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.     

Origin of anhedral Sr-rich calcite in deep-water mixed sediment, north-east Australia

At burial depths of 800-1000 m, within the epicontinental Queensland Trough of north-east Australia (ODP Site 823), microcrystalline inter- and intraskeletal mosaics of anhedral (loaf-shaped, rounded) calcite have Sr²⁺ values ranging from below microprobe detection limits (<150 ppm) to 8100 ppm. Host rocks are well lithified, fine-grained mixed sediment to clayey wackestone and packstone of Middle and Late Miocene age. Petrography demonstrates that calcite precipitation has spanned shallow to deep burial, overlapping formation of framboidal pyrite in the upper 50 m; shallow-burial dolomitization (<300 m); and dedolomitization during sediment consolidation and incipient chemical compaction at greater (>400–500 m) depths. Petrographic observations illustrate that the calcite microfabric formed through coalescing crystal growth resulting from one or a combination of displacive growth in clay, porphyroid neomorphism of aragonite/vaterite, and clay replacement by calcite. Sr²⁺ mean concentrations in calcite between depths of 800 and 1000 m are similar to an expected equilibrium pore-water concentration, using a D^sr of 0.06, and may indicate active calcite precipitation. However, Sr²⁺ variation (2000–5000 ppm) within and among crystals, and concentrations that range well above predicted equilibrium values for a given depth, illustrate either variable Sr²⁺ retention during recrystallization of shelf-derived aragonite (and authigenic local vaterite) or relative uptake of Sr²⁺ during calcite precipitation with burial. Within the context of calcite formation during burial to 1 km, diagenetic attributes that affect the latter process include increased concentrations of pore-water Sr²⁺ with depth associated with aragonite recrystallization/dissolution; upward migration of Sr-rich pore water; and increased D^Sr related to local variation in precipitation/recrystallization rates, differential crystal sector growth rates and/or microvariation in aragonite distribution.     

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。     

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).     

Re-evaluating boron speciation in biogenic calcite and aragonite using B MAS NMR

Understanding the partitioning of aqueous boron species into marine carbonates is critical for constraining the boron isotope system for use as a marine pH proxy. Previous studies have assumed that boron was incorporated into carbonate through the preferential uptake of tetrahedral borate B(OH)₄⁻. In this study we revisit this assumption through a detailed solid state ¹¹B magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopic study of boron speciation in biogenic and hydrothermal carbonates. Our new results contrast with those of the only previous NMR study of carbonates insofar as we observe both trigonal and tetrahedral coordinated boron in almost equal abundances in our biogenic calcite and aragonite samples. In addition, we observe no strict dependency of boron coordination on carbonate crystal structure. These NMR observations coupled with our earlier re-evaluation of the magnitude of boron isotope fractionation between aqueous species suggest that controls on boron isotope composition in marine carbonates, and hence the pH proxy, are more complex that previously suggested.     

Implications for Neoarchaean ocean chemistry from primary carbonate mineralogy of the Campbellrand-Malmani Platform, South Africa

The precipitation of calcite and aragonite as encrustations directly on the seafloor was an important platform‐building process during deposition of the 2560–2520 Ma Campbellrand‐Malmani carbonate platform, South Africa. Aragonite fans and fibrous coatings are common in unrestricted, shallow subtidal to intertidal facies. They are also present in restricted facies, but are absent from deep subtidal facies. Decimetre‐thick fibrous calcite encrustations are present to abundant in all depositional environments except the deepest slope and basinal facies. The proportion of the rock composed of carbonate that precipitated as encrustations or in primary voids ranges from 0% to > 65% depending on the facies. Subtidal facies commonly contain 20–35%in situ precipitated carbonate, demonstrating that Neoarchaean sea water was supersaturated with respect to aragonite, carbonate crystal growth rates were rapid compared with sediment influx rates, and the dynamics of carbonate precipitation were different from those in younger carbonate platforms. The abundance of aragonite pseudomorphs suggests that sea‐water pH was neutral to alkaline, whereas the paucity of micrite suggests the presence of inhibitors to calcite and aragonite nucleation in the mixed zone of the oceans.     

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.     

The solubility of calcite in seawater solutions of various magnesium concentration, It = 0.697 m at 25 °C and one atmosphere total pressure

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.     

