The effect of cobalt ion on nucleation of calcium-carbonate polymorphs

Cobalt, like Mg, may cause the precipitation of aragonite rather than calcite in aqueous solutions due to the adsorption and crystal poisoning of calcite by a hydrated ion. Solutions containing NaCl and CaCl₂, having the ionic strength and Ca content of seawater (35‰ salinity), were spiked with known amounts of CoCl₂. Calcium carbonate was precipitated by the addition of 0.7 ml of 1 M Na₂CO₃. All experimental runs were made at 25°C, and all products were examined by X-ray diffraction. At low concentrations of Co (< 5·^?4M) calcite and vaterite formed. At concentrations from 5·10^?4 M to 2·10^?3M, the products consisted of combinations of calcite and vaterite; aragonite and calcite; aragonite and vaterite; calcite, vaterite and aragonite. In solutions of 3·10^?3M CoCl₂, most precipitates were aragonite with only one sample containing a small amount of calcite. All precipitates from 5·10^?3M CoCl₂ solutions either contained aragonite or were amorphous. Solutions with concentrations of 1 · 10^?2M CoCl₂ produced only amorphous precipitates. All precipitates contained an amorphous violet phase, assumed to be basic cobaltous carbonate (2CoCO₃·Co(OH)₂·H₂O).     

碳酸钙矿物低温化学合成及其同质多象转变矿物学机理研究

通过缓慢分解Ca²⁺-Mg²⁺-HCO₃^--Cl^--H₂O溶液和以菱锶矿(或碳钡矿、白铅矿)为晶种的附晶生长法,在0-90℃温度范围内定向合成了碳酸钙同质多象变体.矿物合成实验结果表明,随着温度升高,有利于亚稳态文石和不稳定六方方解石的生成;随着溶液中Mg²⁺离子浓度增大和Ca(HCO₃)₃溶液浓度减小,均有利于亚稳态文石的形成.以XRD和SEM技术为实验手段,详细研究了碳酸钙同质多象转变过程.结果显示:在流体参与的情况下,文石→方解石和六方方解石→方解石的同质多象转变速率很快,并且其转变的矿物学机理为溶解/再沉淀.     

The distribution of strontium in limestones on Barbuda, West Indies

The Sr²⁺ content of Barbudan limestones is proportional to the aragonite content. The Sr²⁺ content of calcite which has replaced aragonite varies from 3000 p.p.m. in the youngest limestones to 50 p.p.m., average values are approximately 300 p.p.m. The (mSr²⁺/mCa²⁺)_L ratios from well waters within the limestone fall within the predicted values assuming K^Sr_C～0·1. The high (mSr²⁺/mCa)²⁺_L ratios expected by a lower value of K^Sr_C do not occur. The build up of (mSr²⁺/mCa²⁺)_L ratios seen in waters from Barbados is not seen in the well waters from Barbuda. The Sr²⁺ content of calcite is generally lower than is seen in Barbados, but similar to that seen in parts of the Miami Oolite. Diagenesis of aragonite in Barbudan limestones is probably occurring in a more open system than in Barbados.     

室温条件下青海湖水中镁离子浓度对沉淀碳酸钙同质多像类型的调控

青海湖是我国唯一报道过的现代湖底沉积物中白云石、方解石和文石等多种碳酸盐矿物共存的高原内陆咸水湖泊。以青海湖水和除菌青海湖水作为载体,以CaCl_2和MgCl_2·6 H_2O作为反应原料,在实验室常温条件下采取控制变量法制备出不同浓度Mg~(2+)参与下的钙质沉淀物,探讨Mg~(2+)浓度对沉淀物类型的影响。仅添加CaCl_2时,青海湖水中的沉淀物主要是石膏(Ca SO_4·2 H_2O)和球霰石(CaCO_3);在添加CaCl_2的同时添加MgCl_2·6 H_2O,沉淀物的石膏消失,完全转变成碳酸盐矿物,包括方解石和球霰石;当湖水中Mg~(2+)浓度为0.62 mol/L时,球霰石消失,沉淀物变为方解石和文石;随着Mg~(2+)浓度继续升高,文石含量稳步增加,方解石含量则逐渐减少,当Mg~(2+)浓度达到1.22 mol/L或更高时,方解石全部消失,沉淀物仅剩文石。实验结果表明,青海湖水中较高浓度的SO_4~(2-)对碳酸钙晶体生长有抑制作用,而额外加入的Mg~(2+)可以解除SO_4~(2-)的抑制作用,使得Ca~(2+)与HCO_3~-和CO_3~(2-)结合形成碳酸钙。此外,碳酸钙的同质多像类型也明显受到Mg~(2+)浓度的控制,随着湖水中Mg~(2+)浓度增加,方解石、球霰石不再稳定,而文石逐渐占主导地位,当Mg/Ca值达到6.1时,反应产物中仅有文石稳定存在。     

