Effect of orthophosphate on the dissolution kinetics of biogenic magnesian calcites     

Lynn M. Walter  Jeffrey S. Hanor 《Geochimica et cosmochimica acta》1979,43(8):1377-1385

The dissolution behavior of two biogenic Mg-calcites, the echinoid, Tripneustes (12 mol% MgCO₃), and the red alga, Neogoniolithon (18 mol% MgCO₃ plus brucite), was studied using free-drift methods in distilled water and phosphate-spiked solutions at 25°C and P_CO2 = 1 atm. Small concentrations of phosphate strongly inhibit dissolution rates. Inhibition increases with increased phosphate levels and with approach toward saturation. Near saturation, dissolution rates are reduced by 10³ by the presence of 0.6 μmol adsorbed-P/m². The magnitude of phosphate inhibition is similar to that observed for low-Mg calcite, and like calcite, the mechanism of inhibition is probably by adsorption of P at surface kink sites. Phosphate appears to inhibit removal of Mg and Ca equally during Mg-calcite dissolution. Rates of brucite dissolution are unaffected by phosphate.Mg-calcites containing >8.5 mol% MgCO₃ should be thermodynamically unstable relative to aragonite in most natural waters. Recent work, however, shows that in contrast to its effect on the behavior of Mg-calcites. phosphate does not inhibit aragonite dissolution. The presence of phosphate might thus reverse the relative stability of these two minerals during diagenesis of shallow marine carbonate sediments.  相似文献   

The dissolution kinetics of shallow marine carbonates in seawater: A laboratory study     

Lynn M. Walter  John W. Morse 《Geochimica et cosmochimica acta》1985,49(7):1503-1513

The dissolution kinetics of shallow water marine carbonates (low-Mg calcite, aragonite and Mg-calcites) were investigated in seawater (S = 35) at 25°C and a P_CO2 of 10^?2.5 atm. using the pH-stat method. Carbonate dissoluton rates (μmoles g^?1 hr^?1) fit the empirical kinetic expression, R = k(1 - Ω)ⁿ, where R = dissolution rate, k = rate constant, Ω = saturation state, and n = order of reaction. Reaction orders were near 2.9 for low-Mg calcites, 2.5 for aragonites and 3.4 for Mg-calcites.The rate constant, k, expressed as μmoles g^?1 hr^?1, varied by nearly a factor of ten for the different samples, reflecting differences in amount of reactive surface area. Reactive surface area of the biogenic phases ranged from 0.3% to 66% of the total surface area determined by the BET gas adsorption method. The discrepancy between reactive and total surface area was greatest for samples with high BET surface areas (> 1 m² g^?1) and delicate microstructures.Relative dissolution rates of the various biogenic carbonates as a function of seawater calcium carbonate ion molal product (IMP) were related to both mineral stability and grain microstructure. In seawater undersaturated with respect to aragonite, finely crystalline aragonites dissolved more rapidly than thermodynamically less stable high Mg-calcites (15–18 mole% MgCO₃) with lower reactive surface areas. Therefore, under certain conditions, differences in grain microstructural complexity can override thermodynamic constraints and lead to selective dissolution of a thermodynamically more stable mineral phase.  相似文献   

Dissolution of Carbonate Sediments Under Rising <Emphasis Type="Italic">p</Emphasis>CO<Subscript>2</Subscript> and Ocean Acidification: Observations from Devil’s Hole,Bermuda     

Andreas J. Andersson  Nicholas R. Bates  Fred T. Mackenzie 《Aquatic Geochemistry》2007,13(3):237-264

Rising atmospheric pCO₂ and ocean acidification originating from human activities could result in increased dissolution of metastable carbonate minerals in shallow-water marine sediments. In the present study, in situ dissolution of carbonate sedimentary particles in Devil’s Hole, Bermuda, was observed during summer when thermally driven density stratification restricted mixing between the bottom water and the surface mixed layer and microbial decomposition of organic matter in the subthermocline layer produced pCO₂ levels similar to or higher than those levels anticipated by the end of the 21st century. Trends in both seawater chemistry and the composition of sediments in Devil’s Hole indicate that Mg-calcite minerals are subject to selective dissolution under conditions of elevated pCO₂. The derived rates of dissolution based on observed changes in excess alkalinity and estimates of vertical eddy diffusion ranged from 0.2 mmol to 0.8 mmol CaCO₃ m⁻² h⁻¹. On a yearly basis, this range corresponds to 175–701 g CaCO₃ m⁻² year⁻¹; the latter rate is close to 50% of the estimate of the current average global coral reef calcification rate of about 1,500 g CaCO₃ m⁻² year⁻¹. Considering a reduction in marine calcification of 40% by the year 2100, or 90% by 2300, as a result of surface ocean acidification, the combination of high rates of carbonate dissolution and reduced rates of calcification implies that coral reefs and other carbonate sediment environments within the 21st and following centuries could be subject to a net loss in carbonate material as a result of increasing pCO₂ arising from burning of fossil fuels.  相似文献   

