Interaction between dissolved silica and calcium carbonate: 1. Spontaneous precipitation of calcium carbonate in the presence of dissolved silica

The kinetics of spontaneous precipitation of CaCO₃ from aqueous solution in the presence of dissolved silica was investigated by recording pH as a function of time. The presence of dissolved silica, at concentrations below saturation with respect to the amorphous phase, decreases induction time for CaCO₃ nucleation, but does not affect CaCO₃ polymorphism. For a “pure” system without silica, the surface free energy, σ, determined from classical nucleation theory is 42 mJ m⁻². This agrees well with values reported in the literature for vaterite and indicates some degree of heterogeneous nucleation, which can occur because of the relatively low degree of supersaturation used for the experiments. In the presence of 1 and 2 mM silica, σ is 37 and 34 mJ m⁻², indicating an increasing degree of heterogeneous nucleation as the amount of polymeric silica increases. The ratio of Ca²⁺ to CO₃²⁻ activity was a governing parameter for determining which CaCO₃ polymorph precipitated. At high Ca²⁺ to CO₃²⁻ activity ratios, almost all initial solid was vaterite, whereas at low ratios, a mixture of vaterite and calcite was observed. In solutions with low Ca²⁺ to CO₃²⁻ activity ratios, the presence of silica at concentrations above saturation with respect to amorphous silica led to formation of only calcite and strongly influenced the crystalline structure and morphology of the precipitates. At high Ca²⁺ to CO₃²⁻ ratios, system behaviour did not differ from that without silica.     

Microbe–mineral interactions: early carbonate precipitation in a hypersaline lake (Eleuthera Island, Bahamas)

Microbialites (benthic microbial carbonate deposits) were discovered in a hypersaline alkaline lake on Eleuthera Island (Bahamas). From the edge towards the centre of the lake, four main zones of precipitation could be distinguished: (1) millimetre‐sized clumps of Mg‐calcite on a thin microbial mat; (2) thicker and continuous carbonate crusts with columnar morphologies; (3) isolated patches of carbonate crust separated by a dark non‐calcified gelatinous mat; and (4) a dark microbial mat without precipitation. In thin section, the precipitate displayed a micropeloidal structure characterized by micritic micropeloids (strong autofluorescence) surrounded by microspar and spar cement (no fluorescence). Observations using scanning electron microscopy (SEM) equipped with a cryotransfer system indicate that micrite nucleation is initiated within a polymer biofilm that embeds microbial communities. These extracellular polymeric substances (EPS) are progressively replaced with high‐Mg calcite. Discontinuous EPS calcification generates a micropeloidal structure of the micrite, possibly resulting from the presence of clusters of coccoid or remnants of filamentous bacteria. At high magnification, the microstructure of the initial precipitate consists of 200–500 nm spheres. No precipitation is observed in or on the sheaths of cyanobacteria, and only a negligible amount of precipitation is directly associated with the well‐organized and active filamentous cyanobacteria (in deeper layers of the mat), indicating that carbonate precipitation is not associated with CO₂ uptake during photosynthesis. Instead, the precipitation occurs at the uppermost layer of the mat, which is composed of EPS, empty filamentous bacteria and coccoids (Gloeocapsa spp.). Two‐dimensional mapping of sulphate reduction shows high activity in close association with the carbonate precipitate at the top of the microbial mat. In combination, these findings suggest that net precipitation of calcium carbonate results from a temporal and spatial decoupling of the various microbial metabolic processes responsible for CaCO₃ precipitation and dissolution. Theoretically, partial degradation of EPS by aerobic heterotrophs or UV fuels sulphate‐reducing activity, which increases alkalinity in microdomains, inducing CaCO₃ precipitation. This degradation could also be responsible for EPS decarboxylation, which eliminates Ca²⁺‐binding capacity of the EPS and releases Ca²⁺ ions that were originally bound by carboxyl groups. At the end of these processes, the EPS biofilm is calcified and exhibits a micritic micropeloidal structure. The EPS‐free precipitate subsequently serves as a substrate for physico‐chemical precipitation of spar cement from the alkaline water of the lake. The micropeloidal structure has an intimate mixture of micrite and microspar comparable to microstructures of some fossil microbialites.     