Selected geochemical factors influencing diagenesis of eocene carbonate rocks,peninsular Florida,U.S.A.

The geochemical significance of three selected ions (Mg²⁺, Na⁺, and Sr²⁺) supports a model of dolomitization by brackish groundwater. This groundwater zone contains sufficient quantities of Mg²⁺ to facilitate dolomitization ($\text{Mg}\text{Ca}\text{ratios 1}$). Rising and falling of sea level and fluctuations of the phreatic zone related to climatic variations account for the thickness of the dolomite layers and the chemical distributions within these layers. Sodium concentrations in the calcite are 70–185 ppm, indicating formation in brackish water. Dolomite has sodium concentrations between 50–1400 ppm, suggesting formation in waters of similar salinity.Strontium in calcite ranges from 320–600 ppm, suggesting diagenesis in slightly saline waters in an open system. Dolomite contains 241 ppm Sr²⁺ on the average and calcite has 418 ppm Sr²⁺. The Sr²⁺ concentrations of the dolomite are characteristic of diagenesis in water less saline than sea water. Average strontium concentrations in the dolomite occur in two distinct groups, 260 ppm for dolomite with 39–43 mole-% MgCo₃ and 195 ppm for the dolomite with 44–50 mole-% MgCO₃. The difference in the Sr²⁺ concentrations of the two dolomite groups indicates the higher mole-% MgCO₃ dolomite recrystallized in a less saline environment than the lower mole-% MgCO₃ dolomite. These different environments are attributed to a relatively more saline coastal environment and a less saline inland environment.The more nearly stoichiometric dolomite (44–50 mole-% MgCO₃) has less scatter when mole-% MgCO₃ is plotted against Sr²⁺ and Na⁺. This suggests a greater approach to equilibrium with the dolomitizing fluid than the lower mole-% MgCO₃ (39–43) dolomite. The more saline environment has higher Mg/Ca ratios and promotes more calcium-rich dolomite during diagenesis because of the inhibition from competing foreign ions and because it is thermodynamically a more favorable environment which causes more rapid crystallization. The less saline waters allow recrystallization to proceed more slowly, producing better ordering in the dolomites, textural preservation and development of subhedral to euhedral rhombic crystals.     

Sr,Cd, Mn and Co distribution coefficients in calcite as a function of calcite precipitation rate

Distribution coefficients, as a function of precipitation rate, were determined for the metals Sr²⁺, Co²⁺, Mn²⁺ and Cd²⁺in calcite. A pH-stat was used to maintain a constant degree of-saturation, and hence precipitation rate, during each coprecipitation run. The precipitation rate was proportional to the degree of supersaturation and the mass of seed crystal introduced. Distribution coefficients (λ) as a function of rate were determined using radioactive isotopes for solutions with saturations $\text{Ω = 1}$ to $\text{Ω = 5.5}$. Strontium distribution coefficients increased with increasing precipitation rate, while Co, Mn and Cd distribution coefficients decreased with increasing precipitation rate. The following rate expressions (at 25°C) were derived: logλ_Sr = 0.249 log R ?1.57logλ_Mn = ?0.266 log R + 1.35logλ_Co = ?0.173 log R + 0.68logλ_Cd = ?0.194 log R + 1.46 where R is the observed precipitation rate in nmoles CaCO₃ per mg seed crystal per min.In separate experiments the uptake of radioactive isotopes was monitored during the recrystallization of calcite seed crystals. Rates of recrystallization were from 100 to 10, 000 times slower than the pH-stat experiments, but yielded distribution coefficients consistent with the above rate expressions.Using gross estimates of biogenic crystal growth rates, aragonite to calcite transformation rates, and the above Sr rate expression, biogenic calcite and diagenetic calcite Sr contents are estimated. These experiments indicate that in addition to solution composition, precipitation rate is a significant factor influencing the trace metal content of naturally occurring calcite.     

