Nearshore Carbonate Dissolution in the Hawaiian Archipelago?     

Robert W. Thompson  Andrew G. Dickson  Samuel E. Kahng  Christopher D. Winn 《Aquatic Geochemistry》2014,20(5):467-481

Inorganic carbon measurements made in the late 1980s suggest that alkalinity in the waters surrounding the Hawaiian Archipelago is elevated relative to the oligotrophic waters of the North Pacific. These observations have been interpreted as evidence for a “halo” of elevated carbonate saturation state produced by the dissolution of highly soluble magnesium calcites and aragonite on the island platform or in the water column surrounding the islands. If present, this “halo” has implications for air–sea carbon dioxide exchange in Hawaiian waters and may impact the response of coral reef communities to the acidification of the surface waters of the global ocean. The purpose of this study was to assess the magnitude and extent of the elevated calcium carbonate saturation state observed on previous expeditions to this region. Transects were conducted near several atolls in the Northwestern Hawaiian Islands from shallow water adjacent to the forereef to the open ocean 15 km from the island. Hydrographic profiles were collected at each station, and discrete water samples were collected for the measurement of carbon system parameters necessary to compute calcium carbonate saturation state. Our data were compared with observations made at the Hawaii Ocean Time-series site at Station ALOHA and with hydrographic data collected on the WOCE lines in the North Pacific around the archipelago. We did not detect a carbonate dissolution halo around the islands. We conclude that the previously observed halo was probably an analytical artifact, or possibly a result of extreme variability in carbon chemistry surrounding the islands.  相似文献   

Shallow subsurface diagenesis of Pleistocene periplatform ooze: northern Bahamas   总被引：2，自引：0，他引：2  

HENRY T. MULLINS  SHERWOOD W. WISE ANNE F. GARDULSKI  EDWARD J. HINCHEY  PHILIP M. MASTERS  D.I. SIEGEL 《Sedimentology》1985,32(4):473-494

Previous studies on early submarine diagenesis of periplatform carbonates have implied that these originally polymineralic (aragonite, magnesian calcite, calcite) sediments are susceptible to early diagenesis only in current-swept open seaways or where surficially exposed by erosion on the seafloor. It has also been proposed that while in the shallow subsurface, periplatform oozes retain their original mineralogy for at least 200,000–400,000 yr and remain unlithified for tens of millions of years. Evidence is reported here for extensive calcitization and selective lithification of periplatform oozes of late Pleistocene age in two piston cores collected from water depths of ～ 1,000 m north of Little Bahama Bank. It is shown that shallow (<30 m) subsurface diagenesis can significantly alter the original mineralogy of periplatform oozes to predominantly calcite in less than 440,000 yr, and that cementation by calcite can produce chalk-ooze sequences within the same time-frame. Periplatform oozes that originally contain a high percentage of bank-derived magnesian calcite appear to have a higher diagenetic potential than those originally low in magnesian calcite. Shallow subsurface calcitization and fithification greatly reduce the diagenetic potential of periplatform carbonates, and chalk-ooze sequences apparently can persist for tens of millions of years and to burial depths of at least 300 m. Shallow subsurface diagenesis, at water depths > 1,000 m, proceeds via dissolution of magnesian calcite and aragonite and reprecipitation of calcite as allochem fillings, exterior overgrowths and cement. It is speculated that density-driven ‘Kohout convection‘, where seawaters under-saturated with respect to magnesian calcite and aragonite and saturated/supersaturated with respect to calcite flow through the margins of carbonate platforms, is the primary driving mechanism for shallow subsurface diagenesis. Removal of Mg during early stages of deep seafloor and shallow subsurface diagenesis should increase the Mg content of interstitial waters which is likely to increase the ‘dolomitizing potential’ of Kohout convection fluid flow.  相似文献   

Impact of Carbonate Precipitation on Riverine Inorganic Carbon Mass Transport from a Mid-continent, Forested Watershed     