CO₂-water-basalt interaction. Numerical simulation of low temperature CO₂ sequestration into basalts     

Alexander P. Gysi  Andri Stefánsson 《Geochimica et cosmochimica acta》2011,75(17):4728-5509

The interaction between CO₂-rich waters and basaltic glass was studied using reaction path modeling in order to get insight into the water-rock reaction process including secondary mineral composition, water chemistry and mass transfer as a function of CO₂ concentration and reaction progress (ξ). The calculations were carried out at 25-90 °C and pCO₂ to 30 bars and the results were compared to recent experimental observations and natural systems. A thermodynamic dataset was compiled from 25 to 300 °C in order to simulate mineral saturations relevant to basalt alteration in CO₂-rich environment including revised key aqueous species for mineral dissolution reactions and apparent Gibbs energies for clay and carbonate solid solutions observed to form in nature. The dissolution of basaltic glass in CO₂-rich waters was found to be incongruent with the overall water composition and secondary mineral formation depending on reaction progress and pH. Under mildly acid conditions in CO₂ enriched waters (pH <6.5), SiO₂ and simple Al-Si minerals, Ca-Mg-Fe smectites and Ca-Mg-Fe carbonates predominated. Iron, Al and Si were immobile whereas the Mg and Ca mobility depended on the mass of carbonate formed and water pH. Upon quantitative CO₂ mineralization, the pH increased to >8 resulting in Ca-Mg-Fe smectite, zeolites and calcite formation, reducing the mobility of most dissolved elements. The dominant factor determining the reaction path of basalt alteration and the associated element mobility was the pH of the water. In turn, the pH value was determined by the concentration of CO₂ and extent of reaction. The composition of the carbonates depended on the mobility of Ca, Mg and Fe. At pH <6.5, Fe was in the ferrous oxidation state resulting in the formation of Fe-rich carbonates with the incorporation of Ca and Mg. At pH >8, the mobility of Fe and Mg was limited due to the formation of clays whereas Ca was incorporated into calcite, zeolites and clays. Competing reactions between clays (Ca-Fe smectites) and carbonates at low pH, and zeolites and clays (Mg-Fe smectites) and carbonates at high pH, controlled the availability of Ca, Mg and Fe, playing a key role for low temperature CO₂ mineralization and sequestration into basalts. Several problems of the present model point to the need of improvement in future work. The determinant factors linking time to low temperature reaction path modeling may not only be controlled by the primary dissolving phase, which presents challenges concerning non-stoichiometric dissolution, the leached layer model and reactive surface area, but may include secondary mineral precipitation kinetics as rate limiting step for specific reactions such as retrieved from the present reaction path study.  相似文献   

Ca-Mg inter-diffusion in synthetic polycrystalline dolomite-calcite aggregate at elevated temperatures and pressure     

Wuu-Liang Huang  Teh-Ching Liu  Pouyan Shen  Allen Hsu 《Mineralogy and Petrology》2009,95(3-4):327-340

This study measures the reaction rate of dolomite and aragonite (calcite) into Mg-calcite at 800, 850, and 900°C and 1.6 GPa. The dry synthetic dolomite-aragonite aggregate transformed very rapidly into dolomite-calcite polycrystalline aggregate while Mg-calcites formed at a relatively slow rate, becoming progressively richer in Mg with run time. We modeled the reaction progress semi-empirically by the first-order rate law. The temperature dependence of the overall transport rate of MgCO₃ into calcite can be described by the kinetic parameters (E?=?231.7 kJ/mol and A _o ?=?22.69 h^?1). Extrapolation using the Arrhenius equation to the conditions during exhumation of UHPM rocks indicates that the reaction of dolomite with aragonite into Mg-saturated calcite can be completed as the P-T path enters the Mg-calcite stability field in a geologically short time period (<1 Ky). On the other hand, the extrapolation of the rate to prograde metamorphic conditions reveals that the Mg-calcite formed from dolomitic marble in the absence of metamorphic fluid may not reach Mg-saturation until temperatures corresponding to high-grade metamorphism (e.g., >340°C and >10 My). SEM-EDS analysis of individual calcite grains shows compositional gradients of Mg in the calcite grains. The Mg-Ca inter-diffusion coefficient at 850°C is around 1.68?×?10^?14 m²/sec if diffusion is the major control of the reaction. The calculated closure temperatures for Ca-Mg inter-diffusion as a function of cooling rate and grain size reveal that Ca/Mg resetting in calcite in a dry polycrystalline carbonate aggregate (with grain size around 1 mm) may not occur at temperatures below 480°C at a geological cooling rate around 10°C/My, unless other processes, such as short-circuit interdiffusion along grain boundaries and dislocations, are involved.  相似文献   