Stable isotopes of cherts and carbonate cements in the Lake Valley Formation (Mississippian), Sacramento Mts, New Mexico

Oxygen isotopic compositions of chert and calcite cements in the Lake Valley Formation indicate that these diagenetic features cannot be equilibrium co-precipitates in spite of their coexistence in the same interstices. Petrography of megaquartz and non-ferroan calcite cements indicates that both are original precipitates that formed during pre-Pennsylvanian time at shallow burial depths (< 215m) implying precipitation temperatures less than 30°C. Under these constraints the δ¹⁸Os of megaquartz (mean =+27.0^0/00 SMOW; range =+ 24.8 to + 28.9^0/00) and calcite (mean =+ 28.0^0/00 SMOW; range =+ 27.3 to + 28.4^0/00) are best interpreted as unaltered since precipitation; thus, they must reflect the oxygen isotopic composition of pre-Pennsylvanian pore waters. Microquartz and chalcedony are interpreted to have formed from recrystallization of pre-Pennsylvanian opal-CT precursors, and therefore probably re-equilibrated during recrystallization in late or post-Mississippian time. We propose a model integrating the isotopic data with regional petrographic and sedimentological data that explains the greater consistency and generally greater δ¹⁸Os values of the calcites compared to those of the cherts. This model is one of chertification and calcite cementation in a regional meteoric phreatic ground-water system, the seaward terminus of which moved southward during lowering of pre-Pennsylvanian sea level. The calcite cements and some of the opal-CT precursor to microquartz and chalcedony are interpreted to have formed in the more seaward portions of the groundwater system. The megaquartz precipitated in the more inland parts of the phreatic groundwater system where rainfall was isotopically lighter and more variable. As such, the δ¹⁸Os of the megaquartz reflect the isotopic composition of groundwaters in areas undersaturated with respect to calcite.     

Cation exchange reactions controlling desorption of Sr from coarse-grained contaminated sediments at the Hanford site, Washington

Nuclear waste that bore ⁹⁰Sr²⁺ was accidentally leaked into the vadose zone at the Hanford site, and was immobilized at relatively shallow depths in sediments containing little apparent clay or silt-sized components. Sr²⁺, ⁹⁰Sr²⁺, Mg²⁺, and Ca²⁺ was desorbed and total inorganic carbon concentration was monitored during the equilibration of this sediment with varying concentrations of Na⁺, Ca²⁺. A cation exchange model previously developed for similar sediments was applied to these results as a predictor of final solution compositions. The model included binary exchange reactions for the four operant cations and an equilibrium dissolution/precipitation reaction for calcite. The model successfully predicted the desorption data. The contaminated sediment was also examined using digital autoradiography, a sensitive tool for imaging the distribution of radioactivity. The exchanger phase containing ⁹⁰Sr was found to consist of smectite formed from weathering of mesostasis glass in basaltic lithic fragments. These clasts are a significant component of Hanford formation sands. The relatively small but significant cation exchange capacity of these sediments was thus a consequence of reaction with physically sequestered clays in sediment that contained essentially no fine-grained material. The nature of this exchange component explained the relatively slow (scale of days) evolution of desorption solutions. The experimental and model results indicated that there is little risk of migration of ⁹⁰Sr²⁺ to the water table.     

