Solubility Of Aragonite Research Articles

Constraining CaCO3 Export and Dissolution With an Ocean Alkalinity Inverse Model

AbstractOcean alkalinity plays a fundamental role in the apportionment of CO2 between the atmosphere and the ocean. The primary driver of the ocean's vertical alkalinity distribution is the formation of calcium carbonate (CaCO3) by organisms at the ocean surface and its dissolution at depth. This so‐called “CaCO3 counterpump” is poorly constrained, however, both in terms of how much CaCO3 is exported from the surface ocean, and at what depth it dissolves. Here, we created a steady‐state model of global ocean alkalinity using Ocean Circulation Inverse Model transport, biogeochemical cycling, and field‐tested calcite and aragonite dissolution kinetics. We find that limiting CaCO3 dissolution to below the aragonite and calcite saturation horizons cannot explain excess alkalinity in the upper ocean, and that models allowing dissolution above the saturation horizons best match observations. Linking dissolution to organic matter respiration, or imposing a constant dissolution rate both produce good model fits. Our best performing models require export between 1.1 and 1.8 Gt PIC y−1 (from 73 m), but all converge to 1.0 Gt PIC y−1 export at 279 m, indicating that both high‐ and low‐export scenarios can match observations, as long as high export is coupled to high dissolution in the upper ocean. These results demonstrate that dissolution is not a simple function of seawater CaCO3 saturation (Ω) and calcite or aragonite solubility, and that other mechanisms, likely related to the biology and ecology of calcifiers, must drive significant dissolution throughout the water column.

Formation of $${\text {CaCO}}_3$$ varieties from a carbonated aqueous solution

Experimental studies have been conducted to clarify the paragenetic conditions of CaCO3 varieties, calcite and aragonite formed from the same wall rock. In addition, the solubility dependence of calcite, aragonite, and limestone formed from limestone cave in CO2 -saturated solutions was compared with the previous studies. First, the calcite and aragonite were powdered to below 200 meshes. In addition, the powders were, respectively, added into the CO2 -saturated distilled water at 8, 13, 18, and 22∘C and were kept constant for 15 days. The amount of dissolved CaCO3 was then measured. The solubility of aragonite was higher than that of calcite, and the solubility decreased exponentially with increasing temperature. Simultaneous production and growth of calcite and aragonite proceeded only when the saturation of aragonite was reached in aqueous carbonate solution. Conversely, when the dissolved amount of CaCO3 has not been reached, calcite is only formed and grown. In these solutions, aragonite crystals dissolve and calcite crystals grow. The degree of saturation of aragonite can be reached by rapid evaporation of solvent, CO2 gas degassing, and the presence of Mg. However, paragenesis of calcite and aragonite in natural caves can be explained by rapid evaporation of the solvent. A rapid evaporation of the solvent may occur at a place, where a small amount of karst solution flows and a large amount of air flows. In such places, paragenesis of calcite and aragonite is possible.

Calcium and strontium isotope fractionation during precipitation from aqueous solutions as a function of temperature and reaction rate; II. Aragonite