Silicate weathering in anoxic marine sediments     

K. Wallmann  G. Aloisi  P. Tishchenko  J. Greinert  A. Eisenhauer 《Geochimica et cosmochimica acta》2008,72(12):2895-2918

Two sediment cores retrieved at the northern slope of Sakhalin Island, Sea of Okhotsk, were analyzed for biogenic opal, organic carbon, carbonate, sulfur, major element concentrations, mineral contents, and dissolved substances including nutrients, sulfate, methane, major cations, humic substances, and total alkalinity. Down-core trends in mineral abundance suggest that plagioclase feldspars and other reactive silicate phases (olivine, pyroxene, volcanic ash) are transformed into smectite in the methanogenic sediment sections. The element ratios Na/Al, Mg/Al, and Ca/Al in the solid phase decrease with sediment depth indicating a loss of mobile cations with depth and producing a significant down-core increase in the chemical index of alteration. Pore waters separated from the sediment cores are highly enriched in dissolved magnesium, total alkalinity, humic substances, and boron. The high contents of dissolved organic carbon in the deeper methanogenic sediment sections (50-150 mg dm⁻³) may promote the dissolution of silicate phases through complexation of Al³⁺ and other structure-building cations. A non-steady state transport-reaction model was developed and applied to evaluate the down-core trends observed in the solid and dissolved phases. Dissolved Mg and total alkalinity were used to track the in-situ rates of marine silicate weathering since thermodynamic equilibrium calculations showed that these tracers are not affected by ion exchange processes with sediment surfaces. The modeling showed that silicate weathering is limited to the deeper methanogenic sediment section whereas reverse weathering was the dominant process in the overlying surface sediments. Depth-integrated rates of marine silicate weathering in methanogenic sediments derived from the model (81.4-99.2 mmol CO₂ m⁻² year⁻¹) are lower than the marine weathering rates calculated from the solid phase data (198-245 mmol CO₂ m⁻² year⁻¹) suggesting a decrease in marine weathering over time. The production of CO₂ through reverse weathering in surface sediments (4.22-15.0 mmol CO₂ m⁻² year⁻¹) is about one order of magnitude smaller than the weathering-induced CO₂ consumption in the underlying sediments. The evaluation of pore water data from other continental margin sites shows that silicate weathering is a common process in methanogenic sediments. The global rate of CO₂ consumption through marine silicate weathering estimated here as 5-20 Tmol CO₂ year⁻¹ is as high as the global rate of continental silicate weathering.  相似文献   

Application of calcite Mg partitioning functions to the reconstruction of paleocean Mg/Ca     

Franciszek J. Hasiuk  Kyger C Lohmann 《Geochimica et cosmochimica acta》2010,74(23):6751-6763

Calcite Mg/Ca is usually assumed to vary linearly with solution Mg/Ca, that a constant partition coefficient describes the relationship between these two ratios. Numerous published empirical datasets suggests that this relationship is better described by a power function. We provide a compilation of these literature data for biotic and abiotic calcite in the form of Calcite Mg/Ca = F(Solution Mg/Ca)^H, where F and H are empirically determined fitting parameters describing the slope and deviation from linearity, respectively, of the function. This is equivalent to Freundlich sorption behavior controlling Mg incorporation in calcite. Using a power function, instead of a partition coefficient, lowers Phanerozoic seawater Mg/Ca estimates based on echinoderm skeletal material by, on average, 0.5 mol/mol from previous estimates.These functions can also be used to model the primary skeletal calcite Mg/Ca of numerous calcite phases through geologic time. Such modeling suggests that the Mg/Ca of all calcite precipitated from seawater has varied through the Phanerozoic in response to changing seawater Mg/Ca and that the overall range in Mg/Ca measured among various calcite phases would be greatest when seawater Mg/Ca was also high (e.g., “aragonite seas”) and lowest when seawater Mg/Ca was low (e.g., “calcite seas”). It follows that, during times of “calcite seas” when the seawater Mg/Ca is presumed to have been lower, deposition of calcite with low Mg contents would have resulted in a depressed drive for diagenetic stabilization of shelfal carbonate and, in turn, lead to greater preservation of crystal and skeletal microfabrics and primary chemistries in biotic and abiotic calcites.  相似文献   

Use of mineral/solution equilibrium calculations to assess the potential for carnotite precipitation from groundwater in the Texas Panhandle,USA     