Diagenesis of spiculites and carbonates in a Permian temperate ramp succession – Tempelfjorden Group,Spitsbergen, Arctic Norway

This paper explores little investigated diagenesis of spicule‐dominated sediments, based on Permian spiculites and cool‐water carbonates of the Tempelfjorden Group in central Spitsbergen. Field observations, petrography, stable isotope geochemistry, and mineralogical and chemical analyses reveal that the strata have been subjected to multistage diagenesis as the result of silica phase transitions at medium burial depths and deep‐burial overprinting. The growth of silica concretions occurred during the opal‐A/opal‐CT conversion and was controlled by the content and distribution of clay and spicules in the sediment, resulting in a variety of megascopic silica fabrics. Opal‐CT was subsequently dissolved, and all silica is now in a stable quartz stage. Petrographically, the rocks are characterized by a variety of chalcedony and quartz cements which perfectly preserve precursor textures. Most cements precipitated from silica‐oversaturated fluids, and their shapes reflect the silica saturation state and geometry of the pore space. Some microquartz and cryptoquartz also formed by a solid–solid inversion (recrystallization) of chalcedony. The cements have δ ¹⁸O values between +30‰ and +20‰ Standard Mean Ocean Water and display a systematic depletion in ¹⁸O from the first to the last crystallized, interpreted to reflect a gradual increase in temperature during burial. The precipitation of quartz cements started in the Middle Triassic when the strata passed the 19°C isotherm at burial depths of ca 600 m, and was completed in the mid‐Cretaceous, 2·3 km beneath the sea floor at temperatures of 75°C. Late diagenetic overprinting of the chert includes fracturing, brecciation and cementation with carbonate cements having δ ¹⁸O values between +2‰ and −30‰ Pee Dee Belemnite and δ ¹³C values between +4‰ and −14‰ Pee Dee Belemnite; they are linked to hot solutions introduced during Cretaceous volcanism or Palaeogene tectonism. This study illustrates the diagenetic pathway during burial of spicule‐rich sediments in a closed system and thereby provides a baseline for studies of more complexly altered chert deposits.     

Salinity reflux and dolomitization of southern Australian slope sediments: the importance of low carbonate saturation levels

Anomalously saline waters in Ocean Drilling Program Holes 1127, 1129, 1130, 1131 and 1132, which penetrate southern Australian slope sediments, and isotopic analyses of large benthic foraminifera from southern Australian continental shelf sediments, indicate that Pleistocene–Holocene meso‐haline salinity reflux is occurring along the southern Australian margin. Ongoing dolomite formation is observed in slope sediments associated with marine waters commonly exceeding 50‰ salinity. A well‐flushed zone at the top of all holes contains pore waters with normal marine trace element contents, alkalinities and pH values. Dolomite precipitation occurs directly below the well‐flushed zone in two phases. Phase 1 is a nucleation stage associated with waters of relatively low pH (ca 7) caused by oxidation of H₂S diffusing upward from below. This dolomite precipitates in sediments < 80 m below the sea floor and has δ¹³C values consistent with having formed from normal sea water (? 1‰ to + 1‰ Vienna Pee Dee Belemnite). The Sr content of Phase 1 dolomite indicates that precipitation can occur prior to substantial metastable carbonate dissolution (< 300 ppm in Holes 1129 and 1127). Dolomite nucleation is interpreted to occur because the system is undersaturated with respect to the less stable minerals aragonite and Mg‐calcite, which form more readily in normal ocean water. Phase 2 is a growth stage associated with the dissolution of metastable carbonate in the acidified sea water. Analysis of large dolomite rhombs demonstrates that at depths > 80 m below the sea floor, Phase 2 dolomite grows on dolomite cores precipitated during Phase 1. Phase 2 dolomite has δ¹³C values similar to those of the surrounding bulk carbonate and high Sr values relative to Phase 1 dolomite, consistent with having formed in waters affected by aragonite and calcite dissolution. The nucleation stage in this model (Phase 1) challenges the more commonly accepted paradigm that inhibition of dolomitization by sea water is overcome by effectively increasing the saturation state of dolomite in sea water.     

