A conceptual model for near-surface kinetic controls on the trace-element and stable isotope composition of abiogenic calcite crystals

The surface of a crystal in equilibrium with solute-bearing fluid generally has a composition that differs from that of the bulk crystal. If the crystal is growing, the surface composition may be “captured” by the newly formed lattice to a degree that depends upon the growth rate and the mobility of atoms in the near-surface region: rapid growth promotes this growth “entrapment,” high near-surface mobility works against it. Natural calcites may be particularly susceptible to this kind of kinetic disequilibrium, because their precipitation rates from aqueous solution can be relatively high even at near-ambient temperatures, where ion mobility in the critical near-surface region may be limited.Existing laboratory data on trace-element uptake as a function of calcite growth rate are examined here in the context of recent discoveries concerning the structure, chemistry and kinetics of the near-surface region of calcite crystals. Recent demonstrations that ions can be mobile in the outermost few nanometers of the calcite lattice even at room temperature have the greatest potential to affect growth entrapment. The model of Watson and Liang (1995)—which quantifies entrapment efficiency in terms of growth rate, diffusivity and surface-layer thickness—is modified to include a depth-dependent diffusivity and possible depletion (as well as enrichment) of some elements in the near-surface region. With these changes, the model is shown to be qualitatively consistent with the body of experimental data on trace element uptake during calcite precipitation.This apparent success of the model invites application to stable isotopes. Constraining data are few, but available information on oxygen isotope fractionation can be used to show that growth entrapment at ambient temperatures may (depending on model assumptions) produce deviations from calcite/H₂O equilibrium of up to several ‰. The preferred choice of ¹⁸O/¹⁶O for the surface layer is lighter than the lattice equilibrium value, and leads to a reduction in ¹⁸O/¹⁶O of crystals grown at higher growth rates, mimicking “vital effects.”     

Cyclic development of large,complex, calcite dendrite crystals in the Clinton travertine,Interior British Columbia,Canada

Bands of large (up to 4 cm long) three-dimensional crystallographic dendrites form the terrace fronts in an old travertine mound exposed near Clinton, British Columbia. The dendrites, with their long axes perpendicular to the terrace front, are characterized by numerous levels of branching. Each branch is formed of multitudes of skeletal rhombs, four- and six(?)-sided bipyramidal crystals, or prismatic hexagonal crystals that are precisely aligned along crystallographic precepts. Although individual branches are formed of one type of subcrystal, neighbouring branches may be formed of different subcrystal types.Highly supersaturated waters that were generated by rapid CO₂ degassing of the spring water during its turbulent flow over the steep terrace fronts probably drove dendrite precipitation. The presence of growth lines indicates that growth was episodic. Type I growth lines probably formed annually in response to seasonal climate changes whereas Type II growth lines, which formed less frequently, may reflect changes in the flow velocity and/or flow patterns of the spring waters.Early diagenetic modification of the dendrites involved crystal face enlargement, cements formed of trigonal prisms or needle-fiber crystals, microbial infestation that mediated substrate dissolution, and/or deposition of detrital calcite crystals that formed in the water column. Much of the diagenetic modification may have taken place during the periods when the dendrites had temporarily stopped growing.The dendrites in the Clinton travertine are an excellent example of complex, episodic calcite crystal growth that was extensively modified by early diagenetic processes in a surface environment. The same spring waters from which the dendrites were precipitated mediated much of the early diagenesis.     

A geochemical evaluation of perennial spring activity and associated mineral precipitates at Expedition Fjord,Axel Heiberg Island,Canadian High Arctic

Two groups of perennial springs are observed in the Canadian High Arctic at Expedition Fjord on Axel Heiberg Island at Colour Peak and Gypsum Hill. Saline discharge (∼1.3–2.5 molal NaCl) produces a variety of calcite (travertine) and gypsum-rich precipitates. Saturation index calculations of the spring waters at Colour Peak suggest CO₂ degassing from the waters causes calcite precipitation. Gypsum precipitation dominates at Gypsum Hill, where spring waters have lower alkalinity and higher SO₄ concentrations. Mineral accumulations form both channel and rimstone pool morphologies as a result of varying slope conditions. At Colour Peak, confined flow in steep slope areas develop massive structures in contrast to more friable, porous accumulations in areas where waters fan out on shallower slopes; these morphological variations lead to corresponding varying apparent rates of mineral precipitation. Mineral precipitation at Gypsum Hill is far less notable as a result of lower discharge rates and annual degradation by icing formation. Microscopic observations and geochemical analyses of the channel precipitates at Colour Peak reveal alternating light (calcite spar) and dark (anhedral microcrystalline calcite combined with organic matter and non-carbonate minerals) laminae. Rimstone pools forming in lower sections of spring discharge are composed of accumulations of large euhedral calcite crystals interbedded with allochthonous inputs. High concentration of dissolved solids is responsible for slow travertine precipitation rates, which occurs during winter. This precipitation is further retarded during summer months by the introduction of crystal growth inhibitors such as Fe³⁺ and deposition of organic matter and soil sediments.     