Effects of freshwater Synechococcus sp. cyanobacteria pH buffering on CaCO3 precipitation: Implications for CO2 sequestration

In the present study, a mixed-flow steady-state bio-reactor was designed to biomineralize CO₂ as a consequence of photosynthesis from active Synechococcus sp. Dissolved CO₂, generated by constant air bubbling of inorganic and cyanobacteria stock solutions, was the only source of inorganic carbon. The release of hydroxide ion by cyanobacteria from photosynthesis maintained highly alkaline pH conditions. In the presence of Ca²⁺ and carbonate species, this led to calcite supersaturation under steady state conditions. Ca²⁺ remained constant throughout the experiments showing the presence of steady state conditions. Similarly, the Synechococcus sp. biomass concentration remained stable within uncertainty. A gradual pH decrease was observed for the highest Ca²⁺ condition coinciding with the formation of CaCO₃. The high degree of supersaturation, under steady-state conditions, contributed to the stabilization of calcite and maintained a constant driving force for the mineral nucleation and growth. For the highest Ca²⁺ condition a fast crystal growth rate was consistent with rapid calcite precipitation as suggested further by affinity calculations. Although saturation state based kinetic precipitation models cannot accurately reflect the controls on crystal growth kinetics or reliably predict growth mechanisms, the relatively reaction orders obtained from modeling of calcite precipitation rates as function of decreasing carbonate concentration suggest that the precipitation occurred via surface-controlled rate determining reactions. These high reaction orders support in addition the hypothesis that crystal growth proceeded through complex surface controlled mechanisms. In conclusion, the steady state supersaturated conditions generated by a constant cyanobacteria biomass and metabolic activity strongly suggest that these microorganisms could be used for the development of efficient CO₂ sequestration methods in a controlled large-scale environment.     

The kinetics of calcite precipitation from a high salinity water

Calcium carbonate is one of the most common and important scale-forming minerals in oilfield produced water, but the kinetics of CaCO₃ precipitation has been ignored in most scale prediction models because of the lack of reliable precipitation rate model. There are none in the open literature for oilfield conditions (temperature > 100°C, pressure > 200 bar and salinity > 0.5 mol kg− 1). In this work the kinetics of calcite (CaCO₃) precipitation from high salinity waters (up to 2 mol kg⁻¹) have been studied by a pH-free-drift method in a closed water system. This method. is much easier to operate than the often used steady-state method. The experimental results indicate that the calcite precipitation rate is not only affected by the solution CaCO₃ saturation level, but also by the solution pH, ionic strength and the concentration ratios of Ca to HCO₃₋ ions (C_Ca²⁺/C_HCO3⁻). When the concentration ratios of Ca to HCO₃⁻ ions are close to their chemical stoichiometric ratio of 0.5, the calcite growth from a supersaturated solution is believed to be surface reaction controlled. However, at higher C_Ca²⁺C_HCO3⁻ ratios, the transportation of the lattice ions to calcite crystal surface has to be considered.     

Influence of microbial photosynthesis on tufa stromatolite formation and ambient water chemistry, SW Japan

Photosynthetic influences on tufa stromatolite formation and ambient water chemistry were investigated at two well-studied streams depositing tufa in Southwestern Japan (Shirokawa and Shimokuraida). The tufa stromatolites in both streams are composed of fine-grained calcite crystals showing annual lamination, and colonized by a number of filamentous cyanobacteria as well as non-phototrophic bacteria. Microelectrode measurements of pH, O₂, and Ca²⁺ near the stromatolite surface (the diffusive boundary layer; DBL) revealed that the investigated tufa stromatolites are formed by photosynthesis-induced CaCO₃ precipitation (PCP): cyanobacterial photosynthesis induces calcite precipitation under light conditions, while respiration of cyanobacteria and non-phototrophic bacteria inhibits precipitation in the dark. The bulk water chemistry at the lower sites of the investigated streams showed the daytime decreases of Ca²⁺ concentration and alkalinity that was expected for significant influence of PCP, while the other expected change, increased pH, was not observed. In order to examine this discrepancy, a novel approach using semi-in situ microelectrode measurements was applied to perform precise quantitative calculations. The calculation results demonstrated that the observed Ca²⁺ concentration and alkalinity decreases were caused by PCP, and that the concomitant pH increase was expected to be under the detection level of a conventional pH meter. Although the amount of PCP is supposed to be significantly affected by light intensity, observations in Shimokuraida revealed that the amount of PCP on cloudy day nonetheless accounted for about 80% of that on sunny day. Despite the significant role of PCP for tufa stromatolite formation, PCP accounted for only about 10% of the precipitated calcite in the investigated streams, which indicates that tufa stromatolites, the characteristic deposits in the streams, are responsible for only a small portion of calcite precipitation, and the rest is considered to precipitate inorganically at biofilm-free substrates.     