In order to study Strontium (Sr) partitioning and isotope fractionation of Sr and Calcium (Ca) in aragonite we performed precipitation experiments decoupling temperature and precipitation rates (R∗, μmol/m2h) in the interval of about 2.3–4.5μmol/m2h. Aragonite is the only pure solid phase precipitated from a stirred solutions exposed to an atmosphere of NH3 and CO2 gases throughout the spontaneous decomposition of (NH4)2CO3. The order of reaction with respect to Ca ions is one and independent of temperature. However, the order of reaction with respect to the dissolved inorganic carbon (DIC) is temperature dependent and decreases from three via two to one as temperature increases from 12.5 and 25.0 to 37.5°C, respectively. Strontium distribution coefficient (DSr) increases with decreasing temperature. However, R∗ responds differently depending on the initial Sr/Ca concentration and temperature: at 37.5°C DSr increase as a function of increasing R∗ but decrease for 12.5 and 25°C. Not seen at 12.5 and 37.5°C but at 25°C the DSr-R∗ gradient is also changing sign depending on the initial Sr/Ca ratio. Magnesium (Mg) adsorption coefficient between aragonite and aqueous solution (DMg) decreases with temperature but increases with R∗ in the range of 2.4–3.8μmol/m2h. Strontium isotope fractionation (Δ88/86Sraragonite-aq) follows the kinetic type of fractionation and become increasingly negative as a function of R∗ for all temperatures. In contrast Ca isotope fractionation (Δ44/40Caaragonite-aq) shows a different behavior than the Sr isotopes. At low temperatures (12.5 and 25°C) Ca isotope fractionation (Δ44/40Caaragonite-aq) becomes positive as a function of R∗. In contrast, at 37.5°C and as a function of increasing R∗ the Δ44/40Caaragonite-aq show a Sr type like behavior and becomes increasingly negative. Concerning both the discrepant behavior of DSr as a function of temperature as well as for the Ca isotope fractionation as a function of temperature we infer that the switch of sign in the trace element partitioning as well as in the direction of the Ca isotope fractionation is probably due to the switch of complexation from a Ca2+-NH3 complexation at and below 25°C to an Ca2+-H2O aquacomplex at 37.5°C. The DSr–Δ88/86Srcalcite-aq correlation for calcite is independent of temperature in contrast to aragonite. We interpreted the strong DSr-temperature dependency of aragonite, the smaller range of Sr isotope fractionation as well as the shallower Δ88/86Srcalcite-aq–R∗ gradients to be a consequence of the increased aragonite solubility and the “Mg blocking effect”. In contrast to Sr the Ca isotope fractionation values in calcite and aragonite depend both on the complexation in solution and independent on polymorphism.

Hydrochemical controls on aragonite versus calcite precipitation in cave dripwaters

Despite the paleoclimatic relevance of primary calcite to aragonite transitions in stalagmites, the relative role of fluid Mg/Ca ratio, supersaturation and CO32− concentration in controlling such transitions is still incompletely understood. Accordingly, we have monitored the hydrochemistry of 50 drips and 8 pools that are currently precipitating calcite and/or aragonite in El Soplao and Torca Ancha Caves (N. Spain), investigating the mineralogy and geochemistry of the CaCO3 precipitates on the corresponding natural speleothem surfaces. The data reveal that, apart from possible substrate effects, dripwater Mg/Ca is the only obvious control on CaCO3 polymorphism in the studied stalagmites and pools, where calcite- and aragonite-precipitating dripwaters are separated by an initial (i.e. at stalactite tips) Mg/Ca threshold at ≈1.1mol/mol. Within the analyzed ranges of pH (8.2–8.6), CO32− concentration (1–6mg/L), supersaturation (SIaragonite: 0.08–1.08; SIcalcite: 0.23–1.24), drip rate (0.2–81drops/min) and dissolved Zn (6–90μg/L), we observe no unequivocal influence of these parameters on CaCO3 mineralogy. Despite the almost complete overlapping supersaturations of calcite- and aragonite-precipitating waters, the latter are on average less supersaturated because the waters having Mg/Ca above ∼1.1 have mostly achieved such high ratios by previously precipitating calcite. Both calcite and aragonite precipitated at or near oxygen isotopic equilibrium, and Mg incorporation into calcite was consistent with literature-based predictions, indicating that in the studied cases CaCO3 precipitation was not significantly influenced by strong kinetic effects. In the studied cases, the calcites that precipitate at ∼11°C from dripwaters with initial Mg/Ca approaching ∼1.1 incorporate ∼5mol% MgCO3, close to the published value above which calcite solubility exceeds aragonite solubility, suggesting that aragonite precipitation in high-relative-humidity caves is favored from a solubility viewpoint. We also show that unaccounted CaCO3 precipitation in intermediate sampling containers and splash effects may in cases result in underestimating dripwater Ca concentration and alkalinity, potentially leading to incorrect conclusions regarding the role of fluid Mg/Ca ratio and supersaturation on CaCO3 mineralogy. A simple way to elude the first effect is by taking water samples directly from stalactites and by titrating alkalinity in the same containers used to collect dripwaters.

Simulation of the local structure, mixing properties, and stability of Ca x Sr1 − x CO3 solid solutions by the interatomic potential method

Strontianite (SrCO3)-aragonite (CaCO3) solid solutions have been simulated by the interatomic potential method. The composition dependences of the unit cell parameters, the unit cell volume, and bulk modulus have been constructed. It has been shown that the volume of the unit cell and bulk modulus show small negative deviations from additivity. The local structure of solid solutions has been analyzed. It has been established that the enthalpy of mixing is positive and, for the equimolar composition, reaches a maximum of 2.45 kJ/mol. Based on the composition dependences of the Gibbs free energy for the temperature range of 300–650 K, the solvus of the system has been constructed. According to the obtained data, the solubility of aragonite in strontianite under ambient conditions is 5.5 mol %, while that of strontianite in aragonite is 2.8 mol %. The miscibility gap of the system disappears at around 450 K. The calculated results have been compared with the experimental data.