The morphology of calcite crystals grown in a porous medium doped with divalent cations

Calcite crystals were grown in the presence of small concentrations (50, 200, and 600 ppm) of divalent cations (Ba²⁺, Sr²⁺, Co²⁺ and Mn²⁺) in a silica hydrogel medium. The calcite crystals grown in the presence of cations larger than Ca²⁺ (Ba²⁺ or Sr²⁺) developed rhombohedral habits defined by {101¯4} form, similar to the morphology of calcite grown in a pure gel. SEM images show that growth on {101¯4} occurs by lateral advancement of layers bounded by macroscopic dendritic or jagged steps. In the case of calcite crystals grown in a gel doped with cations smaller than Ca²⁺ (Co²⁺ or Mn²⁺), a variety of morphologies was obtained, ranging from blocky crystals (at lower concentrations: 50 and 200 ppm) to peanut-like aggregates, spheres and spherulites (at 600 ppm). The macroscopic morphological characteristics of such doped calcite crystals reflect closely the growth behaviour of calcite {101¯4} surface at a nanoscale, reported by previous AFM studies. Morphological features have been interpreted on the basis of the modification of growing steps characteristics as a consequence of asymmetrical cation incorporation. The use of such morphologies as a criterion of biological activity is, therefore, unreliable.     

Element partitioning during precipitation of aragonite from seawater: A framework for understanding paleoproxies

This study presents the results from precipitation experiments carried out to investigate the partitioning of the alkaline earth cations Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺ between abiogenic aragonite and seawater as a function of temperature. Experiments were carried out at 5 to 75 °C, using the protocol of Kinsman and Holland [Kinsman, D.J.J., Holland, H.D., 1969. The coprecipitation of cations with CaCO₃ IV. The coprecipitation of Sr²⁺ with aragonite between 16 and 96 °C. Geochim. Cosmochim. Acta33, 1-17.] The concentrations of Mg Sr and Ba were determined in the fluid from each experiment by inductively coupled plasma-mass spectrometry, and in individual aragonite grains by secondary ion mass spectrometry. The experimentally produced aragonite grains are enriched in trace components (“impurities”) relative to the concentrations expected from crystal-fluid equilibrium, indicating that kinetic processes are controlling element distribution. Our data are not consistent with fractionations produced kinetically in a boundary layer adjacent to the growing crystal because Sr²⁺, a compatible element, is enriched rather than depleted in the aragonite. Element compatibilities, and the systematic change in partitioning with temperature, can be explained by the process of surface entrapment proposed by Watson and Liang [Watson, E.B., Liang, Y., 1995. A simple model for sector zoning in slowly grown crystals: implications for growth rate and lattice diffusion, with emphasis on accessory minerals in crustal rocks. Am. Mineral.80, 1179-1187] and Watson [Watson, E.B., 1996. Surface enrichment and trace-element uptake during crystal growth. Geochim. Cosmochim. Acta60, 5013-5020; Watson, E.B., 2004. A conceptual model for near-surface kinetic controls on the trace-element and stable isotope composition of abiogenic calcite crystals. Geochim. Cosmochim. Acta68, 1473-1488]. This process is thought to operate in regimes where the competition between crystal growth rate and diffusivity in the near-surface region limits the extent to which the solid can achieve partitioning equilibrium with the fluid. A comparison of the skeletal composition of Diploria labyrinthiformis (brain coral) collected on Bermuda with results from precipitation calculations carried out using our experimentally determined partition coefficients indicate that the fluid from which coral skeleton precipitates has a Sr/Ca ratio comparable to that of seawater, but is depleted in Mg and Ba, and that there are seasonal fluctuations in the mass fraction of aragonite precipitated from the calcifying fluid (“precipitation efficiency”). The combined effects of surface entrapment during aragonite growth and seasonal fluctuations in “precipitation efficiency” likely forms the basis for the temperature information recorded in the aragonite skeletons of Scleractinian corals.     