Nanoscale effects of strontium on calcite growth: An in situ AFM study in the absence of vital effects

This experimental study presents in situ measurements of step migration rates for layer growth of calcite at various levels of superaturation and fluid Sr concentrations. Our results show that Sr has complex behavior as an impurity. At low concentrations, Sr promotes faster growth. This effect may be associated with slight shifts in calcite solubility when Sr is incorporated or may be due to as yet uncharacterized kinetic effects. At higher concentrations, Sr stops step advancement by pinning kink-sites or step edges. The threshold concentration of Sr needed to halt growth is positively correlated with supersaturation.Addition of Sr to the calcite growth system leads to significant changes in hillock morphology. Hillocks become elongate perpendicular to the projection of the c-glide plane, in contrast to the changes previously reported for Mg. Step edges also become scalloped, and the boundary between the obtuse-stepped flanks disappears and is replaced by a new step direction with edges parallel to [010].Incorporation of Sr was measured at two supersaturation levels and identical fluid [Sr]. The results indicate a strong positive correlation between fluid supersaturation and crystal Sr content. Further, Sr is strongly fractionated between obtuse- and acute-stepped flanks by a factor of approximately two. The sensitivity of Sr uptake to supersaturation may explain apparently contradictory results in the literature regarding whether Sr uptake in the calcite produced by one-celled marine organisms is controlled by temperature. In addition, Sr contents of natural calcite samples may be good indicators of the levels of supersaturation at which the crystals grew.Results of this investigation demonstrate the importance of understanding impurity-specific interactions with calcite growth surfaces at the microscopic scale. Despite similar chemical behavior in some systems, Mg and Sr clearly have very different effects on calcite growth. If Sr and other impurities are to be used as robust indicators of growth conditions in natural calcite samples, well grounded understanding of the mechanisms of recording trace element signatures in calcite is an essential step toward correctly deciphering paleoenvironmental signals from fossil calcite compositions.     

Rates of aragonite conversion to calcite in dilute aqueous fluids at 50 to 100°C: experimental calibration using Ca-isotope attenuation

Aragonite was converted to calcite in dilute CaCl₂ fluid at temperatures ranging from 50 to 100°C. Surface areas of aragonite and calcite seed crystals were varied by over an order of magnitude to permit independent assessment of calcite nucleation and growth processes. Aragonite conversion rates were measured using isotopic attenuation of dissolved ⁴⁴Ca, which was added to the fluid at the beginning of each experiment. Measured conversion rates were found to be constant with respect to time and proportional to the initial surface area of aragonite. Rates were independent of the surface area of calcite seed crystals owing to heterogeneous nucleation of calcite on aragonite during experiments. The data imply that calcite nucleates on aragonite surfaces until the level of saturation with respect to calcite reaches a critical threshold value where further nucleation is precluded. Thereafter, conversion to calcite occurs at a steady state rate consistent with aragonite dissolution at a fixed level of saturation. Aragonite converts to calcite under these conditions and in dilute fluids at rates of approximately 10 and 100 microns/yr at 25 and 100°C, respectively.     