In situ Raman study and thermodynamic model of aqueous carbonate speciation in equilibrium with aragonite under subduction zone conditions

Carbonate minerals may be recycled into the mantle at subduction zones. However, the evolution of carbonate minerals in equilibrium with aqueous fluids as well as the nature of the chemical species of dissolved carbon in the deep crust and mantle at high PT conditions are still unknown. In this study, we report an integrated experimental and theoretical study of the equilibration of CaCO3 minerals with pure water at subduction zone conditions over the pressure and temperature ranges 5–80kbar and 300–400°C. The fluid speciation was studied using in situ Raman spectroscopy. The relative amounts of dissolved carbonate and bicarbonate were estimated from the corrected areas of the Raman bands of the carbonate and bicarbonate ions and used to constrain a theoretical thermodynamic model of the fluid speciation and solubility of aragonite. At 300–400°C, our results indicate that the proportion of dissolved C present as CO2 strongly decreases in fluids in equilibrium with aragonite at P>10kbar. CO2 is replaced by HCO3− and CaHCO3+ which predominate until P>40kbar, where CO32− and CaCO30 become the dominant C-species. At higher temperatures, the theoretical model indicates that CO2 again becomes a major species in fluids in equilibrium with aragonite depending on the pressure.

Quaternary glacial cycles: Karst processes and the global CO2 budget

Extensive research has been conducted investigating the relationship between karst processes, carbonate deposition and the global carbon cycle. However, little work has been done looking into the relationship between glaciations, subsequent sea level changes, and aerially exposed land masses in relation to karstic processes and the global carbon budget. During glaciations sea-level exposed the world’s carbonate platforms. With the sub-aerial exposure of the platforms, karst processes can occur, and the dissolution of carbonate material can commence, resulting in the drawdown of CO2 from the atmosphere as HCO3−. Furthermore, the material on the platform surfaces is primarily aragonite which is more readily soluble than calcite allowing karst processes to occur more quickly. During glaciations arctic carbonates and some of the temperate carbonates are blanketed in ice, effectively removing those areas from karst processes. Given the higher solubility of aragonite, and the extent of carbonate platforms exposed during glaciations, this dissolution balances the CO2 no longer taken up by karst processes at higher latitudes that were covered during the last glacial maximum The balance is within 0.001 GtC / yr, using soil pCO2 (0.005 GtC/yr assuming atmospheric pCO2) which is a difference of <1% of the total amount of atmospheric CO2 removed in a year by karst processes. Denudation was calculated using the maximum potential dissolution formulas of Gombert (2002). On a year to year basis the net amount of atmospheric carbon removed through karstic processes is equivalent between the last glacial maximum and the present day, however, the earth has spent more time in a glacial configuration during the Quaternary, which suggests that there is a net drawdown of atmospheric carbon during glaciations from karst processes, which may serve as a feedback to prolong glacial episodes. This research has significance for understanding the global carbon budget during the Quaternary. Keywords: Karst, Global Carbon Budget, Quaternary, Last Glacial Maximum, Carbonate Dissolution. DOI: 10.3986/ac.v42i2-3.661