Kathryn Szramek  Lynn M. Walter 《Aquatic Geochemistry》2004,10(1-2):99-137

Physiochemical controls on the carbonate geochemistry of large river systems are important regulators of carbon exchange between terrestrial and marine reservoirs on human time scales. Although many studies have focused on large-scale river carbon fluxes, there are few investigations of mechanistic aspects of carbonate mass balance and transport at the catchment scale. We determined elemental and carbonate geochemistry and mass balances for net carbonate dissolution fluxes from the forested, mid-latitude Huron River watershed, established on carbonate-rich unconfined glacial drift aquifers. Shallow groundwaters are near equilibrium with respect to calcite at pCO₂ values up to 25 times atmospheric values. Surface waters are largely groundwater fed and exhibit chemical evolution due to CO₂ degassing, carbonate precipitation in lakes and wetlands, and anthropogenic introduction of road salts (NaCl and CaCl₂). Because the source groundwater Mg²⁺/HCO₃ ^? ratio is fairly constant, this parameter permits mass balances to be made between carbonate dissolution and back precipitation after groundwater discharge. Typically, precipitation does not occur until IAP/K calcite values exceed 10 times supersaturation. Stream chemistry changes little thereafter even though streams remain highly supersaturated for calcite. Our data taken together with historical United States Geological Survey (USGS) data show that alkalinity losses to carbonate precipitation are most significant during periods of lowest discharge. Thus, on an annual basis, the large carbon flux from carbonate dissolution in soil zones is only decreased by a relatively small amount by the back precipitation of calcium carbonate.  相似文献   

Low-magnesian calcite limestones forming at the deep-sea floor, Tongue of the Ocean, Bahamas     

W. SCHLAGER  N. P. JAMES 《Sedimentology》1978,25(5):675-702

Carbonate ooze in the deep troughs between the Bahama Banks is a mixture of pelagic and bank-derived material. It consists of aragonite, calcite and magnesium calcite in a ratio of about 3:2:1. Where exposed in erosional cuts at the sea floor, this ooze lithifies within 100,000 years and is transformed into calcite micrite of only 3.5-5 mol % MgCO₃. Where buried, the ooze maintains its original composition for at least 200,000-400,000 years and remains unlithified for tens of millions of years. Quite unexpectedly, the path of sea-floor diagenesis of peri-platform ooze was found to be the same as that of freshwater diagenesis. Most of the aragonite is leached, pteropod shells often leaving cement-lined moulds behind; magnesian calcite recrystallizes and loses magnesium; polyhedral calcite of 2-4 μm size appears as cement. The setting and the carbon-oxygen isotope ratios rule out any freshwater influence. Carbon isotope ratios remain heavy, oxygen ratios shift towards equilibrium with the cold bottom water. The calcite cement has 3.5-5 mol % MgCO₃ and can be interpreted as the least soluble form of calcite emerging from alteration at the sea floor or, alternatively, as a direct precipitate from cold sea water. The change in the composition of calcite cements with water depth supports the second interpretation. In the Bahamas and elsewhere in the world ocean, magnesium in calcite cements decreases from the warm surface waters down to 700-1200 m, i.e. the boundary between intermediate and cold deep-water masses. Below this level, calcite prevails and magnesian calcite and aragonite cements are restricted to semi-enclosed seas with exceptionally warm bottom waters.  相似文献   

Dissolved carbon in pore waters from the carbonate barrier reef of Tahiti (French Polynesia) and its basalt basement     