《Applied Geochemistry》2016

This study investigated the potential for the uranium mineral carnotite (K₂(UO₂)₂(VO₄)₂·3H₂O) to precipitate from evaporating groundwater in the Texas Panhandle region of the United States. The evolution of groundwater chemistry during evaporation was modeled with the USGS geochemical code PHREEQC using water-quality data from 100 groundwater wells downloaded from the USGS National Water Information System (NWIS) database. While most modeled groundwater compositions precipitated calcite upon evaporation, not all groundwater became saturated with respect to carnotite with the system open to CO₂. Thus, the formation of calcite is not a necessary condition for carnotite to form. Rather, the determining factor in achieving carnotite saturation was the evolution of groundwater chemistry during evaporation following calcite precipitation. Modeling in this study showed that if the initial major-ion groundwater composition was dominated by calcium-magnesium-sulfate (>70 precent Ca + Mg and >50 percent SO₄ + Cl) or calcium-magnesium-bicarbonate (>70 percent Ca + Mg and <70 percent HCO₃ + CO₃) and following the precipitation of calcite, the concentration of calcium was greater than the carbonate alkalinity (2mCa⁺² > mHCO₃⁻ + 2mCO₃⁻²) carnotite saturation was achieved. If, however, the initial major-ion groundwater composition is sodium-bicarbonate (varying amounts of Na, 40–100 percent Na), calcium-sodium-sulfate, or calcium-magnesium-bicarbonate composition (>70 percent HCO₃ + CO₃) and following the precipitation of calcite, the concentration of calcium was less than the carbonate alkalinity (2mCa⁺² < mHCO₃^- + 2mCO₃⁻²) carnotite saturation was not achieved. In systems open to CO_2, carnotite saturation occurred in most samples in evaporation amounts ranging from 95 percent to 99 percent with the partial pressure of CO₂ ranging from 10^−3.5 to 10^−2.5 atm. Carnotite saturation occurred in a few samples in evaporation amounts ranging from 98 percent to 99 percent with the partial pressure of CO₂ equal to 10^−2.0 atm. Carnotite saturation did not occur in any groundwater with the system closed to CO₂.  相似文献   

Carbonation of lignite fly ash at ambient T and P in a semi-dry reaction system for CO₂ sequestration     

Markus Bauer  Niklas GassenHelge Stanjek  Stefan Peiffer 《Applied Geochemistry》2011,26(8):1502-1512

The global rise in atmospheric greenhouse gas concentrations calls for practicable solutions to capture CO₂. In this study, a mineral carbonation process was applied in which CO₂ reacts with alkaline lignite ash and forms stable carbonate solids. In comparison to previous studies, the assays were conducted at low temperatures and pressures and under semi-dry reaction conditions in an 8 L laboratory mixing device. In order to find optimum process conditions the pCO₂ (10-20%), stirring rate (500-3000 rpm) and the liquid to solid ratio (L/S = 0.03-0.36 L kg⁻¹) were varied. In all experiments a considerable CO₂ uptake from the gas phase was observed. Concurrently the solid phase contents of Ca and Mg (hydr)oxides decreased and CaCO₃ and MgCO₃ fractions increased throughout the experiments, showing that CO₂ was stabilized as a solid carbonate. The carbonation reaction depends on three factors: Dissolution of CO₂ in the liquid phase, mobilization of Ca and Mg from the mineral surface and precipitation of the carbonate solids. Those limitations were found to depend strongly on the variation of the process parameters. Optimum reaction conditions could be found for L/S ratios between 0.12 and 0.18, medium stirring velocities and pCO₂ between 10% and 20%.Maximum CO₂ uptake by the solid phase was 4.8 mmol g⁻¹ after 120 min, corresponding to a carbonation efficiency for the alkaline material of 53% of the theoretical CO₂ binding capacity. In comparison to previous studies both CO₂ uptake and carbonation efficiencies were in a similar range, but the reaction times in the semi-dry process were considerably shorter. The proposed method additionally allows for a more simple carbonation setup due to low T and P, and produces an easier to handle product with low water content.  相似文献   

Cementation of kerogen-rich marls by alkaline fluids released during weathering of thermally metamorphosed marly sediments. Part I: Isotopic (C,O) study of the Khushaym Matruk natural analogue (central Jordan)     

Serge Fourcade  Laurent Trotignon  Philippe Boulvais  Isabelle Techer  Marcel Elie  Didier Vandamme  Elias Salameh  Hani Khoury 《Applied Geochemistry》2007