Microscopic calcite dendrites in cold-water tufa: implications for nucleation of micrite and cement

Dendritic calcite forms in an active cold-water tufa system in association with extracellular polymeric substances (EPS) that discontinuously coat bryophytes and cyanobacteria. Dendrites consist of 100–200 nm thick calcite fibres that form 3D lattice-like domains. In each dendrite domain, fibres have three structurally equal orientations, which correspond in disposition to radii from the centre of a calcite unit cell to the convex triple face junctions on its surface. Fibres do not form in the orientation of the c-axis. The external form of each dendrite has the shape of half of a shortened octahedron, with an upper triangular surface parallel to the substrate. Dendrite nucleation takes place on or in microbial EPS, whether microbial cells are present or not, and is probably effected by attraction of Ca²⁺ cations to negatively charged EPS, together with CO₂-degassing and concomitant pH increase of supersaturated spring water in stream splash zones. Ensuing dendrite growth is abiogenic and controlled by diffusion. Dendrite c-axes are perpendicular to the substrate, probably because the negative charge of EPS forces the orientation of Ca²⁺ and CO planes within the developing dendrite crystal to be parallel to the EPS film surface. Dendrites are eventually filled and overgrown by solid, syntaxial calcite, which gradually and completely obliterates the dendrites as more familiar calcite crystal forms develop. No trace of the dendritic nucleus remains in the rock record. Calcite crystal nucleation may take place by this mechanism in many marine and meteoric settings, given that microbial EPS is now assumed to be virtually ubiquitous in these environments. This phenomenon could contribute to the development of familiar fabrics such as marine micrite cement and fibrous calcite cement, radial ooids, peloids, ‘abiogenic’ stromatolites, sea floor precipitates, microbialites, tufa, travertine, speleothems, and some meteoric cements. It may also contribute to the substrate-normal orientation of c-axes of common cement fabrics.     

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).     

Kinetics of calcite precipitation induced by ureolytic bacteria at 10 to 20°C in artificial groundwater

The kinetics of calcite precipitation induced in response to the hydrolysis of urea by Bacillus pasteurii at different temperatures in artificial groundwater (AGW) was investigated. The hydrolysis of urea by B. pasteurii exhibited a temperature dependence with first order rate constants of 0.91 d⁻¹ at 20°C, 0.18 d⁻¹ at 15°C, and 0.09 d⁻¹ at 10°C. At all temperatures, the pH of the AGW increased from 6.5 to 9.3 in less than 1 d. Dissolved Ca²⁺ concentrations decreased in an asymptotic fashion after 1 d at 20°C and 15°C, and 2 d at 10°C. The loss of Ca²⁺ from solution was accompanied by the development of solid phase precipitates that were identified as calcite by X-ray diffraction. The onset of calcite precipitation at each temperature occurred after similar amounts of urea were hydrolyzed, corresponding to 8.0 mM NH₄⁺. Specific rate constants for calcite precipitation and critical saturation state were derived from time course data following a second-order chemical affinity-based rate law. The calcite precipitation rate constants and critical saturation states varied by less than 10% between the temperatures with mean values of 0.16 ± 0.01 μmoles L⁻¹ d⁻¹ and 73 ±3, respectively. The highest calcite precipitation rates (ca. 0.8 mmol L⁻¹ d⁻¹) occurred near the point of critical saturation. While unique time course trajectories of dissolved Ca²⁺ concentrations and saturation state values were observed at different temperatures, calcite precipitation rates all followed the same asymptotic profile decreasing with saturation state regardless of temperature. This emphasizes the fundamental kinetic dependence of calcite precipitation on saturation state, which connects the otherwise dissimilar temporal patterns of calcite precipitation that evolved under the different temperature and biogeochemical regimes of the experiments.     

