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).     

Impact of lake‐level changes on the formation of thermogene travertine in continental rifts: Evidence from Lake Bogoria,Kenya Rift Valley

Travertine is present at 20% of the ca 60 hot springs that discharge on Loburu delta plain on the western margin of saline, alkaline Lake Bogoria in the Kenya Rift. Much of the travertine, which forms mounds, low terraces and pool‐rim dams, is sub‐fossil (relict) and undergoing erosion, but calcite‐encrusted artefacts show that carbonate is actively precipitating at several springs. Most of the springs discharge alkaline (pH: 8·3 to 8·9), Na‐HCO₃ waters containing little Ca (<2 mg l^?1) at temperatures of 94 to 97·5°C. These travertines are unusual because most probably precipitated at temperatures of >80°C. The travertines are composed mainly of dendritic and platy calcite, with minor Mg‐silicates, aragonite, fluorite and opaline silica. Calcite precipitation is attributed mainly to rapid CO₂ degassing, which led to high‐disequilibrium crystal morphologies. Stratigraphic evidence shows that the travertine formed during several stages separated by intervals of non‐deposition. Radiometric ages imply that the main phase of travertine formation occurred during the late Pleistocene (ca 32 to 35 ka). Periods of precipitation were influenced strongly by fluctuations in lake level, mostly under climate control, and by related changes in the depth of boiling. During relatively arid phases, meteoric recharge of ground water declines, the lake is low and becomes hypersaline, and the reduced hydrostatic pressure lowers the level of boiling in the plumbing system of the hot springs. Any carbonate precipitation then occurs below the land surface. During humid phases, the dilute meteoric recharge increases, enhancing geothermal circulation, but the rising lake waters, which become relatively dilute, flood most spring vents. Much of the aqueous Ca²⁺ then precipitates as lacustrine stromatolites on shallow firm substrates, including submerged older travertines. Optimal conditions for subaerial travertine precipitation at Loburu occur when the lake is at intermediate levels, and may be favoured during transitions from humid to drier conditions.     

Origin of blocky aragonite cement in Cenozoic glaciomarine sediments,McMurdo Sound,Antarctica

Inorganic aragonite occurs in a wide spectrum of depositional environments and its precipitation is controlled by complex physio-chemical factors. This study investigates diagenetic conditions that led to aragonite cement precipitation in Cenozoic glaciomarine deposits of McMurdo Sound, Antarctica. A total of 42 sandstones that host intergranular cement were collected from the CIROS-1 core, located proximal to the terminus of Ferrar Glacier. Standard petrography, Raman spectroscopy and electron microprobe analysis reveal a prominent aragonite cement phase that occurs as a pore-filling blocky fabric throughout the core. Oxygen isotope compositions (δ¹⁸O = −30·0 to −8·6‰ Vienna Pee-Dee Belemnite) and clumped isotope temperatures (TΔ₄₇ = 13·1 to 31·5°C) determined from the aragonite cements provide precise constraints on isotopic compositions (δ¹⁸O_w) of the parent fluid, which mostly range from −10·8 to −7·2‰ Vienna Standard Mean Ocean Water. The fluid δ¹⁸O_w values are consistent with those of pore water, previously identified as cryogenic brine in the nearby AND-2A core. Petrographic and geochemical data suggest that aragonite cement in the CIROS-1 core precipitated from a similar brine. The brine likely formed and infiltrated sediments in flooded glacial valleys along the western margin of McMurdo Sound during the middle Miocene Climatic Transition, and subsequently flowed basinward in the subsurface. Consequently, the brine forms as a longstanding subsurface fluid that has saturated Cenozoic sediments below southern McMurdo Sound since at least the middle Miocene. Aragonite cementation in the CIROS-1 core is interpreted to reflect its proximal position to sites of brine formation and greater likelihood of experiencing brines with sustained high carbonate saturation states and Mg/Ca ratios. This unusual occurrence expands the range of known natural occurrences of aragonite cement. Given the potential for cryogenic brine formation in glaciomarine settings, blocky aragonite, as the end member of the spectrum of aragonite cement morphology, may be more widespread in glaciomarine sediments than currently thought.     