R. Fichez  P. Harris  G. Cauwet  P. Dejardin 《Aquatic Geochemistry》1997,2(3):255-271

This paper deals with dissolved inorganic carbon (DIC) and organic carbon (DOC) in pore waters from a 150 m deep hole drilled through the carbonate barrier reef of Tahiti and its underlying basalt basement. Alkalinity-pH measurements were used to calculate the DIC species concentration, and DOC was analysed according to the high temperature catalytic oxidation technique. Salinity was used as a conservative tracer to help identify water origin and mixing within the hole. Water mixing, calcium carbonate dissolution and mineralization of organic carbon combined to form three distinct groups of pore water. In the deeper basalt layers, pore water with alkalinity of 1.4 meq kg^?1 pH of 7.6 and p(CO₂) of 1.2 mAtm was undersaturated with respect to both aragonite and calcite. In the intermediate carbonate layer, pore water with alkalinity of more than 2.0 meq kg^?1, pH of 7.70 and p(CO₂) of 1.4 mAtm was supersaturated with respect to both aragonite and calcite. The transition zone between those two groups extended between 80 and 100 m depth. The shift from aragonite undersaturation to supersaturation was mainly attributed to the mixing of undersaturated pore waters from the basalt basement with supersaturated pore waters from the overlaying limestone. In the top of the reef, inputs from a brackish water lens further increased p(CO₂) up to 5.6 times the atmospheric P(CO₂).  相似文献   

Dissolved carbon in pore waters from the carbonate barrier reef of Tahiti (French Polynesia) and its basalt basement     

R. Fichez  P. Harris  G. Cauwet  P. Dejardin 《Aquatic Geochemistry》1996,2(3):255-271

This paper deals with dissolved inorganic carbon (DIC) and organic carbon (DOC) in pore waters from a 150 m deep hole drilled through the carbonate barrier reef of Tahiti and its underlying basalt basement. Alkalinity-pH measurements were used to calculate the DIC species concentration, and DOC was analysed according to the high temperature catalytic oxidation technique. Salinity was used as a conservative tracer to help identify water origin and mixing within the hole. Water mixing, calcium carbonate dissolution and mineralization of organic carbon combined to form three distinct groups of pore water. In the deeper basalt layers, pore water with alkalinity of 1.4 meq kg^–1 pH of 7.6 and p(CO₂) of 1.2 mAtm was undersaturated with respect to both aragonite and calcite. In the intermediate carbonate layer, pore water with alkalinity of more than 2.0 meq kg^–1, pH of 7.70 and p(CO₂) of 1.4 mAtm was supersaturated with respect to both aragonite and calcite. The transition zone between those two groups extended between 80 and 100 m depth. The shift from aragonite undersaturation to supersaturation was mainly attributed to the mixing of undersaturated pore waters from the basalt basement with supersaturated pore waters from the overlaying limestone. In the top of the reef, inputs from a brackish water lens further increased p(CO₂) up to 5.6 times the atmospheric P(CO₂).  相似文献   

Precipitation and lithification of magnesian calcite in the deep-sea sediments of the eastern Mediterranean Sea*     

JOHN D. MILLIMAN  JENS MÜLLER 《Sedimentology》1973,20(1):29-45

Magnesian calcite is an important sedimentary component in the deep-sea sediments of the eastern Mediterranean Sea, comprising an average of 20–50% of the carbonate fraction in most areas. The lack of any obvious biogenic source, plus similarities with magnesian-rich lutites from the Red Sea and deep-sea cements from other areas suggest that this magnesian calcite was precipitated inorganically. Although the exact mode of precipitation is not understood at present, it probably occurred at the water-sediment interface under elevated salinity and temperature conditions, such as those present in the modern eastern Mediterranean. Precipitation did not occur during periods of lower temperatures and/or salinities such as during the stagnant conditions caused by the influx of fresh waters from melting Pleistocene glaciers. The eastern Mediterranean magnesium-rich sediments appear to represent an intermediate stage between normal deep-sea sediments and those from the warm hpyersaline Red Sea. Normal deep-sea carbonates are composed almost entirely of biogenic calcite, whereas the Red Sea magnesian calcite alternates with layers of aragonite that were precipitated under elevated salinity and temperature conditions brought about by lowered stands of sea level.  相似文献   

How do mineral coatings affect dissolution rates? An experimental study of coupled CaCO₃ dissolution—CdCO₃ precipitation     

Pablo Cubillas  Stephan Köhler  Carole Causserand 《Geochimica et cosmochimica acta》2005,69(23):5459-5476