Estimation of dolomite formation: Dolomite precipitation and dolomitization

Reactive-transport models are developed here that produce dolomite via two scenarios: primary dolomite (no CaCO₃ dissolution involved) versus secondary dolomite (dolomitization, involving CaCO₃ dissolution). Using the available dolomite precipitation rate kinetics, calculations suggest that tens of meters of thick dolomite deposits cannot form at near room temperature (25-35°C) by inorganic precipitation mechanism, though this mechanism will provide dolomite aggregates that can act as the nuclei for dolomite crystallization during later dolomitization stage. Increase in supersaturation, Mg⁺²/Ca⁺² ratio and CO₃^-2 on the formation of dolomite at near room temperature are subtle except for temperature.This study suggests that microbial mediation is needed for appreciable amount of primary dolomite formation. On the other hand, reactive-transport models depicting dolomitization (temperature range of 40 to 200°C) predicts the formation of two adjacent moving coupled reaction zones (calcite dissolution and dolomite precipitation) with sharp dolomitization front, and generation of >20% of secondary porosity. Due to elevated temperature of formation, dolomitization mechanism is efficient in converting existing calcite into dolomite at a much faster rate compared to primary dolomite formation.     

The effects of Mg and H on apatite nucleation at silica surfaces

Apatite (Ca₁₀[PO₄]₆[OH]₂) precipitation from aqueous solutions involves multiple steps, such as nucleation of a precursor calcium phosphate phase, cluster aggregation, crystal growth, and transformation to apatite, which are affected by the presence of other ions in solution. I report the mechanisms by which two ions common in natural solutions, Mg²⁺ and H⁺, affect heterogeneous calcium phosphate nucleation on the amorphous silica surface.     

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

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

The formation and transformation mechanism of calcium carbonate in water

Highly supersaturated solutions of Ca²⁺ and CO²⁻₃ ions rapidly precipitate amorphous calcium carbonate, ACC, the logarithmic thermodynamic solubility product of which is about −6.0 at 25°C. The ACC initially formed is transformed to a mixture of several crystalline calcium carbonate polymorphs within several minutes. The transformed polymorphs are vaterite and calcite at low temperature (14 to 30°C), and aragonite and calcite at high temperature (60 to 80°C). At intermediate temperatures (40 to 50°C) the formation of all three polymorphs was observed. Metastable polymorphs are gradually transformed to the stable form, calcite. It takes about 200 min at 25°C and 370 min at 30°C for the complete transformation of vaterite to calcite, and 1000–1300 min for that of aragonite to calcite at 60–80°C. At 50°C, vaterite is predominantly transformed at first to aragonite within 60 min, and then the aragonite is transformed to calcite in about 900 min. The results of the change in the ion activity product of the solution and the abundances of the polymorphs strongly suggest that the polymorphic transformation of vaterite and aragonite to calcite takes place through dissolution of the metastable phase and growth of the stable phase, calcite. The rate-determining step of the transformation is the growth of calcite. The relative abundance of vaterite becomes higher at 25°C with increasing concentrations of calcium and carbonate ions in the supersaturated solution. When the ion activity product of the initial supersaturated solution is lower than the solubility product of ACC at 25°C, only vaterite directly precipitates after some induction period. The vaterite crystals formed are free of calcite seeds and the vaterite saturated solutions are stable for several days.     

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.     

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

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.     