Aragonite relic preservation in Jurassic calcite-replaced bivalves

Shells of the aragonite bivalve Neomiodon (Great Estuarine Group, Jurassic, Scotland) replaced by coarse neomorphic calcite contain oriented relics of the original aragonite ultrastructure. The presence of these relics in such old altered shells, as well as the high Sr content of the replacement calcite, indicate that the process of calcite replacement of aragonite is not a cumulative slow process involving repeated alteration events, but rather a rapid, one-step process. Aragonite relics, once encased in neomorphic spar, will survive as unequivocal evidence of original aragonite mineralogy, barring total remobilization of the enclosing stable calcite, a generally unlikely event. The retention of this residual aragonite and high-Sr calcite supports recent isotopic studies which suggest that the multiple phases of alteration (‘recrystallization’) invoked in earlier literature are unlikely events in the diagenesis of most undolomitized limestones. Retention of aragonite relics appears to be independent of whether alteration occurs in shallow meteoric or, as in the case of our Neomiodon material, deeper burial environments. Pseudopleochroism of the replaced Neomiodon shells appears to be due to organic, largely graphitic, relics, not to the aragonite relics.     

Origin and diagenetic evolution of Ca–Mg–Fe carbonates in some coalfields of Japan

Carbonate concretions, lenses and bands in the Pleistocene, Palaeogene and Upper Triassic coalfields of Japan consist of various carbonate minerals with varied chemical compositions. Authigenic carbonates in freshwater sediments are siderite > calcite > ankerite > dolomite >> ferroan magnesite; in brackish water to marine sediments in the coal measures, calcite > dolomite > ankerite > siderite >> ferroan magnesite; and in the overlying marine deposits, calcite > dolomite >> siderite. Most carbonates were formed progressively during burial within a range of depths between the sediment-water interface and approximately 3 km. The mineral species and the chemical composition of the carbonates are controlled primarily by the initial sedimentary facies of the host sediments and secondarily by the diagenetic evolution of pore water during burial. Based on the regular sequence and burial depth of precipitation of authigenic carbonates in a specific sedimentary facies, three diagenetic stages of carbonates are proposed. Carbonates formed during Stage I (< 500 m) strongly reflect the initial sedimentary facies, e.g. low Ca-Mg siderite in freshwater sediments which are initially rich in iron derived from lateritic soil on the nearby landmass, and Mg calcite and dolomite in brackish-marine sediments whose pore waters abound in Ca²⁺ and Mg²⁺ originating in seawater and calcareous shells. Carbonates formed during Stage II (500–2000 m) include high Ca-Mg siderite, ankerite, Fe dolomite and Fe–Mg calcite in freshwater sediments. The assemblage of Stage II carbonates in brackish-marine sediments in the coal measures is similar to that in freshwater sediments. This suggests similar diagenetic environments owing to an effective migration and mixing of pore water due to the compaction of host sediments. Carbonates formed during Stage III (> 2000 m) are Fe calcite and extremely high Ca-Mg siderite; the latter is exclusively in marine mudstones. The supply of Ca is partly from the alteration of silicates in the sediments at elevated burial temperatures. After uplift, calcite with low Mg content precipitates from percolating groundwater and fills extensional cracks.     

Diagenesis of Barremian-Aptian platform carbonates (the Urgonian Limestone Formation of SE France): near-surface and shallow-burial diagenesis