Coupled CaCO₃ dissolution-otavite (CdCO₃) precipitation experiments have been performed to 1) quantify the effect of mineral coatings on dissolution rates, and 2) to explore the possible application of this coupled process to the remediation of polluted waters. All experiments were performed at 25°C in mixed-flow reactors. Various CaCO₃ solids were used in the experiments including calcite, aragonite, and ground clam, mussel, and cockle shells. Precipitation was induced by the presence of Cd(NO₃)₂ in the inlet solution, which combined with aqueous carbonate liberated by CaCO₃ dissolution to supersaturate otavite. The precipitation of an otavite layer of less than 0.01 μm in thickness on calcite surfaces decreases its dissolution rate by close to two orders of magnitude. This decrease in calcite dissolution rates lowers aqueous carbonate concentrations in the reactor such that the mixed-flow reactor experiments attain a steady-state where the reactive fluid is approximately in equilibrium with otavite, arresting its precipitation. In contrast, otavite coatings are far less efficient in lowering aragonite, and ground clam, mussel, and cockle shell dissolution rates, which are comprised primarily of aragonite. A steady-state is only attained after the precipitation of an otavite layer of 3-10 μm thick; the steady state CaCO₃ dissolution rate is 1-2 orders of magnitude lower than that in the absence of otavite coatings. The difference in behavior is interpreted to stem from the relative crystallographic structures of the dissolving and precipitating minerals. As otavite is isostructural with respect to calcite, it precipitates by epitaxial growth directly on the calcite, efficiently slowing dissolution. In contrast, otavite’s structure is appreciably different from that of aragonite. Thus, it will precipitate by random three dimensional heterogeneous nucleation, leaving some pore space at the otavite-aragonite interface. This pore space allows aragonite dissolution to continue relatively unaffected by thin layers of precipitated otavite. Due to the inefficiency of otavite coatings to slow aragonite and ground aragonite shell dissolution, aragonite appears to be a far better Cd scavenging material for cleaning polluted waste waters.  相似文献   

Carbonate cementation of some Pleistocene temperate marine sediments     

IAN M. WEST 《Sedimentology》1973,20(2):229-249

Carbonate cementation of some carbonate and quartz sands in three raised beaches of temperate origins was investigated. The carbonate of the cements was found to have been derived from the dissolution of skeletal debris. The sandstones, so produced, now possess only low-magnesium calcite, but the original sediments, like adjacent modern beach and blown sands, probably contained low-magnesium calcite, aragonite and some high-magnesium calcite, all of skeletal origin. In meteoric water the dissolution has occurred of all carbonate within minute, tubulelike, volumes of sand. Concurrent deposition in adjacent volumes of sand of low-magnesium calcite formed cements that are irregularly nodular or uneven on a small scale. Aragonite within the minute nodules has been replaced paramorphically by low-magnesium calcite. Additional local carbonate cements were formed at later dates, around and within solution pipes.  相似文献   

Diagenetic evolution of the Carnian Wetterstein platforms of the Eastern Alps   总被引：1，自引：0，他引：1  