The Khushaym Matruk site in central Jordan may represent a natural analogue depicting the interaction of alkaline solutions with a clayey sedimentary formation or with clay-rich confining barriers at the interface with concrete structures in waste disposal sites. In this locality, past spontaneous combustion of organic matter in a clayey biomicritic formation produced a ca. 60 m-thick layer of cement-marble containing some of the high-temperature phases usually found in industrial cements (e.g., spurrite, brucite, and Ca-aluminate). A vertical cross-section of the underlying sediments was used in order to study the interaction between cement-marbles and neighbouring clayey limestones under weathering conditions. A thermodynamic approach of the alteration parageneses (calcite–jennite–afwillite–brucite and CSH phases) in the cement-marbles constrains the interacting solutions to have had pH-values between 10.5 and 12. Over 3 m, the sediments located beneath the metamorphic unit were compacted and underwent carbonation. They display large C and O isotopic variations with respect to “pristine” sediments from the bottom of the section. Low δ¹³C-values down to −31.4‰/PDB show the contribution of CO₂ derived from the oxidization of organic matter and from the atmosphere to the intense carbonation process affecting that particular sedimentary level. The size of the C isotopic anomalies, their geometrical extent and their coincidence with the variations of other markers like the Zn content, the structure of organic matter, the mineralogical composition, all argue that the carbonation process was induced by the percolation of high pH solutions which derived from the alteration of cement-marbles. The temperature of the carbonation process remains conjectural and some post-formation O isotopic reequilibration likely affected the newly-formed carbonate. Carbonation induced a considerable porosity reduction, both in fractures and matrixes. The Khushaym Matruk site may have some bearing to the early life of a repository site, when water saturation of the geological formations hosting the concrete structures is incomplete, enabling simultaneous diffusion of alkaline waters and gaseous CO₂ in the near field.  相似文献   

Holocene meteoric dolomitization of Pleistocene limestones, North Jamaica   总被引：3，自引：0，他引：3  

LYNTON S. LAND 《Sedimentology》1973,20(3):411-424

Wholesale removal of the unstable carbonate phases aragonite and Mg-calcite, and precipitation of calcite and dolomite is currently taking place where phreatic waters (the modern water table) invade 120,000-year-old Pleistocene biolithites (Falmouth Formation), North Jamaica. Pleistocene rocks presently in the vadose zone are relatively unaltered, and consist of mineralogically unstable scleractinian biolithites. At the water table, a narrow zone of solution, a ‘water table cave’ is commonly encountered. Below the water table the rocks are invariably more highly altered than those above. Mg-calcites are very rare, and considerable dissolution of aragonite has commonly occurred. Dolomite occurs as 8–25 μm, subhedral to euhedral crystals replacing micrite, or precipitated as void linings. The isotopic composition of the dolomite (δO¹⁸=-1·0 %0, δC¹³=-8·4 %0), and its high strontium content (3000 p.p.m.) suggest precipitation as CO₂-oversaturated meteoric groundwaters invade the mineralogically unstable biolithites, dissolve Mg-calcites and Sr-rich aragonites, and de-gas. Because some dolomitized rocks are enriched in magnesium relative to unaltered biolithites, addition of magnesium to the system is necessitated, and is probably derived from sea water in the mixing zone. Phreatic meteoric diagenesis is thus demonstrated to be a rapid process, and to be capable of dolomitization.  相似文献   

Geochemical factors for endogenic mineral formation in the bottom sediments of the Tazheran lakes (Baikal area)     

《Russian Geology and Geophysics》2015,56(10):1437-1450

We studied recent sedimentation in small saline and brackish lakes located in the Ol’khon region (western Baikal area) with arid and semiarid climate. The lakes belong to the Tazheran system; it is a series of compactly located closed shallow lakes, with a limited catchment area and different mineralization, under the same landscape, climatic, geologic, and geochemical conditions. Two complementary approaches are applied in the research: (1) a detailed study of individual lake and (2) a comparison of the entire series of lakes, which can be considered a natural model for studying the relationship between endogenic mineral formation and the geochemistry of lake waters. The lake waters and bottom sediments were studied by a set of modern methods of geochemistry, mineralogy, and crystal chemistry. The mineral component of the bottom sediments was analyzed by powder X-ray diffraction (XRD), IR spectroscopy, and electron microscopy. The lakes are characterized by predominant carbonate sedimentation; authigenic pyrite, smectite, chlorite, and illite are detected in assemblage with carbonate minerals in the bottom sediments. Carbonate phases have been identified, and their proportions have been determined in the samples by decomposition of the complex XRD profiles of carbonate minerals into peaks using the Pearson VII function. Mathematical modeling of the XRD profiles of carbonates has revealed that predominantly Mg-calcites with variable Mg content and excess-Ca dolomite accumulate in lake bottom sediments influenced by biogenic processes. Aragonite, monohydrocalcite, and rhodochrosite form in some lakes along with carbonates of the calcite-dolomite series. We show a dependence of the composition of the assemblages of the newly formed endogenic carbonate minerals and their crystallochemical characteristics on the chemical composition of lake waters.  相似文献   

Chemical composition of magnetite in Martian meteorite ALH 84001: Revised appraisal from thermochemistry of phases in Fe-Mg-C-O     