Speleothem microstructure/speleothem ontogeny: a review of Western contributions

Mineral ontogeny is the study of the growth and development of mineral deposits in general and, in the present context, speleothems in particular. Previous researchers, mainly in Russia, have developed a nomenclatural hierarchy based on the forms and habits of individual crystals and the assembly of individual crystals into both monomineralic and polymineralic aggregates (i.e. speleothems). Although investigations of the growth processes of speleothems are sparse, there is a large literature on growth processes of speleothem minerals and related crystals in the geochemical and materials science literature. The purpose of the present paper is to sort through the various concepts of crystal growth and attempt to relate these to observations on speleothems and to the Russian conceptual framework of mineral ontogeny. For calcite, the most common mineral in speleothems, the activation energy for two-dimensional nucleation (required for the growth of large single crystals) is almost the same as the activation energy for three-dimensional nucleation (which would result in the growth of many small crystals) Calcite growth is highly sensitive to minor impurities that may poison growth in certain crystallographic directions or may poison growth altogether. Extensive recent research using the atomic force microscope (AFM) provides many details of calcite growth including the transition from growth on screw dislocations to growth by two-dimensional nucleation. The deposition of aragonite speleothems requires additional supersaturation which is usually ascribed to the impurities Mg2+ and Sr2+. AFM studies reveal that Mg2+ poisons calcite growth by blocking deposition sites on dislocations, thus allowing supersaturation to build up past the aragonite solubility curve. Sr2+ precipitates as a Sr-rich nucleus with the aragonite structure which acts as a template for aragonite growth. The different morphology of gypsum speleothems can be explained by the different growth habit of gypsum. Examples of twinned growth, dendrite growth, and spherulitic growth are common in the crystal growth literature and can be used to interpret the corresponding cave forms. Interpretation of monomineralic aggregate growth follows from individual crystal mechanisms. Interpretation of polymineralic aggregate growth requires knowing the evolving chemistry which in turn requires new methods for the sampling and analysis of microliter or nanoliter quantities of fluid.

Saturation states of carbonate minerals in a freshwater-seawater mixing zone of small tropical island’s aquifer

Groundwater is a crucial resource on the Manukan Island as it is the only source of freshwater available on the island. The aquifer has deteriorated to a high degree, during the last decade. Nine domestic wells were sampled from March 2006 to January 2007 to probe the hydrochemical components that influence the water quality. Geochemical data on dissolved major constituents in groundwater samples from the Manukan Island revealed the main processes responsible for their geochemical evolution. The results using statistical analyses, graphical method and numerical model output (PHREEQC) showed that the groundwater was chemically highly enriched in Na and Cl, indicative of seawater intrusion into the aquifer as also supported from the Na-Cl signature on the Piper diagram. From the PHREEQC simulation model, calcite, dolomite and aragonite solubility showed positive values of the saturation indices (SI), indicating supersaturation which led to mineral precipitation condition of water by these minerals.

Naked corals: Skeleton loss in Scleractinia

Stony corals, which form the framework for modern reefs, are classified as Scleractinia (Cnidaria, Anthozoa, and Hexacorallia) in reference to their external aragonitic skeletons. However, persistent notions, collectively known as the "naked coral" hypothesis, hold that the scleractinian skeleton does not define a natural group. Three main lines of evidence have suggested that some stony corals are more closely related to one or more of the soft-bodied hexacorallian groups than they are to other scleractinians: (i) morphological similarities; (ii) lack of phylogenetic resolution in molecular analyses of scleractinians; and (iii) discrepancy between the commencement of a diverse scleractinian fossil record at 240 million years ago (Ma) and a molecule-based origination of at least 300 Ma. No molecular evidence has been able to clearly reveal relationships at the base of a well supported clade composed of scleractinian lineages and the nonskeletonized Corallimorpharia. We present complete mitochondrial genome data that provide strong evidence that one clade of scleractinians is more closely related to Corallimorpharia than it is to a another clade of scleractinians. Thus, the scleractinian skeleton, which we estimate to have originated between 240 and 288 Ma, was likely lost in the ancestry of Corallimorpharia. We estimate that Corallimorpharia originated between 110 and 132 Ma during the late- to mid-Cretaceous, coinciding with high levels of oceanic CO(2), which would have impacted aragonite solubility. Corallimorpharians escaped extinction from aragonite skeletal dissolution, but some modern stony corals may not have such fortunate fates under the pressure of increased anthropogenic CO(2) in the ocean.

Hydrogeochemistry and carbonate saturation model of groundwater, Khanyounis Governorate—Gaza Strip, Palestine