S. ZEEH  T. BECHSTÄDT  J. McKENZIE†  D. K. RICHTER‡ 《Sedimentology》1995,42(2):199-222

The carbonate platforms of the Wetterstein Formation of the Eastern Alps (Drau Range and Northern Calcareous Alps) show a distinct facies zonation of reefs and lagoons. While some lagoonal areas were episodically emerged and formed lagoonal islands, others remained permanently flooded. The scale of near surface, meteoric or marine diagenesis was related to this lagoonal topography. At shallow burial depth, cementation was dominated by altered marine solutions, which additionally caused recrystallization of metastable constituents of the sediment and earlier marine cements (high magnesian calcite, aragonite) connected with a carbon and oxygen isotopic change to more negative values. Deeper burial cementation shows a succession with two types of saddle dolomite and three types of blocky calcite. Carbon and oxygen isotopic values of these cements show a trend towards more negative values from the first to the last generation, in the following succession: clear saddle dolomite—zoned blocky calcite—cloudy saddle dolomite—post-corrosion blocky calcite—replacive blocky calcite. Fluid inclusion studies of the carbonate cements are interpreted to indicate a deeper burial temperature development that first increases from 175 to 317°C, followed by a temperature decrease to 163–260°C, and subsequent increase up to 316°C, whereby the samples of the Drau Range always show the lowest values. Calculations of the isotopic composition of the water, from which the carbonate cements were precipitated, yielded positive δ¹⁸O values from 6.66 to 17.81%o (SMOW), which are characteristic for formation and/or metamorphic waters. Also, the isotopic compositions of the palaeofluids probably changed during deeper burial diagenesis, following the temperature development.  相似文献   

Shallow-marine carbonate cementation in Holocene segments of the calcifying green alga Halimeda     

Thomas Mann  Andr Wizemann  Marleen Stuhr  Yannis Kappelmann  Alexander Janßen  Jamaluddin Jompa  Hildegard Westphal 《Sedimentology》2022,69(1):282-300

Early-diagenetic cementation of tropical carbonates results from the combination of numerous physico-chemical and biological processes. In the marine phreatic environment it represents an essential mechanism for the development and stabilization of carbonate platforms. However, diagenetic cements that developed early in the marine phreatic environment are likely to become obliterated during later stages of meteoric or burial diagenesis. When lithified sediment samples are studied, this complicates the recognition of processes involved in early cementation, and their geological implications. In this contribution, a petrographic microfacies analysis of Holocene Halimeda segments collected on a coral island in the Spermonde Archipelago, Indonesia, is presented. Through electron microscopical analyses of polished samples, this study shows that segments are characterized by intragranular cementation of fibrous aragonite, equant High-Mg calcite (3.9 to 7.2 Mol% Mg), bladed Low-Mg calcite (0.4 to 1.0 Mol% Mg) and mini-micritic Low-Mg calcite (3.2 to 3.3 Mol% Mg). The co-existence and consecutive development of fibrous aragonite and equant High-Mg calcite results initially from the flow of oversaturated seawater along the aragonite template of the Halimeda skeleton, followed by an adjustment of cement mineralogy towards High-Mg calcite as a result of reduced permeability and fluid flow rates in the pores. Growth of bladed Low-Mg calcite cements on top of etched substrates of equant High-Mg calcite is explained by shifts in pore water pH and alkalinity through microbial sulphate reduction. Microbial activity appears to be the main trigger for the precipitation of mini-micritic Low-Mg calcite as well, based on the presumable detection of an extracellular polymeric matrix during an early stage of mini-micrite Low-Mg calcite cement precipitation. Radiocarbon analyses of five Halimeda segments furthermore indicate that virtually complete intragranular cementation in the marine phreatic environment with thermodynamically/kinetically controlled aragonite and High-Mg calcite takes place in about 100 years. Collectively, this study shows that early-diagenetic cements are highly diverse and provides new quantitative constraints on the rate of diagenetic cementation in tropical carbonate factories.  相似文献   

Land–sea carbon and nutrient fluxes and coastal ocean CO2 exchange and acidification: Past,present, and future     

Fred T. Mackenzie  Andreas J. Andersson  Rolf S. Arvidson  Michael W. Guidry  Abraham Lerman 《Applied Geochemistry》2011