Allan H. Treiman  Eric J. Essene 《Geochimica et cosmochimica acta》2011,75(18):5324-5335

Martian meteorite Allan Hills (ALH) 84001 contains sub-micron magnetite grains, suggested to be of biogenic origin, in its globules of Fe-Mg carbonate mineral. There is disagreement on whether the low Mg content of the magnetite could only arise from biological metabolism ( [Treiman, 2003] and [Thomas-Keprta et al., 2009]). However, constraints on the magnetite’s biogenicity are far less certain than had been inferred. The thermochemical bases for the equilibrium calculations are reviewed in detail; there are inconsistencies and gaps in fundamental data for siderite, macromolecular carbons, and magnesioferrite. The calculations of Treiman (2003), assuming formation of magnetite via “siderite = magnetite + CO₂ + CO”, are incorrect because of a flaw in the computer code used. The corrected location of this equilibrium (Thomas-Keprta et al., 2009) is no longer crucial, because of recent finds that the magnetite grains are associated with macromolecular carbon; this implies that the dominant magnetite-forming reaction was “siderite = magnetite + CO₂ + C”. From the location of this equilibrium, using the corrected computer code and best available thermochemical data, the Mg-poor magnetite grains (and macromolecular carbon) in carbonates in ALH 84001 could have formed by decomposition of the carbonates at geologically reasonable pressures and temperatures. The low-Mg compositions of the magnetite grains remain consistent with an abiotic origin within the known geological history of ALH 84001.  相似文献   

Biogeochemical transformation of Fe minerals in a petroleum-contaminated aquifer     

John M. Zachara  Ravi K. Kukkadapu  Alice Dohnalkova  Todd Anderson 《Geochimica et cosmochimica acta》2004,68(8):1791-1805

The Bemidji aquifer in Minnesota, USA is a well-studied site of subsurface petroleum contamination. The site contains an anoxic groundwater plume where soluble petroleum constituents serve as an energy source for a region of methanogenesis near the source and bacterial Fe(III) reduction further down gradient. Methanogenesis apparently begins when bioavailable Fe(III) is exhausted within the sediment. Past studies indicate that Geobacter species and Geothrix fermentens-like organisms are the primary dissimilatory Fe-reducing bacteria at this site. The Fe mineralogy of the pristine aquifer sediments and samples from the methanogenic (source) and Fe(III) reducing zones were characterized in this study to identify microbiologic changes to Fe valence and mineral distribution, and to identify whether new biogenic mineral phases had formed. Methods applied included X-ray diffraction; X-ray fluorescence (XRF); and chemical extraction; optical, transmission, and scanning electron microscopy; and Mössbauer spectroscopy.All of the sediments were low in total Fe content (≈ 1%) and exhibited complex Fe-mineralogy. The bulk pristine sediment and its sand, silt, and clay-sized fractions were studied in detail. The pristine sediments contained Fe(II) and Fe(III) mineral phases. Ferrous iron represented approximately 50% of Fe_TOT. The relative Fe(II) concentration increased in the sand fraction, and its primary mineralogic residence was clinochlore with minor concentrations found as a ferroan calcite grain cement in carbonate lithic fragments. Fe(III) existed in silicates (epidote, clinochlore, muscovite) and Fe(III) oxides of detrital and authigenic origin. The detrital Fe(III) oxides included hematite and goethite in the form of mm-sized nodular concretions and smaller-sized dispersed crystallites, and euhedral magnetite grains. Authigenic Fe(III) oxides increased in concentration with decreasing particle size through the silt and clay fraction. Chemical extraction and Mössbauer analysis indicated that this was a ferrihydrite like-phase. Quantitative mineralogic and Fe(II/III) ratio comparisons between the pristine and contaminated sediments were not possible because of textural differences. However, comparisons between the texturally-similar source (where bioavailable Fe(III) had been exhausted) and Fe(III) reducing zone sediments (where bioavailable Fe(III) remained) indicated that dispersed detrital, crystalline Fe(III) oxides and a portion of the authigenic, poorly crystalline Fe(III) oxide fraction had been depleted from the source zone sediment by microbiologic activity. Little or no effect of microbiologic activity was observed on silicate Fe(III). The presence of residual “ferrihydrite” in the most bioreduced, anoxic plume sediment (source) implied that a portion of the authigenic Fe(III) oxides were biologically inaccessible in weathered, lithic fragment interiors. Little evidence was found for the modern biogenesis of authigenic ferrous-containing mineral phases, perhaps with the exception of thin siderite or ferroan calcite surface precipitates on carbonate lithic fragments within source zone sediments.  相似文献   

Climatic signals in the Holocene carbonate sedimentary record of Namshi-Nur lake,West Baikal region     