Groundwater is a critical resource in Khanyounis city as it is the main source of water. The aquifer has deteriorated to a high degree, during the last two to three decades, in quality and quantity. More than 90% of the population get their drinking water from brackish water desalination plants. Fifteen domestic wells were sampled in 2002 to probe the hydrogeochemical components that influence the water quality. Na, K, Ca, Mg, Cl, SO4, NO3, and HCO3 were analyzed. The data were statistically treated and plotted on the Piper diagram. A hydrogeochemical numerical model for carbonate minerals was constructed using the PHREEQ package. The results show that the groundwater is polluted with Cl, from seawater, and NO3, sourced from fertilizers and sewage. The regression analysis shows that there are three groups of elements that are significantly and positively correlated. Na–Cl signature and plot show that seawater intrusion is advancing into the aquifer. The main hydrochemical facies of the aquifer (Na+K−Cl+SO4), represents 60% of the total wells. Whereas 32.3% of the wells are located in the ‘no pair up’ and ‘no pair down’ fields on the Piper diagram. Calcite, dolomite, and aragonite solubility were assessed in terms of the saturation index where they show positive values indicating supersaturation. The hydrogeochemical behavior is rather complicated and is affected by anthropogenic and natural parameters.

Shell preservation of Limacina inflata (Pteropoda) in surface sediments from the Central and South Atlantic Ocean: a new proxy to determine the aragonite saturation state of water masses

Over 300 surface sediment samples from the Central and South Atlantic Ocean and the Caribbean Sea were investigated for the preservation state of the aragonitic test of Limacina inflata. Results are displayed in spatial distribution maps and are plotted against cross-sections of vertical water mass configurations, illustrating the relationship between preservation state, saturation state of the overlying waters, and overall water mass distribution. The microscopic investigation of L. inflata (adults) yielded the Limacina dissolution index (LDX), and revealed three regional dissolution patterns. In the western Atlantic Ocean, sedimentary preservation states correspond to saturation states in the overlying waters. Poor preservation is found within intermediate water masses of southern origin (i.e. Antarctic intermediate water (AAIW), upper circumpolar water (UCDW)), which are distinctly aragonite-corrosive, whereas good preservation is observed within the surface waters above and within the upper North Atlantic deep water (UNADW) beneath the AAIW. In the eastern Atlantic Ocean, in particular along the African continental margin, the LDX fails in most cases (i.e. less than 10 tests of L. inflata per sample were found). This is most probably due to extensive “metabolic” aragonite dissolution at the sediment-water interface combined with a reduced abundance of L. inflata in the surface waters. In the Caribbean Sea, a more complex preservation pattern is observed because of the interaction between different water masses, which invade the Caribbean basins through several channels, and varying input of bank-derived fine aragonite and magnesian calcite material. The solubility of aragonite increases with increasing pressure, but aragonite dissolution in the sediments does not simply increase with water depth. Worse preservation is found in intermediate water depths following an S-shaped curve. As a result, two aragonite lysoclines are observed, one above the other. In four depth transects, we show that the western Atlantic and Caribbean LDX records resemble surficial calcium carbonate data and δ 13C and carbonate ion concentration profiles in the water column. Moreover, preservation of L. inflata within AAIW and UCDW improves significantly to the north, whereas carbonate corrosiveness diminishes due to increased mixing of AAIW and UNADW. The close relationship between LDX values and aragonite contents in the sediments shows much promise for the quantification of the aragonite loss under the influence of different water masses. LDX failure and uncertainties may be attributed to (1) aragonite dissolution due to bottom water corrosiveness, (2) aragonite dissolution due to additional CO 2 release into the bottom water by the degradation of organic matter based on an enhanced supply of organic matter into the sediment, (3) variations in the distribution of L. inflata and hence a lack of supply into the sediment, (4) dilution of the sediments and hence a lack of tests of L. inflata, or (5) redeposition of sediment particles.

断熱材用シリカバルーン回収のための温水浮選によるアラゴナイトの除去

Among nearly thirty types of calcium silicate hydrates, hydrothermally synthesized porous xonotlite is being used as fire resistant building material and heat resister. The molded body can be synthesized to have the necessary bulk density, strength and low thermal conductivity. When the porous amorphous silica (silica balloon) is synthesized through the removal of calcium from calcium silicate, the volume of ultrafine pores increases and the heat conductivity is further reduced. But, during the above process beside silica balloon, the needle shaped aragonite is also obtained. Since the aragonite not porous, the thermal conductivity of the slurry becomes five times that of silica glass. Therefore, to improve the thermal insulation aragonite has to dissolved using hydrochloric acid, a method that is costly and also the reuse of aragonite becomes impossible. In this study, we have examined the viability of separating aragonite and silica balloon using flotation and have arrived at the following conclusions.(1) When silica balloon and aragonite were floated separately with sodium oleate as collector, the floatability of aragonite was low and silica balloon did not float at all. But, in the flotation of aragonite-silica ballon mixture increment in floatability was observed in the case of aragonite due to large average diameter of the particle and the floatability of silica ballon also increased due to calcium ion activated surface and consequently the separation became difficult.(2) In the flotation of aragonite only, beside the collector sodium oleate, frother alcohol also was added. The floatability improved when the number of carbon atoms in the alkyl group was more than three. But, in the case of aragonite-silica mixture, silica balloon also floated due to the presence of dissolved calcium ions and the separation was difficult.(3) At the elevated temperatures the solubility of aragonite decreases leading to a decrease in the calcium ion concentration in the suspension. As a result the separation of aragonite and silica balloon becomes possible at temperatures higher than 353 K using sodium oleate as collector.