Origin of quartz cements in some sandstones from the Jurassic of the Inner Moray Firth (UK)

The extent of quartz cementation in shallow marine sandstones of the Brora Arenaceous Formation (Oxfordian) is closely related to the occurrence and abundance of Rhaxella perforata sponge spicules. Three cement morphologies are identified, chalcedonic quartz, microquartz and mesoquartz. Chalcedonic quartz forms matrix-supported cements which preserve moulds of Rhaxella spicules. Chalcedonic quartz crystals have inequant development of crystal faces, on average 0·1 μm in diameter, and are the first formed cement and reveal homogeneous dark grey tones on the SEM-CL/BEI. Microquartz forms 5–10 μm diameter crystals, which commonly grow on chalcedonic quartz substrates and show various grey tones under SEM-CL/BEI. Mesoquartz crystals grow in optical continuity with their host grains, have >20 μm a-axial diameter crystals, and exhibit distinctly zoned luminescence. Although no opaline silica is preserved, the quartz cement is interpreted to have formed from an opaline precursor. Detrital quartz has an average δ¹⁸O composition of + 12·2‰ and mesoquartz (syntaxial overgrowth) has an average δ¹⁸O composition of +20·0‰. Estimates of the δ¹⁸O compositions of microquartz and chalcedonic quartz are complicated by the problem of isolating the two textural types; mixtures of the two give consistently higher δ¹⁸O compositions than mesoquartz, the higher estimate being +39·2‰. From oxygen isotope data the formation of quartz, microquartz and chalcedonic quartz is interpreted to have taken place between 35 and 71°C in marine derived pore waters. Organic and inorganic maturation data constrain the upper temperature limit to less than 60°C.     

The thermodynamic properties and phase relations of some minerals in the system CaO-AI2O3-SiO2-H2O

The heat capacities of lawsonite, margante, prehnite and zoisite have been measured from 5 to 350 K with an adiabatic-shield calorimeter and from 320 to 999.9 K with a differential-scanning calorimeter. At 298.15 K, their heat capacities, corrected to end-member compositions, are 66.35, 77.30, 79.13 and 83.84 cal K^?1 mol^?1; their entropies are 54.98, 63.01, 69.97 and 70.71 cal K^?1 mol^?1, respectively. Their high-temperature heat capacities are described by the following equations (in calories, K, mol): Lawsonite (298–600 K): Cp° = 66.28 + 55.95 × 10^?3T ? 15.27 × 10⁵T^?2 Margarite (298–1000 K): Cp° = 101.83 + 24.17 × 10^?3T ? 30.24 × 10⁵T^?2 Prehnite (298–800 K): Cp° = 97.04 + 29.99 × 10^?3T ? 25.02 × 10⁵T^?2 Zoisite (298–730 K): Cp° = 98.92 + 36.36 × 10^?3T ? 24.08 × 10⁵T^?2 Calculated Clapeyron slopes for univariant equilibria in the CaO-Al₂O₃-SiO₂-H₂O system compare well with experimental results in most cases. However, the reaction zoisite + quartz = anorthite + grossular + H₂O and some reactions involving prehnite or margarite show disagreements between the experimentally determined and the calculated slopes which may possibly be due to disorder in experimental run products. A phase diagram, calculated from the measured thermodynamic values in conjunction with selected experimental results places strict limits on the stabilities of prehnite and assemblages such as prehnite + aragonite, grossular + lawsonite, grossular + quartz, zoisite + quartz, and zoisite + kyanite + quartz. The presence of this last assemblage in eclogites indicates that they were formed at moderate to high water pressure.     

