratios to be envisaged could be as much as a factor of three.Notation A defined by Eq. 8 - a, b individual values of any element in Eq. 1 - c concentration in moles/m3 - C 0 initial concentration moles/m3 - i running parameter - F area of precipitation in m2 - k p rate constant of pth order reaction in s · m3/molesp - R linear (one-dimensional) growth rate in moles/m2 · s - p order of growth reaction - s distance from entry of solution in m - s 0 vertical extension of a vein in m - t time in s - v flow rate of hydrothermal solution in m/s - v0 standard flow rate in m/s - r relative flow rate in multiple of v0 - fraction of total precipitation - 0 fraction of precipitation under reference conditions when the hydrothermal solution leaves the vein - defining the sign in Eq. 1 for elements that are en riched (= +1) or impoverished (= -1) - logarithmic partition coefficient in Eq. 10 - (R) logarithmic partition coefficient as a function of variable growth rate - [ ], { } concentration ratios of fluids and solids, respectively - EL/Ca calculated ratio of El/Ca in the calcite surface zone after Eq. 11  相似文献   

20.
All creations, except mankind, on this Universe are well organized under a natural universal system. They struggle for their survival within the territorial limits of their making. They do not have special barriers between, particularly similar to International Boundaries of Mankind. They even move from one physical region to another if the basic requirements, necessary for their survival are exhausted. Mankind is recognized as supreme to all creations, but diversity of their character, behavior, suspicious, and indifferent political ideology with uncomfortable mask on faces, have created an ending growth of conflicts through passion and reason within and outside the limits of their access, and set a criterion of moving power, to control the other limits on this universe.The basic object of writing this paper is to construct a framework or show a path leading to its construction for uniting mankind on one political platform, free from the influence of power and pressure. Keeping in mind the teaching of religious doctrine and their concept of world orders and the philosophical approaches, particularly the recent political writing of Kant towards inidvidual rights and freedom under the controlling factors of reason and passion, a framework for the new world order is possible to establish, leading to the final goal of creating a global system.  相似文献   

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