Epochs of changing atmospheric CO₂ and seawater CO₂–carbonic acid system chemistry and acidification have occurred during the Phanerozoic at various time scales. On the longer geologic time scale, as sea level rose and fell and continental free board decreased and increased, respectively, the riverine fluxes of Ca, Mg, DIC, and total alkalinity to the coastal ocean varied and helped regulate the C chemistry of seawater, but nevertheless there were major epochs of ocean acidification (OA). On the shorter glacial–interglacial time scale from the Last Glacial Maximum (LGM) to late preindustrial time, riverine fluxes of DIC, total alkalinity, and N and P nutrients increased and along with rising sea level, atmospheric PCO₂ and temperature led, among other changes, to a slightly deceasing pH of coastal and open ocean waters, and to increasing net ecosystem calcification and decreasing net heterotrophy in coastal ocean waters. From late preindustrial time to the present and projected into the 21st century, human activities, such as fossil fuel and land-use emissions of CO₂ to the atmosphere, increasing application of N and P nutrient subsidies and combustion N to the landscape, and sewage discharges of C, N, P have led, and will continue to lead, to significant modifications of coastal ocean waters. The changes include a rapid decline in pH and carbonate saturation state (modern problem of ocean acidification), a shift toward dissolution of carbonate substrates exceeding production, potentially leading to the “demise” of the coral reefs, reversal of the direction of the sea-to-air flux of CO₂ and enhanced biological production and burial of organic C, a small sink of anthropogenic CO₂, accompanied by a continuous trend toward increasing autotrophy in coastal waters.  相似文献   

海水化学演化对生物矿化的影响综述   总被引：1，自引：1，他引：0       下载免费PDF全文

刘喜停  颜佳新 《古地理学报》2009,11(4):446

显生宙非骨屑碳酸盐矿物经历了文石海和方解石海的交替,主要造礁生物和沉积物生产者的骨骼矿物与非骨屑碳酸盐矿物具有同步变化的趋势。这种长期的变化趋势可以用海水化学Mg/Ca摩尔比的变化来解释。流体包裹体、同位素和微量元素等证据也证实了海水化学在地质历史中经历过剧烈的变化。虽然生物诱导矿化和生物控制矿化的相对重要性一直存在争议,但古生物地层记录和人工海水养殖实验结果都表明,海水化学演化对生物矿化有重要的影响,体现在造礁生物群落的兴衰、生物起源时对骨骼矿物类型的选择以及微生物碳酸盐岩在地质历史中的分布等。这些为研究前寒武纪海水化学演化、古气候和古环境的重建、同位素地层对比以及碳酸盐的沉积和成岩等问题提供了新的思路。  相似文献   

Magnesian calcite stabilities: A reevaluation     

Lynn M. Walter 《Geochimica et cosmochimica acta》1984,48(5):1059-1069

Equilibrium constants at stoichiometric saturation with respect to various magnesian calcite compositions were measured using free-drift dissolution rate data and inverse time plots to estimate equilibrium pH. The equilibrium constants determined for two ultrasonically cleaned and annealed biogenic magnesian calcites (12 and 18 mole % MgCO₃) in CaCl₂ + MgCl₂ media at two Mg:Ca molar ratios (1:5 and 5:1) are about three times smaller than those previously reported by Plummer and Mackenzie (1974). These equilibrium constants are not affected by changes in initial pH value, solid:solution ratio, or solution Mg:Ca molar ratio when the ion activity product is expressed in the fractional exponent form. Other models for expression of the equilibrium ion activity product fail to yield consistent values in solutions of different Mg:Ca molar ratios.Experiments performed using crushed samples not ultrasonically cleaned and annealed yield equilibrium constants which vary with solid:solution ratio. Those performed at high solid:solution ratios yield values which approach those previously reported. Submicron size particles and crystal strain induced by crushing the biogenic carbonates may cause more rapid dissolution rates and, hence, overestimation of the solubility of samples not prepared so as to minimize these effects. Thus, the large range in reported solubilities of magnesium calcites may be a result of differences in sample preparation procedure.The results of these measurements shift the thermodynamic equivalence point of aragonite and magnesian calcite from 7.5 mole % MgCO₃ up to 12 mole % MgCO₃ and prompt a reassessment of models for carbonate diagenetic reactions in natural environments.  相似文献   

Aragonite preservation in late Quaternary sediment cores on the Brazilian Continental Slope: implications for intermediate water circulation     