The diagenesis of carbonate platform sediments is controlled by the original facies and mineralogy, climate, sea-level changes and burial history; these controls are clearly seen in the diagenesis of the Urgonian platform carbonates of SE France. Early diagenesis in the Urgonian platform included the precipitation of marine cements, dissolution of rudist shells and minor karstification. Diagenetic features produced during this phase were controlled by several falls in relative sea-level during the Barremian to mid-Aptian punctuating platform sedimentation, the original mineralogy of the sediment and the prevailing semi-arid/arid climate in the region at this time. Following a relative sea-level rise and further sedimentation, progressive burial of the platform led to minor compaction, followed by precipitation of coarse, equant, zoned to non-luminescent, calcite cement. This cement was cut by later stylolites, suggesting a relatively shallow-burial origin. Stable isotope (mean values - 7.94%δ¹⁸O and 0.36%δ¹³C) and trace element (mean values of Fe 334 ppm, Mn 92 ppm and Sr 213 ppm) data suggest that these cements precipitated from meteoric fluids at temperatures slightly elevated relative to depositional temperatures. A variable thickness of replacive dolomite which occurs preferentially within the shelf-margin facies of the lower part of the Urgonian post-dates mechanical fracturing and chemical compaction, but pre-dates the main phase of stylolitization. It is probable that the dolomitizing fluid was sourced by the early compaction-driven release of connate fluids held within the underlying muddy units. The burial history of these rocks suggests that calcite cementation and dolomitization took place at relatively shallow burial depths (1–1.5 km). The overall diagenetic history of the Urgonian Limestone Formation is a reflection of the pre-conditioning of the platform limestones by climate, sea level, tectonics and the shallow burial depths experienced by the platform during the later Mesozoic.     

The dolomitization of CaCO3: an experimental study at 252–295°C

The results of experiments on the hydrothermal dolomitization of calcite (between 252 and 295°C) and aragonite (at 252°C) by a 2 M CaCl₂-MgCl₂ aqueous solution are reported and discussed. Dolomitization of calcite proceeds via an intermediate high (ca. 35 mole %) magnesian calcite, whereas that of aragonite is carried out through the conversion of the reactant into a low (5.6 mole %) magnesian calcite which in turn transforms into a high (39.6 mole %) magnesian calcite. Both the intermediate phases and dolomite crystallize through a dissolution-precipitation reaction. The intermediate phases form under local equilibrium within a reaction zone surrounding the dissolving reactant grains. The volume of the reaction zone solution can be estimated from Sr²⁺ and Mg²⁺ partitioning equations. In the case of low magnesian calcite growing at the expense of aragonite at 252°C, the total volume of these zones is in the range of 2 × 10^?5 to 2 × 10^?4 1., out of 5 × 10^?3 1., the volume of the bulk solution.The apparent activation energies for the initial crystallization of high magnesian calcite and dolomite are 48 and 49 kcal/mole, respectively.Calcite transforms completely into dolomite within 100 hr at 252°C. The overall reaction time is reduced to approximately 4 hr at 295°C. The transformation of aragonite to dolomite at 252°C occurs within 24 hr. The nature of the reactant dictates the relative rates of crystallization of the intermediate phases and dolomite. With calcite as reactant, dolomite growth is faster than that of magnesian calcite; this situation is reversed when aragonite is dolomitized.Coprecipitation of Sr²⁺ with dolomite is independent of temperature (within analytical error) between 252 and 295°C. Its partitioning, with respect to calcium, between dolomite and solution results in distribution coefficients in the range of 2.31 × 10^?2 to 2.78 × 10^?2.     

Calcite cementation during bacterial manganese, iron and sulphate reduction in Jurassic shallow marine carbonates

Faunally restricted argillaceous wackestones from the Middle Jurassic of eastern England contain evidence of early diagenetic skeletal aragonite dissolution and stabilization of the carbonate matrix, closely followed by precipitation of zoned calcite cements, and precipitation of pyrite. Distinctive cathodoluminescence and trace element trends through the authigenic calcites, their negative δ¹³C compositions and the location of pyrite in the paragenetic sequence indicate that calcite precipitation took place during sequential bacterial Mn, Fe and sulphate reduction. Calcite δ¹⁸O values are compatible with cementation from essentially marine pore fluids, although compositions vary owing to minor contamination with ¹⁸O-depleted ‘late’cements. Mg and Sr concentrations in the calcites are lower than those in recent marine calcite cements. This may be a result of kinetic factors associated with the shallow burial cementation microenvironments. Bicarbonate for sustained precipitation of the authigenic calcites was derived largely from aragonite remobilization, augmented by that produced through anaerobic organic matter oxidation in the metal and sulphate reduction environments. Aragonite dissolution is thought to have been induced by acidity generated during aerobic bacterial oxidation of organic matter. Distinction of post-oxic metal reduction and anoxic sulphate reduction diagenetic environments in modern carbonate sediments is uncommon outside pelagic settings, and early bacterially mediated diagenesis in modern platform carbonates is associated with extensive carbonate dissolution. High detrital Fe contents of the Jurassic sediments, and their restricted depositional environment, were probably the critical factors promoting early cementation. These precipitates constitute a unique example of calcite authigenesis in shallow water limestones during bacterial Mn and Fe reduction.     