Aragonite stromatolitic buildups from Santorini (Aegean Sea,Greece): Geochemical and palaeontological constraints of the caldera palaeoenvironment prior to the Minoan eruption (ca 3600 yr bp)

The pyroclastic deposits of the Minoan eruption (ca 3600 yr bp ) in Santorini contain abundant xenoliths. Most of these deposits are calcareous blocks of laminated‐botryoidal, stromatolite‐like buildups that formed in the shallow waters of the flooded pre‐Minoan caldera; they consist of (i) light laminae, of fibrous aragonite arranged perpendicular to layering, and (ii) dark laminae, with calcified filaments of probable biological origin. These microstructures are absent in the light laminae, suggesting a predominant inorganic precipitation of aragonite on substrates probably colonized by microbes. Internal cavities contain loose skeletal grains (molluscs, ostracods, foraminifera and diatoms) that comprise taxa typical of shallow marine and/or lagoon environments. Most of these forms are typical of warm water environments, although no typical taxa from hydrothermal vents have been observed. Past gasohydrothermal venting is recorded by the occurrence of barite, pyrolusite and pyrite traces. The most striking features of the stable isotopic data set are: (i) an overall wide range in δ¹³C_PDB (0·16 to 12·97‰) with a narrower variation for δ¹⁸O_PDB (?0·23 to 4·33‰); and (ii) a relatively uniform isotopic composition for the fibrous aragonite (δ¹³C = 12·40 ± 0·43‰ and δ¹⁸O = 2·42 ± 0·77‰, n = 21). The δ¹³C and δ¹⁸O values from molluscs and ostracods display a covariant trend, which reflects a mixing between sea water and a fluid influenced by volcano‐hydrothermal activity. Accordingly, ⁸⁷Sr/⁸⁶Sr from the studied carbonates (0·708758 to 0·709011 in fibrous aragonite and 0·708920 to 0·708991 in molluscs) suggests that the aragonite buildups developed in sea water under the influence of a hydrothermal/volcanic source. Significant differences in trace elements have been detected between the fibrous aragonite and modern marine aragonite cements. The caldera water from which the fibrous aragonite crusts formed received an input from a volcano‐hydrothermal system, probably producing diffuse venting of volcanogenic CO₂ gas and of a fluid enriched in Ca, Mn and Ba, and depleted in Mg and probably in Sr.     

Strain rates from snowball garnet

Spiral inclusion trails in garnet porphyroblasts are likely to have formed due to simultaneous growth and rotation of the crystals, during syn‐metamorphic deformation. Thus, they contain information on the strain rate of the rock. Strain rates may be interpreted from such inclusion trails if two functions are known: (1) The relationship between rotation rate and shear strain rate; (2) the growth rate of the crystal. We have investigated details of both functions using a garnetiferous mica schist from the eastern European Alps as an example. The rotation rate of garnet porphyroblasts was determined using finite element modelling of the geometrical arrangement of the crystals in the rock. The growth rate of the porphyroblasts was determined by using the major and trace element distributions in garnet crystals, thermodynamic pseudosections and information on the grain size distribution. For the largest porphyroblast size fraction (size L=12 mm) we constrain a growth interval between 540 and 590 °C during the prograde evolution of the rock. Assuming a reasonable heating rate and using the angular geometry of the spiral inclusion trails we are able to suggest that the mean strain rate during crystal growth was of the order of =6.6 × 10^?14 s^?1. These estimates are consistent with independent estimates for the strain rates during the evolution of this part of the Alpine orogen.     

Surface studies of feldspar dissolution using surface replication combined with electron microscopic and spectroscopic techniques

The replica of a microcline cleavage surface was examined before and at various stages of interaction with water and acid solutions at 70°C. For up to 14 weeks in demineralized water the surface as a whole underwent very little change, except some micrometre-sized particles were found on parts of the surface after only one week. Similar particles were found on the actual cleavage surface and on the surfaces of other microcline powders similarly leached at 22°C. These particles were made up of aluminum and silicon with little or no potassium. They were likely formed in some preexisting activated feldspar lattice, either by solid transformation or by local supersaturation and precipitation from solution.Further leaching for 48 hours in a 0.01 mol·L^?1 solution of hydrochloric acid caused only minor pitting of the same cleavage surface, probably due to enhanced dissolution, while contact with a 0.01 mol · L^?1 solution of hydrofluoric acid caused extensive formation of dissolution pits and channels along crystal defects leading to the removal of large portions of the surface. Neither acid appeared to dissolve the newly formed aluminum silicate particles appreciably.Hence during the incongruent dissolution of a feldspar, most of the reactions, dissolution and formation of authigenic Al-silicate phases, occur preferentially along crystal defects. Since the authigenic phases occur as discrete particles occupying only a small fraction of the parent surface their presence will not affect the bulk composition or the overall dissolution rate of the surface.     