The role of magnesium in the crystal growth of calcite and aragonite from sea water

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

Strontium incorporation into calcite generated by bacterial ureolysis

Strontium incorporation into calcite generated by bacterial ureolysis was investigated as part of an assessment of a proposed remediation approach for ⁹⁰Sr contamination in groundwater. Urea hydrolysis produces ammonium and carbonate and elevates pH, resulting in the promotion of calcium carbonate precipitation. Urea hydrolysis by the bacterium Bacillus pasteurii in a medium designed to mimic the chemistry of the Snake River Plain Aquifer in Idaho resulted in a pH rise from 7.5 to 9.1. Measured average distribution coefficients (D_EX) for Sr in the calcite produced by ureolysis (0.5) were up to an order of magnitude higher than values reported in the literature for natural and synthetic calcites (0.02-0.4). They were also higher than values for calcite produced abiotically by ammonium carbonate addition (0.3). The precipitation of calcite in these experiments was verified by X-ray diffraction. Time-of-flight secondary ion mass spectrometry (ToF SIMS) depth profiling (up to 350 nm) suggested that the Sr was not merely sorbed on the surface, but was present at depth within the particles. X-ray absorption near edge spectra showed that Sr was present in the calcite samples as a solid solution. The extent of Sr incorporation appeared to be driven primarily by the overall rate of calcite precipitation, where faster precipitation was associated with greater Sr uptake into the solid. The presence of bacterial surfaces as potential nucleation sites in the ammonium carbonate precipitation treatment did not enhance overall precipitation or the Sr distribution coefficient. Because bacterial ureolysis can generate high rates of calcite precipitation, the application of this approach is promising for remediation of ⁹⁰Sr contamination in environments where calcite is stable over the long term.     

淡水珍珠中球文石的XRD谱

球文石是CaCO3的同质多象变体，在自然界中很少出现。对不同质量淡水珍珠进行XRD物相分析，结果表明不同颜色的优质淡水珍珠中几乎全部由文石组成，方解石不发育；劣质淡水珍珠中主要含有文石、球文石；在劣质的淡水无光珠发现有球文石，可能与这些珍珠混有较多的有机物有关，文中例举了含球文石与不含球文石的淡水珍珠XRD谱。     

Were kinetics of Archean calcium carbonate precipitation related to oxygen concentration?

Archean carbonates commonly contain decimetre- to metre-thick beds consisting entirely of fibrous calcite and neomorphosed fibrous aragonite that precipitated in situ on the sea floor. The fact that such thick accumulations of precipitated carbonate are rare in younger marine carbonates suggests an important change in the modes of calcium carbonate precipitation through time. Kinetics of carbonate precipitation depend on the concentration of inhibitors to precipitation that reduce crystallization rates and crystal nuclei formation, leading to kinetic maintenance of supersaturated solutions. Inhibitors also affect carbonate textures by limiting micrite precipitation and promoting growth of older carbonate crystals on the sea floor. Fe2+, a strong calcite-precipitation inhibitor, is thought to have been present at relatively high concentrations in Archean seawater because oxygen concentrations were low. The rise in oxygen concentration at 2.2-1.9 Ga led to the removal of Fe2+ from seawater and resulted in a shift from Archean facies, which commonly include precipitated beds, to Proterozoic facies, which contain more micritic sediment and only rare precipitated beds.     

室温常压下 Ca2+-Mg2+-HCO31--H2O 体系的试验研究

世界上很多海域中的现代碳酸盐沉积正在形成,如巴哈马滩、美国的佛罗里达湾、古巴的巴塔诺湾、中东的波斯湾等地,以及丹麦的某些近海地区。产于这些海域中的现代碳酸盐沉积物,其矿物组成主要是文石,其次为镁方解石,纯方解石较少,现代白云石沉积更为少见。我国的现代碳酸盐沉积见于南海诸岛及海南岛的沿海地带。作者曾利用粉晶照相鉴定了采自我国南海二十余种珊瑚、瓣鳃类、腹足类、有孔虫等现代海相生物壳体的物相,发现除有孔虫和海胆壳是由镁方解石构成外,其余生物壳体皆由文石构成。     

On the Direction and Magnitude of Oxygen Isotope Fractionation Between Calcite and Aragonite at Thermodynamic Equilibrium

Oxygen isotope fractionation factors between calcium carbonates and water have been applied to ancient marine geochemistry principally for the purpose of geothermometry. The problem was encountered, however, with respect to the direction and magnitude of oxygen isotope fractionation between calcite and aragonite at thermodynamic equilibrium. This basically involves sound understanding of both thermodynamics and kinetics of oxygen isotope fractionation between inorganically precipitated carbonate and water at low temperatures. Thus the crucial issues are to acknowledge the processes of chemical reaction and isotopic exchange during precipitation of CaCO₃ minerals in solution, the kinetic mechanism of isotope equilibrium or disequilibrium, the effect of polymorphic transition from metastable aragonite to stable calcite under hydrous or anhydrous conditions, and the presence or absence of isotope salt effect on oxygen isotope exchange between carbonate and water in response to the hydrous or anhydrous conditions at thermodynamic equilibrium. Because good agreements exist in carbonate–water oxygen isotope fractionation factors between theoretical calculations and experimental determinations, it is encouraging to applying the thermodynamic and kinetic data to isotopic paleothermometry and geochemical tracing.     