In-situ Growth of Calcite at Devils Hole, Nevada: Comparison of Field and Laboratory Rates to a 500,000 Year Record of Near-Equilibrium Calcite Growth

Calcite grew continuously for 500,000 years on the submerged walls of an open fault plane (Devils Hole) in southern Nevada, U.S.A. at rates of 0.3 to 1.3 mm/ka, but ceased growing approximately 60,000 years ago, even though the fault plane remained open and was continuously submerged. The maximum initial in-situ growth rate on pre-weighed crystals of Iceland spar placed in Devils Hole (calcite saturation index, SI, is 0.16 to 0.21 at 33.7 °C) for growth periods of 0.75 to 4.5 years was 0.22 mm/ka. Calcite growth on seed crystals slowed or ceased following initial contact with Devils Hole groundwater. Growth rates measured in synthetic Ca-HCO₃ solutions at 34 °C, CO₂ partial pressures of 0.101, 0.0156 (similar to Devils Hole groundwater) and 0.00102 atm, and SI values of 0.2 to 1.9 were nearly independent of P_{CO 2}, decreased with decreasing saturation state, and extrapolated through the historical Devils Hole rate. The results show that calcite growth rate is highly sensitive to saturation state near equilibrium. A calcite crystal retrieved from Devils Hole, and used without further treatment of its surface, grew in synthetic Devils Hole groundwater when the saturation index was raised nearly 10-fold that of Devils Hole water, but the rate was only 1/4 that of fresh laboratory crystals that had not contacted Devils Hole water. Apparently, inhibiting processes that halted calcite growth in Devils Hole 60,000 years ago continue today.     

Calcite from the Quaternary spring waters at Tylicz, Krynica, Polish Carpathians

At Tylicz, near Krynica Spa (Polish Carpathians), spelean deposits fill fissures and caverns in Eocene flysch rocks. They occur as: (1) clastic cave sediments transformed into hard crusts due to cementation by finely crystalline low-Mg calcite, (2) drusy calcite that covers crust surfaces and fills voids in the crust and (3) colloform calcite. Two varieties of drusy calcite are distinguished: acicular and columnar. The acicular calcite is built up of crystallites forming spherulitic fans or cones. In places it is syntaxially covered with colloform calcite. The drusy calcite is low-Mg ferroan calcite with non-ferroan subzones, whereas the colloform calcite is a low-Mg non-ferroan variety. The columnar calcite crystals form fan-like bundles. Cross-sections cut perpendicular to the c-axes of columnar crystals are equilateral triangular in shape, although some have slightly curved edges. The columnar crystals have steep rhombic terminations and most have curved triangular faces, i.e. gothic-arch calcite. Saddle crystals have also been observed. The columnar crystals are composed of radially orientated crystallites whose long dimension is parallel to the c-axis. The curved crystal faces of such polycrystals are interpreted as a result of differential growth rates of the crystallites. The spelean calcites precipitated from CO₂-saturated water. The high rate of CaCO₃ precipitation is thought to be responsible for the formation of radial structures. Finely crystalline calcite formed within pore spaces of clastic sediments close to the water-air interface, drusy calcite crystallized beneath the water-air interface, and colloform calcite precipitated from thin films of water.     

Growth patterns and implications of complex dendrites in calcite travertines from Lýsuhóll, Snæfellsnes, Iceland

Calcite dendrite crystals are important but poorly understood components of calcite travertine that forms around many hot springs. The Lýsuhóll hot-spring deposits, located in western Iceland, are formed primarily of siliceous sinters that were precipitated around numerous springs that are now inactive. Calcite travertine formed around the vent and on the discharge apron of one of the springs at the northern edge of the area. The travertine is formed largely of two types (I and II) of complex calcite dendrite crystals, up to 1 cm high, that grew through the gradual addition of trilete sub-crystals. The morphology of the dendrite crystals was controlled by flow direction and the competition for growth space with neighbouring crystals. Densely crowded dendrites with limited branching characterize the rimstone dams whereas widely spaced dendrites with open branching are found in the pools. Many dendrite bushes in the pools nucleated around plant stems. Growth of the dendrite crystals was seasonal and incremental. Calcite precipitation was driven by rapid CO₂ degassing of CO₂-rich spring waters during the spring and summer. During winter, when snow covered the ground and temperatures were low, opal-A precipitated on the exposed surfaces of the dendrites. Segmentation of dendrite branches by discontinuities coated with opal-A and overgrowth development around sub-crystals resulted from this seasonal growth cycle. The calcite dendrite crystals in the Lýsuhóll travertine differ in morphology from those at other hot springs, such as those at Lake Bogoria, Kenya, and Waikite in New Zealand. Comparison with the calcite dendrite crystals found at those sites shows that dendrite morphology is site-specific and probably controlled by carbonate saturation levels that, in turn, are controlled by the rate of CO₂ degassing and location in the spring outflow system.     