Solotchina  E. P.  Sklyarov  E. V.  Vologina  E. G.  Solotchin  P. A.  Stolpovskaya  V. N.  Sklyarova  O. A.  Izokh  O. P.  Ukhova  N. N. 《Doklady Earth Sciences》2011,436(2):295-300

A new high-resolution Holocene climate record of the Western Baikal region from the evaporite sediments of one of the small saline lakes with the carbonate type of sedimentation are obtained on the basis of detailed mineralogical and crystallochemical studies of chemogenic carbonates. All carbonate phases occurring in the sediment are identified by decomposition of complex XRD-profiles of carbonates into individual peaks using the Pearson VII function, and the quantitative relationships between them are determined. Mg-calcites provide the major paleoclimatic information. The carbonate record contains data on the stratigraphic distribution of Mg-calcites, in which the number and ratio between the phases of different magnesium contents are determined by the past values of the Mg/Ca ratio, salinity, and total alkalinity of lake water that vary according to climatic cycles and fluctuations of the lake level. The high potential of the approach proposed for paleoclimatic reconstructions is demonstrated.  相似文献   

Reconstruction of the Holocene climate based on a carbonate sedimentary record from shallow saline Lake Verkhnee Beloe (western Transbaikalia)     

E.P. Solotchina  E.V. Sklyarov  P.A. Solotchin  E.G. Vologina  V.N. Stolpovskaya  O.A. Sklyarova  N.N. Ukhova 《Russian Geology and Geophysics》2012,53(12):1351-1365

We present results of mineralogical and crystallochemical studies of the Holocene carbonate sediments of a small saline lake localized in the Borgoi dry-steppe region, western Transbaikalia. Mg-calcites with a varying Mg content are predominant in the assemblage of endogenic carbonate minerals from bottom sediments. Mathematical modeling of the XRD spectra of carbonates permitted us to identify excess-Ca dolomites, which are an indicator of a shallow (playa) lake. The studies showed that the lacustrine Mg-calcites do not form a continuous series from low- to high-Mg varieties. We discuss the cause of this phenomenon and also consider the existing viewpoints of the structure of low-temperature Mg-calcites and excess-Ca dolomites and their formation conditions in lacustrine sediments. Juxtaposing the carbonate record with the data of lithological analysis, determined stable isotopes (δ¹⁸O and δ¹³C), and distribution of some geochemical indicators of climatic changes, we reconstructed the intricate evolution of Lake Verkhnee Beloe, which was controlled by the regional climate since the postglacial period till the present day.  相似文献   

Detailed Holocene climate record from the carbonate section of saline Lake Tsagan-Tyrm (West Baikal area)     

E.V. Sklyarov  E.P. Solotchina  E.G. Vologina  N.V. Ignatova  O.P. Izokh  N.V. Kulagina  O.A. Sklyarova  P.A. Solotchin  V.N. Stolpovskaya  N.N. Ukhova  V.S. Fedorovskii  O.M. Khlystov 《Russian Geology and Geophysics》2010,51(3):237-258

We present results of a complex study of evaporite sediments from one of the small saline lakes with carbonate sedimentation in the Ol’khon area and substantiate their high significance for paleoclimatic reconstructions. The mineral composition of the bottom sediments was studied by XRD analysis, IR spectroscopy, scanning electron microscopy, elemental analysis (SR-XFA), etc. By decomposition of the complex XRD profiles of carbonate minerals into individual peaks by Pearson VII function, we identified carbonate phases in each sample and determined their proportions. A high-resolution carbonate record has been obtained for the first time for the lacustrine sediments. It bears the information about the stratigraphic distribution of Mg-calcites (a continuous series of structurally disordered low- to high-Mg calcites, up to Ca-dolomites), in which the amount and proportions of phases with different Mg contents are controlled by Mg/Ca, salinity, and total alkalinity of the lake water changing depending on the climatic cycles and lake level fluctuations. Comparison of the carbonate record for the Holocene section dated by the radiocarbon (¹⁴C) method with results of lithological, diatom, and palynological analyses, data on stable isotopes (δ¹⁸O and δ¹³C), and the distribution of some geochemical indicators of climatic changes permitted the reconstruction of the intricate evolution of the Lake Tsagan-Tyrm basin, which was controlled by the regional climate from the Atlantic period to the present time. The directed change in various characteristics of essentially carbonate sediments evidences that the Ol’khon regional climate has become more arid in recent 6.5 kyr. Moreover, drastic frequent changes of climate and, correspondingly, the Lake Tsagan-Tyrm water level in different periods of its existence have been revealed. The widespread saline and brackish lakes in southern East Siberia, Mongolia, and North China and the highly informative (in terms of paleoclimate and paleolimnology) carbonate sediments might help to recognize the general tendencies of paleoclimate changes and local fluctuations in Central Asia.  相似文献   

Can the long-term potential for carbonatization and safe long-term CO2 storage in sedimentary formations be predicted?     