The steady-state calcium carbonate ion activity product of recent shallow water carbonate sediments in seawater: a comparison of field observations and laboratory experiments

Closed system equilibration experiments between natural seawater and shallow water calcium carbonate-rich sediments from the Bahamas yielded steady-state calcium carbonate ion activity products (CCIAP). Results obtained from initially supersaturated and undersaturated solutions were in good agreement. Experiments conducted with the addition of a biocide and/or the destruction of sediment organic matter gave results similar to those obtained in systems where these treatments were not used. Excellent agreement was also found between CCIAP values for 8 day and more than 50 day equilibration times. Our results, therefore, meet the major criteria for at least metastable equilibrium between the solution and carbonate sediment. Fine-grained samples produced a CCIAP close to the value predicted for aragonite, which is the major carbonate phase in all samples. Coarse-grained sediments produced larger CCIAP values of up to 2.8 times that predicted for aragonite equilibrium. The CCIAP for the coarse-grained sediments is probably produced by high-Mg calcite which is a significant component of these sediments. Oolite samples were among the coarse-grained sediment samples studied. They also produced results much greater than expected for aragonite equilibrium. This brings into question their use as material for measuring aragonite solubility as has been done in the past. The CCIAP measured in the laboratory experiments are in good agreement with field observations of pore-water CCIAP values from the fine-grained sediments. Coarse-grained sediments showed greater variability, with higher CCIAP values generally occurring in the pore waters than in the laboratory experiments. Since the overlying waters were always at a higher CCIAP than the pore waters, the major factor causing this difference is believed to be the short residence time of pore waters in the coarse-grained sediments, which is the result of the high-energy hydrodynamic environments in which they reside.

The solubilities of calcite, aragonite and vaterite in CO 2-H 2O solutions between 0 and 90°C, and an evaluation of the aqueous model for the system CaCO 3-CO 2-H 2O

Calculations based on approximately 350 new measurements (Ca T -PCO 2) of the solubilities of calcite, aragonite and vaterite in CO 2-H 2O solutions between 0 and 90°C indicate the following values for the log of the equilibrium constants K C , K A , and K V respectively, for the reaction CaCO 3(s) = Ca 2+ + CO 2− 3: Log K C = −171.9065 − 0.077993T + 2839.319 T + 71.595 log T Log K A = −171.9773 − 0.077993T + 2903.293 T +71.595 log T Log K V = −172.1295 − 0.077993T + 3074.688 T + 71.595 log T where T is in oK. At 25°C the logarithms of the equilibrium constants are −8.480 ± 0.020, −8.336 ± 0.020 and −7.913 ± 0.020 for calcite, aragonite and vaterite, respectively. The equilibrium constants are internally consistent with an aqueous model that includes the CaHCO + 3 and CaCO 0 3 ion pairs, revised analytical expressions for CO 2-H 2O equilibria, and extended Debye-Hückel individual ion activity coefficients. Using this aqueous model, the equilibrium constant of aragonite shows no PCO 2-dependence if the CaHCO + 3 association constant is Log K Cahco + 3 = 1209.120 + 0.31294T — 34765.05 T − 478.782 log T between 0 and 90°C, corresponding to the value log K Cahco + 3 = 1.11 ± 0.07 at 25°C. The CaCO 0 3 association constant was measured potentiometrically to be log K CaCO 0 3 = −1228.732 − 0.299444T + 35512.75 T + 485.818 log T between 5 and 80°C, yielding log K CaCO 0 3 = 3.22 ± 0.14 at 25°C. The CO 2-H 2O equilibria have been critically evaluated and new empirical expressions for the temperature dependence of K H , K 1 and K 2 are log K H = 108.3865 + 0.01985076T − 6919.53 T − 40.45154 log T + 669365. T 2 , log K 1 = −356.3094 − 0.06091964T + 21834.37 T + 126.8339 log T — 1684915. T 2 and log K 2 = −107.8871 − 0.03252849 T + 5151.79/ T + 38.92561 log T − 563713.9/ T 2 which may be used to at least 250°C. These expressions hold for 1 atm. total pressure between 0 and 100°C and follow the vapor pressure curve of water at higher temperatures. Extensive measurements of the pH of Ca-HCO 3 solutions at 25°C and 0.956 atm PCO 2 using different compositions of the reference electrode filling solution show that measured differences in pH are closely approximated by differences in liquid-junction potential as calculated by the Henderson equation. Liquid-junction corrected pH measurements agree with the calculated pH within 0.003-0.011 pH. Earlier arguments suggesting that the CaHCO + 3 ion pair should not be included in the CaCO 3-CO 2-H 2O aqueous model were based on less accurate calcite solubility data. The CaHCO + 3 ion pair must be included in the aqueous model to account for the observed PCO 2-dependence of aragonite solubility between 317 ppm CO 2 and 100% CO 2. Previous literature on the solubility of CaCO 3 polymorphs have been critically evaluated using the aqueous model and the results are compared.