'Sediment'–cement relationships in a Pleistocene speleothem from Italy: a possible analogue for 'replacement' cements and Archaeolithoporella in ancient reefs

Ancient carbonate buildups may contain extraordinarily large amounts of early diagenetic precipitates. In some, host rock lamination may be traced into inclusion bands within the 'cement' crystals, suggesting that the crystals are replacive. By analogy with a Pleistocene speleothem from the Sorrento Peninsula, however, these relationships can be explained differently. In the speleothem, large, repeatedly split and dendritic calcite crystals occur within a laminated carbonate. Lamination consists of sub-mm alternations of micrite and microspar. Micritic laminae pass laterally into inclusion-rich growth bands in the dendritic calcite crystals, and have replaced an aragonitic cement, whereas the microspar laminae were primary calcite cements. Three types of inclusion-rich bands occur in the dendrite crystals: (1) with aragonite relicts, (2) 'ribbon calcite' and (3) with oriented micropores. When aragonite precipitated, the calcite dendrite branches were unable to keep growing as single crystals and split into crystallites (separated by micropores, some forming ribbon calcite), whereas during episodes of calcite lamina precipitation, the larger crystals were regenerated by crystallite coalescence. Calcite crystals are primary: they did not replace a micritic precursor. By analogy with the Italian speleothem, some ancient reefal sparry carbonates may not be replacements of earlier laminated sediments, but may have grown concurrently with them. It is also probable that some ancient laminated sediments were instead sea-floor precipitates, and that stromatolites containing cross-cutting crystal fabrics, and the alternating micrite-microspar laminae typical of Archaeolithoporella , could be largely abiotic crystal growths.     

Origin and evolution of major salts in the Darling pans,Western Cape,South Africa

Sediment and water samples from 12 saline pans on the semi-arid west coast of South Africa were analysed to determine the origin of salts and geochemical evolution of water in the pans. Pans in the area can be subdivided into large, gypsiferous coastal pans with 79–150 g/kg total dissolved salt (TDS), small inland brackish to saline (2–64 g/kg TDS) pans and small inland brine (168-531 g/kg TDS) pans that have a layer of black sulphidic mud below a halite crust. The salinity of coastal pan waters varies with the seasonal influx of dilute runoff and dissolution of relict Pleistocene marine evaporite deposits. In contrast, inland pans are local topographic depressions, bordered on the north by downslope lunette dunes, where solutes are concentrated by evaporation of runoff, throughflow and groundwater seepage. The composition of runoff and seepage inflow waters is determined by modification of coastal rainfall by weathering, calcite precipitation and ion exchange reactions in the predominantly granitic catchment soils. Evaporation of pan waters leads to precipitation of calcite, Mg–calcite, dolomite, gypsum and halite in a distinct stratigraphic succession in pan sediments. Bicarbonate limits carbonate precipitation, Ca limits gypsum precipitation and Na limits halite precipitation. Dolomitisation of calcite is enhanced by the high Mg/Ca ratio of brine pan waters. Brine pan waters evolve seasonally from Na–Cl dominated brines in the wet winter months to Mg–Cl dominated brines in the dry summer months, when 5–20 cm thick halite crusts cover pan surfaces. Pan formation was probably initiated during a drier climate period in the early Holocene. More recent replacement of natural vegetation by cultivated land may have accelerated salt accumulation in the pans.     

Methane-derived high-Mg calcite submarine cement in Holocene nodules from the Fraser Delta, British Columbia, Canada

Carbonate nodules and slabs in late Holocene shelly terrigenous deposits of the modern Fraser River delta (～49°N) are formed close to the seafloor by precipitation from saline pore waters of mainly fibrous to bladed crystals of high-Mg (～ 10–20 mol% MgCO₃) calcite cement as coalescing isopachous crusts on grains. Previous reports that the cement is low-Mg calcite are not supported by this study. Highly negative δ¹³C values of ? 7 to ? 59‰ for the cements indicate that the bulk of their carbonate carbon was derived from the microbiological degradation of organic matter in the deltaic deposits during shallow burial. In particular, the production of biogenic methane (CH₄) by anaerobic bacterial fermentation, its upward migration, chemical or biological oxidation to CO₂ and neutralization in the near-surface sediment, and diffusion to microenvironments relatively enriched in organic components, are a possible set of conditions influencing the process and sites of carbonate cementation. Methane-derived Mg-calcite appears also to be the major submarine cement in several other modern occurrences of lithified shallow-water terrigenous sands and muds at non-tropical latitudes.     