Aragonite–calcite veins of the ‘Erzberg’ iron ore deposit (Austria): Environmental implications from young fractures

The well‐known Erzberg site represents the largest siderite (FeCO₃) deposit in the world. It consists of various carbonates accounting for the formation of prominent CaCO₃ (dominantly aragonite) precipitates filling vertical fractures of different width (centimetres to decimetres) and length (tens of metres). These commonly laminated precipitates are known as ‘erzbergite’. This study focuses on the growth dynamics and environmental dependencies of these vein fillings. Samples recovered on‐site and from mineral collections were analyzed, and these analyses were further complemented by modern water analyses from different Erzberg sections. Isotopic signatures support meteoric water infiltration and sulphide oxidation as the principal hydrogeochemical mechanism of (Ca, Mg and Fe) carbonate host rock dissolution, mobilization and vein mineralization. Clumped isotope measurements revealed cool formation temperatures of ca 0 to 10°C for the aragonite, i.e. reflecting the elevated altitude Alpine setting, but unexpectedly low for aragonite nucleation. The ²³⁸U–²³⁴U–²³⁰Th dating yielded ages from 285·1 ± 3·9 to 1·03 ± 0·04 kyr bp and all samples collected on‐site formed after the Last Glacial Maximum. The observed CaCO₃ polymorphism is primarily controlled by the high aqueous Mg/Ca ratios resulting from dissolution of Mg‐rich host rocks, with Mg/Ca further evolving during prior CaCO₃ precipitation and CO₂ outgassing in the fissured aquifer. Aragonite represents the ‘normal’ mode of erzbergite formation and most of the calcite is of diagenetic (replacing aragonite) origin. The characteristic lamination (millimetre‐scale) is an original growth feature and mostly associated with the deposition of stained (Fe‐rich) detrital particle layers. Broader zonations (centimetre‐scale) are commonly of diagenetic origin. Petrographic observations and radiometric dating support an irregular nature for most of the layering. Open fractures resulting from fault tectonics or gravitational mass movements provide water flow routes and fresh chemical reaction surfaces of the host rock carbonates and accessory sulphides. If these prerequisites are considered, including the hydrogeochemical mechanism, modern water compositions, young U‐Th ages and calculated precipitation rates, it seems unlikely that the fractures had stayed open over extended time intervals. Therefore, it is most likely that they are geologically young.     

The interaction of magnesium with calcite during crystal growth at 25–90°C and one atmosphere

Calcite crystals were grown in a closed system by recrystallization of synthetic and natural aragonite crystals, in the presence of various CaCl2-MgCl2 solutions with and without NaCl.The distribution of Mg2+ between calcite and solution at the entire temperature range is heterogeneous, closely following the Doerner-Hoskins (Doerner and Hoskins, 1925) distribution law. λMg2+C is strongly dependent on temperature, being: 0·0573 ± 0·0017 at 25°C, 0·0681 ± 0·0019 at 35°C, 0·0778 ± 0.0022 at 50°C, 0·0973 ± 0·0021 at 70°C, and 0·1163 ±0 ·0034 at 90°C. λMg2+C is independent of the absolute concentration of Ca2+ in solution as well as of the presence of NaCl.Relatively high λMg2+C values are obtained during the initial reaction stages when too-highly reactive synthetic aragonites are recrystallized. SEM micrographs show that calcite crystals grown from such aragonites are imperfect and that their earlier formed Mg-rich cores redissolve later, resulting in apparently inconsistent λMg2+C values.Calculations applying the new λMg2+C value for 25°C and the solubility data for magnesian calcites (Chaveet al., 1962) demonstrate that although no calcite should be expected to precipate directly from open sea water, its direct precipitation (or recrystallization from aragonite) is possible in closed diagenetic systems which still contain marine solutions, provided a temporary increase in the dissolved calcium concentration takes place.The λMg2+C values obtained allow for a new insight into processes of calcite cementation of reefs and a variety of other carbonate sediments, and for a more precise definition of dedolomitization chemistry.     