Adsorption and Desorption of Phosphate on Calcite and Aragonite in Seawater

The adsorption and desorption of phosphate on calcite and aragonite were investigated as a function of temperature (5–45 °C)and salinity (0–40) in seawater pre-equilibrated with CaCO₃. An increase in temperature increased the equilibrium adsorption; whereas an increase in salinity decreased the adsorption. Adsorption measurements made in NaCl were lower than the results in seawater. The higher values in seawater were due to the presence of Mg²⁺ and Ca²⁺ ions. The increase was 5 times greater for Ca²⁺ than Mg²⁺. The effects ofCa²⁺ and Mg²⁺ are diminished with the addition of SO₄ ^2- apparently due to the formation of MgSO₄ and CaSO₄ complexes in solution and/or SO₄ ^2- adsorption on the surface of CaCO₃. The adsorbed Ca²⁺ and Mg²⁺ on CaCO₃ (at carbonate sites) may act as bridges to PO₄ ^3- ions. The bridging effect of Ca²⁺is greater than Mg²⁺ apparently due to the stronger interactions of Ca²⁺ with PO₄ ^3-.The apparent effect of salinity on the adsorption of PO₄ was largely due to changes in the concentration of HCO₃ ^- in the solutions. An increase in the concentration of HCO₃ ^- caused the adsorption of phosphate to decrease, especially at low salinities. The adsorption at the same level of HCO₃ ^- (2 mM) was nearly independent of salinity. All of the adsorption measurements were modeled empirically using a Langmuir-type adsorption isotherm[ [PO₄]_ad = K_mC_m[PO₄]_T/(1 +K_m [PO₄]_T) , ]where [PO₄]_ad and [PO₄]_T are the adsorbed and total dissolved phosphate concentrations, respectively. The values of C_m (the maximum monolayer adsorption capacity, (mol/g) and K_m (the adsorption equilibrium constant, g/(mol) over the entire temperature (t, °C) and salinity (S) range were fitted to[ C_m = 17.067 + 0.1707t - 0.4693S + 0.0082S² ( = 0.7) ][ ln K_m = - 2.412 + 0.0165t - 0.0004St - 0.0008S² ( = 0.1) ]These empirical equations reproduce all of our measurements of[PO₄]_ad up to 14 mol/g and within ±0.7 mol/g.The kinetic data showed that the phosphate uptake on carbonate minerals appears to be a multi-step process. Both the adsorption and desorption were quite fast in the first stage (less than 30 min) followed by a much slower process (lasting more than 1 week). Our results indicate that within 24 hours aragonite has a higher sorption capacity than calcite. The differences between calcite and aragonite become smaller with time. Consequently, the mineral composition of the sediments may affect the short-term phosphate adsorption and desorption on calcium carbonate. Up to 80 % of the adsorbed phosphate is released from calcium carbonate over one day. The amount of PO₄ left on the CaCO₃ is close to the equilibrium adsorption. The release of PO₄ from calcite is faster than from aragonite. Measurements with Florida Bay sediments produced results between those for calcite and aragonite. Our results indicate that the calcium carbonate can be both a sink and source of phosphate in natural waters.     

The coprecipitation of Sr2+ with calcite at 25°C and 1 atm

The incorporation of Sr²⁺ into calcite at earth surface aqueous conditions is affected by the absolute concentration of Sr²⁺, the presence of Ba²⁺ and NaCl in the solution, and the rate of precipitation. At solution ratios (molar) of Sr²⁺ to Ca²⁺ in the low 10⁻³ range, which yield calcites with several hundred ppm Sr²⁺, K^sr_calcite typically assumes a value between 0.10 and 0.20. Above these concentrations the value of k^Sr_calcite drops to approximately 0.06. Furthermore, if minor amounts of Ba²⁺ or large amounts of Na⁺ (0.48 M) are added to a dilute Sr²⁺ solution, a value around 0.06 for k^Sr_calciteis found. This “strontium concentration effect” and the associated “competitive cation effect” suggest that small amounts of Sr²⁺ may be incorporated into a limited number of nonlattice sites in calcite. Incorporation of Sr²⁺ into these sites, presumably defects, noticeably affects k^Sr_calcite only at low Sr²⁺ concentrations and in the absence of competition from other large cations.An increase in k^Sr_calcite with rate of precipitation, qualitatively similar to that found in other studies, was observed only when precipitation times were decreased from days to hours.For many geologic settings a partition coefficient for Sr²⁺ into calcite of 0.06 appears appropriate, but there are situations—very low Sr²⁺ concentrations, the presence of Mg²⁺, and fast precipitation rates—in which a larger value might better approximate natural partitioning.     

The coprecipitation of Sr into calcite precipitates induced by bacterial ureolysis in artificial groundwater: Temperature and kinetic dependence

A suite of experiments was performed to investigate the partitioning of Sr²⁺ (to mimic the radionuclide ⁹⁰Sr) between calcite and artificial groundwater in response to the hydrolysis of urea (ureolysis) by Bacillus pasteurii under simulated in situ aquifer conditions. Experiments were performed at 10, 15, and 20°C over 7 days in microcosms inoculated with B. pasteurii ATCC 11859, containing an artificial groundwater and urea (AGW) or an AGW including a Sr contaminant treatment. During the experiments, the concentration of ammonium generated by bacterial ureolysis increased asymptotically, and derived rate constants (k_urea) that were between 13 and 10 times greater at 20°C than at 15 and 10°C. Calcite precipitation was initiated after similar amounts of urea had been hydrolyzed (∼ 4.0 mmol L^-1) and a similar critical saturation state (mean S_critical = 53, variation = 20%) had been reached, independent of temperature and Sr treatment. Because of the positive relationship between the rate of ureolysis and temperature, precipitation began by the end of day 1 at 20°C, and between days 1 and 2 at 15 and 10°C. The rate of calcite precipitation increased with, and was fundamentally controlled by calcite saturation state (S), irrespective of temperature. The presence of Sr slightly slowed calcite precipitation rates at equivalent values of S, which may reflect the screening of active nucleation and crystal growth sites by Sr. Homogeneous partitioning coefficients (D_Sr) exhibited a positive association with calcite precipitation rates, but were greater at higher experimental temperatures at equivalent precipitation rates (20°C mean = 0.46; 15°C mean = 0.24; 10°C mean = 0.29).     