《Applied Geochemistry》2013

A sedimentary formation perturbated by supercritical CO₂ reacts by dissolving primary minerals and forming new secondary phases. In this process CO₂ may be trapped in stable carbonate minerals and may thereby be immobilized for long time spans. The potential for mineral trapping can be estimated by solving kinetic expressions for the reservoir minerals and possible secondary phases. This is, however, not trivial as kinetic data are uncertain or even lacking for the minerals of interest. Here, the rate equations most commonly used for CO₂ storage simulations have been solved, and the rate parameters varied, to obtain sensitivity on the total amount of CO₂ stored as mineral carbonate. As various expressions are in use to estimate growth rates of secondary carbonates, three formulations were compared, including one taking into account mineral nucleation preceding growth. The sensitivity studies were done on two systems, the Utsira Sand being representative for a cold quartz-rich sand (37 °C, 100 bar CO₂), and the Gulf Coast Sediment, being representative for a medium temperature quartz–plagioclase-rich system (75 °C, 300 bar CO₂).The simulations showed that the total predicted CO₂ mineral storage is especially sensitive to the choice of growth rate model and the reactive surface area. The largest sensitivity was found on α, fraction of total surface area available for reactions, with a reduction of one order of magnitude for all reacting phases leading to 3–4 times lower predicted CO₂ mineral storage. Because the reactive surface area is highly uncertain for natural systems, the range in predicted results may be even larger. The short-term predictions (<100–1000 a), such as the onset of carbonate growth, were highly sensitive to nucleation and growth rates. Moreover, the type of carbonate minerals formed was shown to be model dependent, with the simplest model predicting an unlikely carbonate assemblage at low temperature (i.e., formation of dolomite at 37 °C). Therefore, to use kinetic models to upscale short-term (<months) laboratory experiments in time, to identify the past reactions and physical conditions of natural CO₂ storage analogues, and finally to predict the potential for CO₂ trapping in existing and future storage projects, more knowledge has to be collected, especially on the reactive surface area of CO₂ storage reservoirs, and on the rate of secondary carbonate nucleation and growth.  相似文献   

Formation of magnesium‐smectite during lacustrine carbonates early diagenesis: Study case of the volcanic crater lake Dziani Dzaha (Mayotte – Indian Ocean)     

Vincent P. Milesi  Didier Jzquel  Mathieu Debure  Pierre Cadeau  Franois Guyot  Grard Sarazin  Francis Claret  Emmanuelle Vennin  Carine Chaduteau  Aurlien Virgone  Eric C. Gaucher  Magali Ader 《Sedimentology》2019,66(3):983-1001

The volcanic crater lake of Dziani Dzaha in Mayotte is studied to constrain the geochemical settings and the diagenetic processes at the origin of Mg‐phyllosilicates associated with carbonate rocks. The Dziani Dzaha is characterized by intense primary productivity, volcanic gases bubbling in three locations and a volcanic catchment of phonolitic/alkaline composition. The lake water has an alkalinity of ca 0·2 mol l^?1 and pH values of ca 9·3. Cores of the lake sediments reaching up to one metre in length were collected and studied by means of carbon–hydrogen–nitrogen elemental analyzer, X‐ray fluorescence spectrometry and X‐ray powder diffraction. In surface sediments, the content of total organic carbon reaches up to 20 weight %. The mineral content consists of aragonite and hydromagnesite with minor amounts of alkaline feldspar and clinopyroxene from the volcanic catchment. Below 30 cm depth, X‐ray diffraction analyses of the <2 μm clay fraction indicate the presence of a saponite‐like mineral, a Mg‐rich smectite. The saponite‐like mineral accumulates at depth to reach up to ca 30 weight %, concurrent with a decrease of the contents of hydromagnesite and organic matter. Thermodynamic considerations and mineral assemblages suggest that the evolution of the sediment composition resulted from early diagenetic reactions. The formation of the saponite‐like mineral instead of Al‐free Mg‐silicates resulted from high aluminum availability, which is favoured in restricted lacustrine environments hosted in alkaline volcanic terrains commonly emplaced during early stages of continental rifting. Supersaturation of the lake water relative to saponite is especially due to high pH values, themselves derived from high primary productivity. This suggests that a genetic link may exist between saponite and the development of organic‐rich carbonate rocks, which may be fuelled by the input of CO₂‐rich volcanic gases. This provides novel insights into the composition and formation of saponite‐rich deposits under a specific geodynamic context such as the Cretaceous South Atlantic carbonate reservoirs.  相似文献   

Sequestration of CO₂ after reaction with alkaline earth metal oxides CaO and MgO     

Martin Back  Markus BauerHelge Stanjek  Stefan Peiffer 《Applied Geochemistry》2011,26(7):1097-1107

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