Comment on “The solubility of aragonite in seawater”

Comment on “The solubility of aragonite in seawater”

The solubility of aragonite in seawater at 25.0°C and 32.62‰ salinity

The apparent solubility product of aragonite in 32‰ seawater at 25.0°C is reported as K′ sp = (0.869±0.049) × 10 −6( mol 2 kg seawater −2) thus confirming the value of R.A. Berner, 1976 (Am. J. Sci., 276: 713–730). The apparent solubility product ratio for aragonite and calcite is reported as K′ aragonite K′ calcite = 2.05 The deviation of this value from the thermodynamic ratio is atttributed to the formation of a stable low Mg-calcite coating on pure calcite in seawater measurements of solubility.

The solubility of aragonite in seawater—I. Effect of pH and water chemistry at one atmosphere

The effect of water chemistry on the solubility of aragonite in seawater has been defined experimentally as a series of apparent solubility products measured with respect to pH at one atmosphere. The dominant control of the apparent solubility product of aragonite is the carbonate ion concentration, and this is primarily a function of pH. In the light of this fact, we have reconciled our data with 81 other reported values of aragonite solubility by simply examining the water chemistry of the waters in which they were determined.

Solubility of aragonite in seawater—II. Effect of pressure on the onset and maintenance of dissolution

The apparent solubility product ( K' sp ) of aragonite in a variety of seawater compositions has been determined at pressures from 0 to 1019 atm and a nomogram developed to allow the determination of the K' sp when the apparent ion product (AIP) at one atmosphere and the collection depth of a water sample are known. This nomogram provides a basis from which the onset of aragonite dissolution can be determined for conditions representative of aragonite sedimentation through the changing water masses of the open ocean.

The solubility of calcite and aragonite in seawater of 35%. salinity at 25°C and atmospheric pressure

The solubilities of synthetic, natural and biogenic aragonite and calcite, in natural seawater of 35%. salinity at 25°C and 1 atm pressure, were measured using a closed system technique. Equilibration times ranged up to several months. The apparent solubility constant determined for calcite of 4.39(±0.20) × 10 −7 mol 2 kg −2 is in good agreement with other recent solubility measurements and is constant after 5 days equilibration. When we measured aragonite solubility we observed that it decreased with increasing time of equilibration. The value of 6.65(±0.12) × 10 −7 mol 2 kg −2, determined for equilibration times in excess of 2 months, is significantly less than that found in other recent measurements, which employed equilibration times of only a few hours to days. No statistically significant difference was found among the synthetic, natural and biogenic material. Solid to solution ratio, contamination of aragonite with up to 10 wt% calcite and recycling of the aragonite made no statistically significant difference in solubility when long equilibration times were used. Measured apparent solubility constants of aragonite and calcite are respectively 22( ± 3)% and 20( ± 2)% less than apparent solubility constants calculated from thermodynamic equilibrium constants and seawater total activity coefficients. These large differences in measured and calculated apparent solubility constants may be the result of the formation of surface layers of lower solubility than the bulk solid.