Dissolution experiment and transformation condition analysis of Paleogene aragonite in the Jiyang Depression,China

In general, aragonite exists as a metastable carbonate mineral under near-surface conditions, and is commonly transformed into calcite under the subsurface and during diagenesis. It is thus seldom found in sedimentary rocks, but aragonite is common in the Paleogene lacustrine shales in the Jiyang Depression in eastern China. Dissolution experiments were conducted on the Paleogene aragonite-enriched and calcite-enriched shales at different temperatures, pressures and acetic acid concentrations, and in different types of solution. The results show that aragonite is insoluble in the in situ formation water but dissolved more readily under acetic acid conditions than calcite with the degree of dissolution increasing with increasing temperature, pressure and acetic acid concentrations. During the shallow burial diagenesis of the Paleogene sediment sequence in the Jiyang Depression, aragonite was relatively stable and was not dissolved by the connate pore water in the shales. Increasing burial (temperature) and maturity of the organic matter produced large amounts of organic acids that accelerated the dissolution of aragonite. In the late stage, as the organic matter became over-matured, the pore water changed from acidic to alkaline, and calcite precipitated from the carbonate-rich solution. Therefore, the conditions provided by organic acids enabled the conversion of aragonite to calcite during sedimentary diagenesis in the Paleogene lacustrine shales in the Jiyang Depression. This transformation corresponded to the thermal evolution of the organic matter within the shale sequence.     

The impact of solution chemistry on Mytilus edulis calcite and aragonite

Magnesium/calcium, Sr/Ca, and Na/Ca atom ratios were determined in the calcite and aragonite regions of Mytilus edulis shells which were grown in semi-artificial ‘seawater’ solutions having varying Mg/Ca, Sr/Ca, and Na/Ca ratios. These ratios were measured by instrumental neutron activation, atomic absorption, and electron microprobe analytical techniques. Strontium/calcium ratios in both calcite and aragonite were linearly proportional to solution Sr/Ca ratios. Magnesium/calcium ratios in calcite increased exponentially when solution Mg/Ca ratios were raised above the normal seawater ratio; whereas in aragonite, Mg/Ca ratios increased linearly with increases in solution Mg/Ca ratios. Sodium/calcium and sulfur/calcium ratios in calcite covaried with Mg/Ga solution ratios. Conversely, in aragonite, Na/Ca ratios varied linearly with solution Na/Ca ratios.Magnesium is known to inhibit calcite precipitation at its normal seawater concentration. We infer from the results of the work reported here that Mytilus edulis controls the Mg activity of the outer extrapallial fluid, thus facilitating the precipitation of calcitic shell. Increases in sulfur content suggest that changes in shell organic matrix content occur as a result of environmental stress. Certain increases in Mg content may also be correlated to stress. Sodium/calcium variations, and their absolute amounts in calcite and aragonite, are best explained by assuming that a substantial amount of Na is adsorbed on the calcium carbonate crystal surface. Strontium/calcium ratios show more promise than either Mg/Ca or Na/Ca ratios as seawater paleochemistry indicators, because the Sr/Ca distribution coefficients for both aragonite and calcite are independent of seawater Ca and Sr concentrations.     

Boron isotope systematics in large rivers: implications for the marine boron budget and paleo-pH reconstruction over the Cenozoic

The chemical composition of the oceans and long-term climate changes are believed to be linked. Reconstruction of seawater pH evolution is desirable as pH may be related to atmospheric pCO₂, and hence to climate evolution. Boron isotopes in oceanic carbonates have been suggested to be a proxy for oceanic paleo-pH reconstruction. Nevertheless, the calculation of paleo-pH values over geological periods requires a precise knowledge of the boron isotopic composition of the oceans when calcite precipitated. We present the systematics of boron isotopic composition of the world's main rivers. We deduce a continental boron flux to the oceans of 38×10¹⁰ gB/year with a mean isotopic composition of +10‰. These results lead to a balanced boron budget in the oceans and allow the development of a model for the marine boron secular evolution over the past 100 Myr. It is shown that the oceanic boron cycle is mainly controlled by the boron continental discharge and the boron uptake from the oceans during low temperature alteration of oceanic crust. However, the recent important increase of the clastic sediment supply, linked to the Himalayan erosion, impacts the oceanic boron budget by enhancing significantly the boron uptake by adsorption on sediments. We predict a boron isotopic composition in the oceans lower during the Cenozoic and slightly higher during the Cretaceous than today. The modelled values for the marine boron isotopes follow the variations of boron isotopes in carbonates over the Cenozoic era provided by previous studies, suggesting that the variations of the seawater pH may not have been important on this time scale. If this is the case, it involves that buffering mechanisms occur in the oceans to maintain seawater pH at a roughly constant value against past atmospheric pCO₂ variations.     