Calcite and aragonite saturation States of Kamaran strait surface seawater, Yemen: summer time

Surface seawater samples from Kamaran Strait of Yemen were collected for physical and chemical parameter determinations. This work reports the results of air and surface seawater temperature, salinity, pH, and total alkalinity measurements. The air temperature ranged from 29.9°C to 36.5°C with an average value of 31.5?±?1.5°C, whereas the seawater surface temperature ranged from 34.0°C to 36.0°C with a mean value of 34.5?±?0.5°C. The salinity was observed to be high, ranging from 38.03 to 38.81 with an average value of 38.45?±?0.22. The pH ranged from 7.74 to 8.27 with a mean value of 8.11?±?0.10. The total alkalinity was found to range from 2.3860 to 2.5000 meq L^?1 with an average value of 2.4288?±?0.0351 meq L^?1. The result of the study showed that there was a negative correlation between the pH and surface seawater temperature and salinity. The surface seawater of the Kamaran Strait was found to be several fold supersaturated with respect to calcium carbonate. The measured percent degree of saturation ranged from 454% to 668% with respect to calcite and from 246% to 361% with respect to aragonite. The lowest value of supersaturation with respect to both calcite and aragonite were found in front of as-Salif port, where human and developmental activities are intensively increased. The visual inspection of coral reefs distribution and their intensity were obviously observed in areas of high value of supersaturation with respect to both minerals, high transparency of seawater column, and low human activities. Further studies are needed to investigate the occurrence, distribution, and mineralogy of corals and the effects of physical and chemical parameters upon their growth in the region.     

The effects of undercooling and deformation rates on the crystallization kinetics of Stromboli and Etna basalts

We have investigated the effect of undercooling and deformation on the evolution of the texture and the crystallization kinetics of remelted basaltic material from Stromboli (pumice from the March 15, 2007 paroxysmal eruption) and Etna (1992 lava flow). Isothermal crystallization experiments were conducted at different degrees of undercooling and different applied strain rate (T = 1,157–1,187 °C and $ \dot{\gamma }_{i} $ γ · i  = 4.26 s^?1 for Stromboli; T = 1,131–1,182 °C and $ \dot{\gamma }_{i} $ γ · i  = 0.53 s^?1 for Etna). Melt viscosity increased due to the decrease in temperature and the increase in crystal content. The mineralogical assemblage comprises Sp + Plg (dominant) ± Cpx with an overall crystal fraction (?) between 0.06 and 0.27, increasing with undercooling and flow conditions. Both degree of undercooling and deformation rate deeply affect the kinetics of the crystallization process. Plagioclase nucleation incubation time strongly decreases with increasing ΔT and flow, while slow diffusion-limited growth characterizes low ΔT—low deformation rate experiments. Both Stromboli (high strain rate) and Etna (low strain rate) plagioclase growth rates (G) display relative small variations with Stromboli showing higher values (4.8 ± 1.9 × 10^?9 m s^?1) compared to Etna (2.1 ± 1.6 × 10^?9 m s^?1). Plagioclase average nucleation rates J continuously increase with undercooling from 1.4 × 10⁶ to 6.7 × 10⁶ m^?3 s^?1 for Stromboli and from 3.6 × 10⁴ to 4.0 × 10⁶ m^?3 s^?1 for Etna. The extremely low value of 3.6 × 10⁴ m^?3 s^?1 recorded at the lowest undercooling experiment for Etna (ΔT = 20 °C) indicates that the crystallization process is growth-dominated and that possible effects of textural coarsening occur. G values obtained in this paper are generally one or two orders of magnitude higher compared to those obtained in the literature for equivalent undercooling conditions. Stirring of the melt, simulating magma flow or convective conditions, facilitates nucleation and growth of crystals via mechanical transportation of matter, resulting in the higher J and G observed. Any modeling pertaining to magma dynamics in the conduit (e.g., ascent rate) and lava flow emplacement (e.g., flow rate, pāhoehoe–‘a‘ā transition) should therefore take the effects of dynamic crystallization into account.     