S. Gerhardt  H. Groth  C. Rühlemann  R. Henrich 《International Journal of Earth Sciences》2000,88(4):607-618

We present late Quaternary records of aragonite preservation determined for sediment cores recovered on the Brazilian Continental Slope (1790–2585 m water depth) where North Atlantic Deep Water (NADW) dominates at present. We have used various indirect dissolution proxies (carbonate content, aragonite/calcite contents, and sand percentages) as well as gastropodal abundances and fragmentation of Limacina inflata to determine the state of aragonite preservation. In addition, microscopic investigations of the dissolution susceptibility of three Limacina species yielded the Limacina Dissolution Index which correlates well with most of the other proxies. Excellent preservation of aragonite was found in the Holocene section, whereas aragonite dissolution gradually increases downcore. This general pattern is attributed to an overall increase in aragonite corrosiveness of pore waters. Overprinted on this early diagenetic trend are high-frequency fluctuations of aragonite preservation, which may be related to climatically induced variations of intermediate water masses. Received: 9 November 1998 / Accepted: 25 August 1999  相似文献   

Changes in Surface Morphology of Calcite Exposed to the Oceanic Water Column     

Paul J. Troy  Yuan-Hui Li  Fred T. Mackenzie 《Aquatic Geochemistry》1997,3(1):1-20

Reactions occurring on the surfaces of biogenic carbonate minerals can have important consequences for the biogeochemical cycle of carbon. In this study, carbonate mineral surface reactions with ambient seawater were investigated by atomic force microscopy (AFM). A sampling method was developed in which calcite surfaces were hung at discrete depths on a sediment trap array line for a three-day deployment period in subtropical North Pacific waters. Changes in surface morphologies were examined at nanometer resolution and evaluated using as a constraint the depth profile of calcite saturation in these waters. Evidence suggests that: (1) organic films which develop on carbonate surfaces exposed to shallow seawater may be responsible for the oversaturated state of the upper oceanic water column, (2) dissolution of carbonate minerals within the shallow warm layer of the ocean could be responsible for part of the alkalinity anomaly observed in the North Pacific.  相似文献   

The solubility of calcite in seawater solutions of various magnesium concentration, $\text{I}{}_{\mathrm{t}}\text{= 0.697}\text{m}$ at 25 °C and one atmosphere total pressure     

Alfonso Mucci  John W. Morse 《Geochimica et cosmochimica acta》1984,48(4):815-822

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   

Recrystallization of Magnesian Calcite Overgrowths on Calcite SeedsSuspended in Seawater     

Jane S. Tribble  Fred T. Mackenzie 《Aquatic Geochemistry》1998,4(3-4):337-360

The formation and subsequent reactions of magnesiancalcite overgrowths on calcite were investigated bymeans of closed system seeded precipitationexperiments. These experiments demonstrated that(1) thin overgrowths of magnesian calcite are precipitatedon calcite seeds suspended in seawater;(2) the solubilities of the coatings increase outward from theseed crystals as a linear function of the log ofrelative coating thickness;(3) during the period ofthese experiments (up to 5.5 months), the magnesiancalcite coatings continued to increase in thickness,but became less soluble in composition. Thestabilization reaction, referred to asrecrystallization, can be described by the followingequation:Cax Mg(1-x) CO3 + [z + y(x + z)]Ca2++ 2yHCO3- ]= (1 + y)Ca(x + z)Mg(1 - x -z)CO3 + [z + y(x + z - 1)]Mg2++ y CO2 + yH20;]4) recrystallization rate is dependent on solutionsaturation state, with a reaction order of 3.2 forartificial seawater and 4.0 for natural seawater; and(5) by the cessation of the closed system experiments,overgrowth compositions approached that of the stablecalcite (a few mol % MgCO3).Armoring of suspended carbonate particles in thesurface oceans with magnesian calcite overgrowthswould provide an effective barrier to release of theoceanic supersaturation with respect to calcite. Thicknesses of such coatings would be limited by therecrystallization rate of the magnesian calcite. Estimates based on the recrystallization ratesdetermined in this work indicate coatings on the orderof 0.02 µm in thickness could form on particles asthey sink through the mixed layer. According to thesecalculations, the total amount of carbon precipitatedannually in magnesian calcite overgrowths iscomparable to the riverine flux of dissolved carbon tothe oceans. Field observations of severalinvestigators indicate the likely presence ofmagnesian calcite coatings on planktonic particles,and provide evidence for possible recrystallization ofbiogenic magnesian particles in the marineenvironment.  相似文献   