Influence of lysozyme on the precipitation of calcium carbonate: a kinetic and morphologic study

Several mechanisms have been proposed to explain the interactions between proteins and mineral surfaces, among them a combination of electrostatic, stereochemical interactions and molecular recognition between the protein and the crystal surface. To identify the mechanisms of interaction in the lysozyme-calcium carbonate model system, the effect of this protein on the precipitation kinetics and morphology of calcite crystals was examined. The solution chemistry and morphology of the solid were monitored over time in a set of time-series free-drift experiments in which CaCO₃ was precipitated from solution in a closed system at 25°C and 1 atm total pressure, in the presence and absence of lysozyme. The precipitation of calcite was preceded by the precipitation of a metastable phase that later dissolved and gave rise to calcite as the sole phase. With increasing lysozyme concentration, the nucleation of both the metastable phase and calcite occurred at lower Ω_calcite, indicating that lysozyme favored the nucleation of both phases. Calcite growth rate was not affected by the presence of lysozyme, at least at protein concentrations ranging from 0 mg/mL to 10 mg/mL.Lysozyme modified the habit of calcite crystals. The degree of habit modification changed with protein concentration. At lower concentrations of lysozyme, the typical rhombohedral habit of calcite crystals was modified by the expression of {110} faces, which resulted from the preferential adsorption of protein on these faces. With increasing lysozyme concentration, the growth of {110}, {100}, and finally {001} faces was sequentially inhibited. This adsorption sequence may be explained by an electrostatic interaction between lysozyme and calcite, in which the inhibition of the growth of {110}, {100}, and {001} faces could be explained by a combined effect of the density of carbonate groups in the calcite face and the specific orientation (perpendicular) of these carbonate groups with respect to the calcite surface. Overgrowth of calcite in the presence of lysozyme demonstrated that the protein favored and controlled the nucleation on the calcite substrate. Overgrowth crystals nucleated epitaxially in lines which run diagonal to rhombohedral {104} faces.     

The energetics of nanophase calcite

Calcium carbonate (CaCO₃) is an important component of the near-surface environment. Understanding the nature of its precipitation is important for a variety of environmental processes, as well as for the geologic sequestration of anthropogenic carbon dioxide. Calcite is the most thermodynamically stable bulk polymorph, but energy crossovers may exist that could favor the precipitation of vaterite or aragonite with decreasing particle size. The purpose of this study is to determine the surface energy of calcite, which is the first step towards understanding the effect of particle size on thermodynamic stability in the calcium carbonate system. The enthalpies of five well-characterized calcite samples (four nanophase and one bulk) were measured by acid solution isothermal and water adsorption calorimetric techniques. From the calorimetric data, the surface energies of calcite were determined to be 1.48 ± 0.21 and 1.87 ± 0.16 J/m² for hydrous and anhydrous surfaces. These values are similar to those measured for many oxides but larger than predicted from computational models for idealized calcite surfaces. The surfaces of synthetic CaCO₃ particles contain a range of planes and defect structures, which may give rise to the difference between the experimental and modeled values.     

TEMPERATURE EFFECT ON PRECIPITATION OF CALCIUM CARBONATE FROM CALCIUM BICARBONATE SOLUTIONS AND ITS APPLICATION TO CAVERN ENVIRONMENTS

Solutions of calcium bicarbonate were allowed to lose carbon dioxide and evaporate to dryness under controlled temperature conditions. With filtered solutions prepared from spar calcite, precipitates were 100% calcite in the 2° to 100°C temperature range. When, in analogous experiments, coralline aragonite was the starting material, the precipitates were 100% calcite. Essentially the same was true when carbonate rocks from karst areas were used to prepare the experimental solutions. An artificially prepared mixture (maximum crystal size of about 7 u) of 70% aragonite and 30% calcite was also used in the study. The precipitates from this starting material were apparently affected by seed nuclei which passed through the filter. The stability of calcium carbonate seed nuclei appears to vary with temperature. Natural calcium bicarbonate solutions from caves yielded only calcite at 25°C. Calcite should be the dominant or only polymorph of CaCO₃ formed by the loss of carbon dioxide and evaporation of natural calcium bicarbonate solutions if temperature is the controlling factor. Since appreciable amounts of aragonite are found in many cave deposits, factors other than temperature must influence the polymorphs formed. POBEGUIN (1955) proposed that rapid evaporation and slow diffusion of solutions favor aragonite. If so, layers of aragonite and calcite in speleothems may reprsent alternate wet and dry paleoclimates. During these periods, rate of introduction of solution and rate of evaporation would change markedly.