Syn-sedimentary hydrothermal dolomites in a lacustrine rift basin: Petrographic and geochemical evidence from the lower Cretaceous Erlian Basin,Northern China

Dolomites occur extensively in the lower Cretaceous along syn-sedimentary fault zones of the Baiyinchagan Sag, westernmost Erlian Basin, within a predominantly fluvial–lacustrine sedimentary sequence. Four types of dolomite are identified, associated with hydrothermal minerals such as natrolite, analcime and Fe-bearing magnesite. The finely-crystalline dolomites consist of anhedral to subhedral crystals (2 to 10 μm), evenly commixed with terrigenous sediments that occur either as matrix-supporting grains (Fd1) or as massive argillaceous dolostone (Fd2). Medium-crystalline (Md) dolomites are composed of subhedral to euhedral crystals aggregates (50 to 250 μm) and occur in syn-sedimentary deformation laminae/bands. Coarse-crystalline (Cd) dolomites consist of non-planar crystals (mean size >1 mm), and occur as fracture infills cross-cutting the other dolomite types. The Fd1, Md and Cd dolomites have similar values of δ¹⁸O (−20·5 to −11·0‰ Vienna PeeDee Belemnite) and δ¹³C (+1·4 to +4·5‰ Vienna PeeDee Belemnite), but Fd2 dolomites are isotopically distinct (δ¹⁸O −8·5 to −2·3‰ Vienna PeeDee Belemnite; δ¹³C +1·4 to +8·6‰ Vienna PeeDee Belemnite). Samples define three groups which differ in light rare-earth elements versus high rare-earth elements enrichment/depletion and significance of Tb, Yb and Dy anomalies. Medium-crystalline dolomites have signatures that indicate formation from brines at very high temperature, with salinities of 11·8 to 23·2 eq. wt. % NaCl and T_h values of 167 to 283°C. The calculated temperatures of Fd1 and Cd dolomites extend to slightly lower values (141 to 282°C), while Fd2 dolomites are distinctly cooler (81 to 124°C). These results suggest that the dolomites formed from hydrothermal fluid during and/or penecontemporaneous with sediment deposition. Faults and fractures bounding the basin were important conduits through which high-temperature Mg-rich fluids discharged, driven by an abnormally high heat flux associated with local volcanism. It is thought that differing amounts of cooling and degassing of these hydrothermal fluids, and of mixing with lake waters, facilitated the precipitation of dolomite and associated minerals, and resulted in the petrographic and geochemical differences between the dolomites.     

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

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

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.     

9,400 yr B.P.: the mortality of mollusk shell (<Emphasis Type="Italic">Mya truncata</Emphasis>) at high Arctic is associated with a sudden cooling event

An 118-cm-long, well-preserved sediment profile was collected from a paleo-notch formed by ocean wave action before rising to the terrace on Ny-Ålesund, Svalbard, Norway. A large number of mollusk shell fragments, predominantly Mya truncata, were found in the sediment profile. AMS ¹⁴C dating and stable oxygen and carbon isotope analyses were performed on the shell fragments samples. The reservoir-corrected radiocarbon ages averaged ~9,400 yr B.P., which accurately dates the raised terrace and the upper marine limit after Kongsfjorden was completely deglaciated. The calibrated aragonite isotopic temperature equation was established for Ny-Ålesund by comparing the δ¹⁸O profiles of modern mollusks as follows: T (°C) = 16.26 ? 3.68(δ¹⁸O_{aragonite–PDB} ? δ¹⁸O_{water–VSMOW}). The reconstructed paleotemperature range was ?0.52 to +4.78°C, warmer than today by about 1°C, which was further confirmed by reconstructed sea surface temperature (SST) in west Svalbard. Moreover, the mortality of mollusks was very likely caused by an abrupt cooling event at about 9,400 yr B.P., which was triggered by reduced insolation, weakened thermohaline circulation, and abruptly decreased SST. More evidences for this distinct but short cooling event centered at about 9,400 yr B.P. were found in Northern Siberia, North Atlantic, Alps, and Eastern Europe.     