Pressure effect on magnesian calcite coating calcite and synthetic magnesian calcite seeds added to seawater in a closed system

When pure crystalline calcite seeds are added to supersaturated seawater, precipitation results in a coating which with time equilibrates at atmospheric pressure with seawater and corresponds to a calcite containing probably only 2 or 3% of MgCO₃ (mole fraction).If synthetic crystalline magnesian calcite is added, the surface layer equilibrates not only with respect to seawater but also in relation with the crystalline sites initiating precipitation. Adding Mg_0.03Ca_0.97CO₃ results in a coating with a solubility close to that of calcite. This confirms that the surface coating on pure calcite seeds contains about 2 or 3% MgCO₃ (K'_sp = 10?6.30).The surface layer precipitated on a synthetic Mg_0.08Ca_0.92CO₃ equilibrates finally with a carbonate more soluble than calcite (K'_sp = 10?5.94) corresponding to the seeds composition.Experiments at 1000 kg cm t-2 imply that when magnesian calcites are precipitated at the surface of calcite or magnesian calcite seeds, the precipitate must be hydrated, otherwise pressure accelerated recrystallization or rearrangement with loss of Mg would thermodynamically be impossible.By changing the pressure of a seawater sample originally saturated with a solid carbonate phase, changes in pH result from the effect of pressure on the dissociation constants of carbonic acid and boric acid causing either undersaturation or supersaturation with respect to the solid. By changing pressure we can show whether precipitation, dissolution and recrystallization are reversible processes if pH is taken as criteria of reversibility.     

Kinetics of gypsum nucleation and crystal growth from Dead Sea brine

The Dead Sea brine is supersaturated with respect to gypsum (Ω = 1.42). Laboratory experiments and evaluation of historical data show that gypsum nucleation and crystal growth kinetics from Dead Sea brine are both slower in comparison with solutions at a similar degree of supersaturation. The slow kinetics of gypsum precipitation in the Dead Sea brine is mainly attributed to the low solubility of gypsum which is due to the high Ca²⁺/SO₄²⁻ molar ratio (115), high salinity (∼280 g/kg) and to Na⁺ inhibition.Experiments with various clay minerals (montmorillonite, kaolinite) indicate that these minerals do not serve as crystallization seeds. In contrast, calcite and aragonite which contain traces of gypsum impurities do prompt precipitation of gypsum but at a considerable slower rate than with pure gypsum. This implies that transportation inflow of clay minerals, calcite and local crystallization of minerals in the Dead Sea does not prompt significant heterogeneous precipitation of gypsum. Based on historical analyses of the Dead Sea, it is shown that over the last decades, as inflows to the lake decreased and its salinity increased, gypsum continuously precipitated from the brine. The increasing salinity and Ca²⁺/SO₄²⁻ ratio, which results from the precipitation of gypsum, lead to even slower kinetics of nucleation and crystal growth, which resulted in an increasing degree of supersaturation with respect to gypsum. Therefore, we predict that as the salinity of the Dead Sea brine continues to increase (accompanied by Dead Sea water level decline), although gypsum will continuously precipitate, the degree of supersaturation will increase furthermore due to progressively slower kinetics.     

Effects of seed material and solution composition on calcite precipitation

We studied the effects of seed material and solution composition on calcite crystal precipitation using a pH-stat system. The seed materials investigated included quartz, dolomite, two calcites with different particle size and specific surface area, and two dried precipitates from precipitative softening water treatment plants. Our results indicated that, of the seed materials examined, only calcite had the ability to initiate calcite precipitation in a solution with a degree of supersaturation of 5.3 over a period of two hours, and that the precipitation rate was proportional to the available surface area of the seed. For different solution compositions with the same degree of supersaturation, the calcite precipitation rate increased with increasing carbonate/calcium ratio, which contradicts the generally accepted empirical rate expression that the degree of supersaturation is the sole factor controlling precipitation kinetics. By applying a surface complexation model, the surface concentrations of two species, >CO₃⁻ and >CaCO₃⁻, appear to be responsible for catalyzing calcite precipitation.