An experimental study of calcite dissolution rates at acidic conditions and 25 °C in the presence of NaPO3 and MgCl2

Dissolution rates of single calcite crystals were determined from sample weight loss using free-drift rotating disk techniques. Experiments were performed at 25 °C in aqueous HCl solutions over the bulk solution pH range −1 to 3 and in the presence of trace concentrations of aqueous NaPO₃ and MgCl₂. These salts were chosen for this study because aqueous magnesium and phosphate are known to strongly inhibit calcite dissolution at neutral to basic pH. Reactive solutions were undersaturated with respect to possible secondary phases. Neither an inhibition or enhancement of calcite dissolution rates was observed in the presence of aqueous MgCl₂ at pH 1 and 3. The presence of trace quantities of NaPO₃, which dissociates in solution to Na⁺ and H₂PO₄⁻, decreased the overall calcite dissolution rate at pH≤2. This contrasting behavior could be attributed to the different adsorption behavior of these dissolved species. As calcite surfaces are positively charged in acidic solutions, aqueous Mg²⁺ may not adsorb, whereas aqueous phosphate, present as either the anion H₂PO₄⁻ or the neutral species H₃PO₄⁰, readily adsorbs on calcite surfaces leading to significant dissolution inhibition.     

Unravelling the fluid flow evolution and precipitation mechanisms recorded in calcite veins in relation to Pangea rifting–Newark Basin,USA

Calcite veins hosted in the Triassic Stockton, Lockatong and Passaic formations of the Newark Basin are investigated to reconstruct the fluid evolution. To constrain the parameters of calcite precipitation, a microthermometry study was carried, which reveals precipitation of calcite from a low to moderate saline H₂O-NaCl fluid (0.4 to 13.2 wt% NaCl equiv.) under low to moderate hydrothermal (137 °C to 232 °C) conditions. This fluid composition is interpreted to reflect mixing between a deep basement-derived heated diluted fluid and relatively low to moderate saline diagenetic formation waters hosted in the different Triassic formations. Carbon and strontium isotope analysis on the vein calcites suggests that these elements are derived from the pre-Triassic basement and the sedimentary cover through fluid-rock interactions. The aforementioned geochemical findings are supported by Rare Earth Elements and Yttrium (REY) systematics and oxygen isotope data.The Late Triassic extensional activity and gravity-driven fluid flow mechanism facilitated the infiltration of meteoric waters to deeper lithostratigraphic units (i.e., Precambrian-Paleozoic basement-Triassic Stockton Formation) where they became heated. In response to the extensional tectonics, the deep-seated hydrothermal basement-derived diluted fluids migrated upward along the tectonic-related fractures and the major faults to upper shallow crustal levels. Here, the heated, diluted meteoric waters were mixed with low, moderately saline, and relatively cooler formation waters, leading to calcite precipitation. The pH increase is suggested to be a contributing factor in the precipitation of calcite.     

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.     

Effects of phosphate ions on intergranular pressure solution in calcite: An experimental study

Intergranular pressure solution (IPS) is a coupled chemical-mechanical process of widespread importance that occurs during diagenesis and low-temperature deformation of sedimentary rocks. Laboratory experiments on IPS in halite, quartz, and calcite have largely concentrated on the mechanical aspects of the process. In this study, we report the effects of pore fluid chemistry, specifically varying phosphate ion concentration, on the mechanical compaction by IPS of fine-grained calcite powders at room temperature and 1 to 4 MPa applied effective stress. Phosphate was investigated because of its importance as a biogenic constituent of sea and pore waters. Increasing the pore fluid phosphate concentration from 0 to 10⁻³ mol/L systematically reduced compaction strain rates by up to two orders of magnitude. The sensitivity of the compaction strain rate to phosphate concentration was the same as the sensitivity of calcite precipitation rates to the addition of phosphate ions reported in the literature, suggesting that the rate of IPS in phosphate-bearing samples was controlled by calcite precipitation on pore walls. The results imply that IPS and associated porosity/permeability reduction rates in calcite sediments may be strongly reduced when pore fluids are enriched in phosphates, for example, through high biologic productivity or a seawater origin. Future modeling of IPS-related processes in carbonates must therefore take into account the effects of pore fluid chemistry, specifically the inhibition of interfacial reactions.     