Fluid production rate during the regional metamorphism of a pelitic schist

Phase equilibria modeling of the pressure–temperature (P–T) path of regional metamorphism and associated fluid expulsion, combined with constraints on the timescale of garnet growth by Sm–Nd geochronology, elucidates the fluid production rate and fluid flux during Barrovian metamorphism of pelitic rocks from Townshend Dam, VT, USA. This modeling builds on a published companion study that utilized Sm–Nd geochronology of concentric growth zones in multiple garnet grains, to constrain the duration of garnet growth in a large sample of schist at Townshend Dam to 3.8?±?2.2 million years (Gatewood et al., Chem Geol 401:151–168, 2015). P–T pseudosections combined with observed mineral compositions constrain garnet growth conditions, and were utilized to construct P–T path-dependent thermodynamic forward models. These models determine that garnet growth was initiated at ~?0.6 GPa and ~?525 °C, with a roughly linear loading and heating P–T trajectory to >?0.8 GPa and ~?610 °C. Loading and heating rates of 2.4 km·Myear^?1 (with a range of 1.6 to 5.8 km·million year^?1) and 23 °C·million year^?1 (with a range of 14 to 54 °C·million year^?1), respectively, are consistent with model estimates and chronologic constraints for tectono-metamorphic rates during orogenesis. Phase equilibria modeling also constrains the amount of water release during garnet growth to be ~?0.7 wt% (or >?2 vol%), largely resulting from the complete consumption of chlorite. Coupling this estimate with calculated garnet growth durations provides a fluid production rate of 5.2 kg·m^?3·million year^?1 (with a range of 3.2 to 12.2 kg·m^?3·million year^?1) and when integrated over the overlying crustal column, a regional-scale fluid flux of 0.07–0.37 kg·m^?2·million year^?1. This range of values is consistent with those derived by numerical models and theory for regional-scale, pervasive fluid flow. This study signifies the first derivation of a fluid production rate and fluid flux in regional metamorphism using a direct chronology of water-producing (garnet-forming) reactions and can provide a framework for future studies on elucidating the nature and timescales of fluid release.     

Fluid transfer of gold,palladium, and rare earth elements and genesis of ore occurrences in the Subpolar Urals

To estimate the behavior of Au, Pd, REE, and Y in magmatic and postmagmatic processes, a series of experimental studies on the solubility of noble metals and REE in magma, magmatic fluid, and hydrothermal solutions has been performed in wide temperature and pressure ranges (300–400°C, 860–1350°C; 1–14 kbar). The coefficients of Au and Pd partitioning (D ^F/L) between fluid and tholeiitic melt have been determined. Depending on P, T, and the composition of the system, they vary from 1 to 11 for Au and 0.02 to 1 for Pd. The phase solubility technique was used to determine Au and Pd solubility in hydrothermal fluid. The effects of temperature, composition, and fluid acidity on Au and Pd solubility have been estimated. The high solubility of these metals in aqueous chloride solutions has been established for both Au (28–803 mg/kg at T = 300°C, 305–1123 mg/kg at T = 350°C, and 330–1400 mg/kg at T = 400°C) and Pd (40–126 mg/kg at T = 300°C, 62–152 mg/kg at T = 350°C, and 20–210 mg/kg at T = 400°C). The coefficients of REE and Y partitioning (D ^F/L) between fluid and tholeiitic or alkaline melts have been determined. They vary from 0.00n to 2 depending on P, T, and fluid composition. The experimental data on Au and Pd solubility in solutions and magmatic fluids and the wide variation of REE D ^F/L between fluid and melt show that magmatic and hydrothermal fluids are efficient agents of Au, Pd, and REE transfer and fractionation. The obtained experimental data were used for elucidating sources of fluids and their role in the genesis of Au-Pd-REE occurrences in the Subpolar Urals.     