Calcium carbonate dissolution in deep sea sediments: reconciling microelectrode, pore water and benthic flux chamber results   总被引：1，自引：0，他引：1  

Richard A. Jahnke  Deborah B. Jahnke 《Geochimica et cosmochimica acta》2004,68(1):47-59

We report the benthic fluxes of O₂, titration alkalinity (TA), Ca²⁺, NO₃⁻, PO₄³⁻, and Si(OH)₄ from in situ benthic flux chamber incubations on the Ceara Rise and Cape Verde Plateau and compare them to previously published results. We find within analytical uncertainty that the TA flux is twice the calcium flux, suggesting that dissolution/precipitation of CaCO₃ is the principal mechanism controlling benthic TA and Ca²⁺ fluxes. At sites where the sediments contain significant (>35%) CaCO₃ and the overlying waters are supersaturated with respect to CaCO₃, the ratios of the total dissolution rate to the remineralization rate are significantly less than at all other study sites. We propose that these observations can be explained by precipitation of fresh CaCO₃ at the supersaturated sediment surface followed by redissolution deeper in the sediments because of metabolically-produced CO₂. A numerical simulation is presented to demonstrate the feasibility of this explanation. In addition, surface exchange reactions in high-CaCO₃ sediments coupled with high rates of particle mixing may also impact rates of metabolic dissolution and depress chamber-derived estimates of carbonate alkalinity and calcium benthic fluxes. These results suggest that at supersaturated, high CaCO₃ locations, previous models of sediment diagenesis may have overestimated the impact of metabolic dissolution on the preservation of CaCO₃ deposited on the sea floor.  相似文献   

Aragonite and calcite preservation in sediments from Lake Iznik related to bottom lake oxygenation and water column depth          下载免费PDF全文

Patricia Roeser  Sven O. Franz  Thomas Litt 《Sedimentology》2016,63(7):2253-2277

This study examines the forcing mechanisms driving long‐term carbonate accumulation and preservation in lacustrine sediments in Lake Iznik (north‐western Turkey) since the last glacial. Currently, carbonates precipitate during summer from the alkaline water column, and the sediments preserve aragonite and calcite. Based on X‐ray diffraction data, carbonate accumulation has changed significantly and striking reversals in the abundance of the two carbonate polymorphs have occurred on a decadal time scale, during the last 31 ka cal bp . Different lines of evidence, such as grain size, organic matter and redox sensitive elements, indicate that reversals in carbonate polymorph abundance arise due to physical changes in the lacustrine setting, for example, water column depth and lake mixing. The aragonite concentrations are remarkably sensitive to climate, and exhibit millennial‐scale oscillations. Extending observations from modern lakes, the Iznik record shows that the aerobic decomposition of organic matter and sulphate reduction are also substantial factors in carbonate preservation over long time periods. Lower lake levels favour aragonite precipitation from supersaturated waters. Prolonged periods of stratification and, consequently, enhanced sulphate reduction favour aragonite preservation. In contrast, prolonged or repeated exposure of the sediment–water interface to oxygen results in in situ aerobic organic matter decomposition, eventually leading to carbonate dissolution. Notably, the Iznik sediment profile raises the hypothesis that different states of lacustrine mixing lead to selective preservation of different carbonate polymorphs. Thus, a change in the entire lake water chemistry is not strictly necessary to favour the preservation of one polymorph over another. Therefore, this investigation is a novel contribution to the carbon cycle in lacustrine systems.  相似文献