The Great Barrier Reef: a 700 000 year diagenetic history

A deep borehole through Ribbon Reef 5 in the Great Barrier Reef off north‐eastern Australia has identified a variety of cements, including epitaxial, radial prismatic and spherular aragonite, together with blocky, prismatic and fibrous calcite. These cements are discontinuously arranged within the sequence that consists predominantly of grainstones but locally includes clotted muddy and filamentous textures that may be of microbial origin. Calcite cements vary in morphology with groups of crystals that include acute scalenohedral, rhombohedral and flattened concordant terminations; these show varying densities of inclusions that locally define growth zones and in some terminations divide in the manner of ‘split crystals’ to form fibrous fringes. Morphological changes in calcite are inferred to reflect changes in water chemistry and crystal growth rates at the time of growth, allied to their relationship to the palaeo‐water table, and linked in turn to changes in sea‐level. Neomorphism and dissolution are widespread and variations in the severity of both imply response to the degree of undersaturation of pore waters that at times were probably balanced within very narrow limits. A total of 10 depositional units are identified. Those units at the base of the borehole reflect deposition and diagenesis within a marine environment. The influence of meteoric waters, indicated by stable isotopes, is first apparent at the top of Unit 1 and in Unit 2 (184 to 155 m below sea floor). Petrographic evidence of vadose conditions appears at the tops of Unit 3 (131 to 99 m below sea floor). Units 4 to 8, all deposited under marine conditions, provide isotopic evidence of meteoric or mixing‐zone waters and petrographic indicators of vadose conditions, typically at the top of the units. Evidence indicates that in Unit 5 the water table was mobile and Units 6a, 6b, 7 and 8, all characterized by ultraviolet fluorescent cements, are capped by sub‐aerial erosion surfaces. Unit 9 (the Holocene) reflects the recent re‐establishment of marine conditions. The extent of alteration of the entire sequence reflects the substantial and pervasive influence of meteoric waters. This effect is interpreted as a result of a greater rainfall and river flow from the mainland during early and late stages of interstadial periods. The study reflects progress in the ability to recognize the diagenetic signal generated by sea‐level change. However, whereas the isotopic results reflect the changing relationships between vadose and phreatic zones in groundwater systems beneath successive emergent surfaces, their correspondence with petrographic features is expressed only weakly and commonly lacks the systematic sequential overprinting implied by the distribution of cathodoluminescent zones of cements in many ancient limestones.     

The mineralogy of primary inclusions in apatite crystals extracted from Alnö ijolite

Apatite crystals extracted from altered Alnö ijolite pegmatites contain primary aqueous saline inclusions and solid inclusions. The solid inclusions consists mainly of calcite, but the aqueous saline inclusions contain a variety of daughter minerals which include nahcolite (NaHCO₃), alkali halides and sulphates. These inclusions represent samples of a concentrated, highly alkaline aqueous solution and were originally trapped as homogeneous liquids during the growth of apatite. In the samples studied these fluids are late-stage and are thought to be responsible for the alteration seen in the host ijolite.     

Effects of temperature and transport conditions on calcite growth in the presence of Mg: Implications for paleothermometry

This study links direct measurement of Mg-calcite growth kinetics with high-spatial-resolution analysis of Mg contents in experimental crystals, with particular attention to the effects of temperature on growth rate and reactant transport conditions on Mg distribution. In contrast to previous experiments on Mg partitioning into calcite, here the layer-growth mechanism was observed in situ and step speeds precisely measured with fluid cell atomic force microscopy over a range of temperatures, degrees of supersaturation, and solution Mg concentrations. Data collected from 15° to 30°C yield an activation energy for calcite precipitation of 33 kJ/mol for solutions with [Mg] = 5 × 10⁻⁵ molal. Electron microprobe analyses of large hillocks grown at corresponding conditions demonstrate that Mg has a strong preference for incorporation at negative (acute) step edges, rather than at positive (obtuse) edges when growth rate is limited by surface reactions. This preference is reversed when growth is instead limited by diffusion of reactants through a boundary layer at the mineral-solution interface. These findings show that temperature is not the only strong control on the extent of Mg incorporation and distribution in calcite; transport conditions during mineral growth may also be a first-order factor governing the compositions of natural calcite samples.     

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.