Columnar calcites as testimony of diagenetic overprinting at the boundary between Upper Tournaisian dolomites and limestones (Belgium): multiple origins for apparently similar features

In topographic flat areas, sedimentary settings may vary from one outcrop to another. In these settings, calcite precipitates may yield macroscopically similar columnar features, although they are products of different sedimentary or diagenetic processes. Three columnar calcite crystal fabrics, i.e. rosettes, palisade crusts and macro-columnar crystal fans, have been differentiated near and at the contact between Upper Tournaisian dolomites and limestones along the southern margin of the Brabant-Wales Palaeohigh. Their petrographic characteristics, and geochemical and fluid inclusion data provide information on the (dia)genetic processes involved. Rosettes composed of non-luminescent columnar calcite crystal fans (1–5 cm in diameter) developed on top of one another, forming discrete horizons in repetitive sedimentary cycles. The cycles consist of three horizons: (I) a basal horizon with fragments from the underlying horizon, (II) a micrite/microspar horizon with incipient glaebules, (III) an upper horizon consisting of calcite rosettes, with desiccation features. The petrographical features and δ¹⁸O signatures of −10·0 to −5·5‰ and δ¹³C values of −5·5 to −3·2‰ support either evaporative growth, an evaporative pedogenic origin, or overprinting of marine precipitates. Palisade crusts, composed of a few to 10 mm long non-luminescent calcite crystals, coat palaeokarst cavities. Successive palisade growth-stages occur which are separated by thin laminae of micrite or detrital quartz, displaying a geopetal arrangement. Palisade crusts are interpreted as intra-Mississippian speleothems. This interpretation is supported by their petrographic characteristics and isotopic signature (δ¹⁸O = −8·7 to −6·5‰ and δ¹³C = −4·8 to −2·5‰). Macro-columnar crystals, 1–50 cm long, developed mainly perpendicular to cavity walls and dolomite clasts. Crystal growth stages in the macro-columnar crystals are missing. δ¹⁸O values vary between −16·4 and −6·8‰ and δ¹³C values between −5·2 and −0·9‰. These features possibly support a late diagenetic high temperature precipitation in relation to hydrothermal karstification.     

Groundwater flow dynamics of weathered hard-rock aquifers under climate-change conditions: an illustrative example of numerical modeling through the equivalent porous media approach in the north-western Pyrenees (France)

A numerical groundwater model of the weathered crystalline aquifer of Ursuya (a major water source for the north-western Pyrenees region, south-western France) has been computed based on monitoring of hydrological, hydrodynamic and meteorological parameters over 3 years. The equivalent porous media model was used to simulate groundwater flow in the different layers of the weathered profile: from surface to depth, the weathered layer (5?·?10^?8?≤?K?≤?5?·? 10^?7 m s^?1), the transition layer (7?·?10^?8?≤?K?≤?1?·? 10^?5 m s^?1, the highest values being along major discontinuities), two fissured layers (3.5?·?10^?8?≤?K?≤?5?·?? 10^?4 m s^?1, depending on weathering profile conditions and on the existence of active fractures), and the hard-rock basement simulated with a negligible hydraulic conductivity (K = 1 10 ^?9 ). Hydrodynamic properties of these five calculation layers demonstrate both the impact of the weathering degree and of the discontinuities on the groundwater flow. The great agreement between simulated and observed hydraulic conditions allowed for validation of the methodology and its proposed use for application on analogous aquifers. With the aim of long-term management of this strategic aquifer, the model was then used to evaluate the impact of climate change on the groundwater resource. The simulations performed according to the most pessimistic climatic scenario until 2050 show a low sensitivity of the aquifer. The decreasing trend of the natural discharge is estimated at about ?360 m³ y^?1 for recharge decreasing at about ?5.6 mm y^?1 (0.8 % of annual recharge).