Diagenesis of silica-rich mound-bedded chalk,the Coniacian Arnager Limestone,Denmark

The Coniacian Arnager Limestone Formation is exposed on the Danish island of Bornholm in the Baltic Sea. It is composed of mound-bedded siliceous chalk, and X-ray diffraction and scanning electron microscopy indicate a content of 30–70% insoluble minerals, including authigenic opal-CT, quartz, clinoptilolite, feldspars, calcite, dolomite, and barite. Opal-CT and clinoptilolite are the most common and constitute 16–53% and 2–9%, respectively. The content of insoluble minerals varies laterally both within the mounds and in planar beds, and the opal-CT content varies by up to 10% vertically. The mounds consist of two microfacies, spiculitic wackestone and bioturbated spiculitic wackestone, containing 10–22% and 7–12% moulds after spicules, respectively.Subsequent to deposition and shallow burial, dissolution of siliceous sponge spicules increased the silica activity of the pore water and initiated precipitation of opal-CT. The opal-CT formed at temperatures around 17 °C, the precipitation lowered the silica activity and the Si/Al ratio of the pore water, resulting in precipitation of clinoptilolite, feldspar and smectite. Calcite formed synchronously with the latest clinoptilolite. Minor amounts of quartz precipitated in pore water with low silica activity during maximum burial, probably to depths of 200–250 m. The dissolution of sponge spicules and decomposition of the sponge tissue also resulted in the release of Ba²⁺, Sr²⁺, Mg²⁺, Ca²⁺ and CO₃^2?, facilitating precipitation of barite and dolomite. Precipitation of especially opal-CT reduced the porosity to an average of 40% and cemented the limestone. The study highlights the diagenetic pathways of bio-siliceous chalk and the effects on preservation of porosity and permeability.     

Strontium behavior in the aragonite-calcite transformation: An experimental study at 40–98°C

The behavior of strontium during the replacement of aragonite by calcite, in a closed system between 40°C and 98°C, has been experimentally investigated. The experiments were conducted in CaCl₂ solutions, with and without NaCl. The distribution coefficient of strontium in calcite (λ_Sr^2+C) was found to be affected only slightly by temperature changes, and almost insignificantly by the presence of NaCl. λ_Sr^2+C values at 0.01 m_Ca²⁺ (its concentration in normal sea water) are: 0.055 at 40°C and 0.058 at 98°C. These results indicate that the low (around 500 ppm) concentration of strontium in ancient limestones could have been brought about by aragonite-to-calcite transformation in a system open to sea water, and are not necessarily indicative of replacement in fresh waters.     

Microspar development during early marine burial diagenesis: a comparison of Pliocene carbonates from the Bahamas with Silurian limestones from Gotland (Sweden)

Comparison of ultrastructures in Pliocene periplatform carbonates from the Bahamas with Silurian limestones from Gotland (Sweden) reveals that despite the differences in primary sediment composition and age, they reflect a similar mechanism of lithification. In both sequences calcite microspar was formed as a primary cement at an early stage of marine burial diagenesis. Neither significant compression nor meteoric influence are necessary for the formation of calcite microspar. A model is proposed for the process of microsparitic cementation of fine-grained aragonite needle muds comprising four stages: (1) unconsolidated, aragonite-dominated carbonate mud; (2) precipitation of microspar that engulfs aragonite needles; (3) dissolution of aragonite, resulting in pitted surfaces of the microspar crystals; and (4) slight recrystallization. Our results contradict the widespread opinion that microspar necessarily is a product of secondary recrystallization of a previously lithified micrite.