Controls of temperature and mineral growth rate on Mg incorporation in aragonite

International audienceThe incorporation of Mg in aragonite was experimentally investigated as a function of mineral growth rate at 5, 15 and 25 °C using the constant addition technique. Aragonite growth rate was found to be the major parameter affecting the Mg partitioning coefficient (i.e. ) between aragonite and fluid, whereas the effect of temperature is smaller but measurable. At similar surface normalized growth rates, DMg values decrease as temperature increases from 5 to 25 °C. The magnitude of decrease as a function of temperature is similar for all the experiments of this study where growth rate varied in the range 10-8.6 ≤ rp ≤ 10-7.1 (mol/m2/s). The combined effect of aragonite growth rate and temperature on DMg can be described by the linear equation:Log DMg = 0.583(±0.020) Log rp − 0.026(±0.001) T + 0.863(±0.153); R2 = 0.97.where T is the temperature in degrees Celsius.The increase of DMg values at decreasing temperatures in experiments conducted at similar growth rates is consistent with the increase of fluid supersaturation with respect to aragonite. Thus, it can be inferred that increased Mg incorporation at higher supersaturation is associated with the greater presence of defect sites on the growing mineral surface, similar to the incorporation of other incompatible ions in carbonate minerals. Overall, the relationship between Mg content of aragonite with the degree of saturation of the fluid with respect to this mineral phase suggests that DMg values or Mg/Ca ratio in natural aragonites can be used as a proxy for saturation degree of the formation fluid with respect to CaCO3 minerals

Solubility investigations in the amorphous calcium magnesium carbonate system

International audienceAmorphous precursors are known to occur in the early stages of carbonate mineral formation in both biotic and abiotic environments. Although the Mg content of amorphous calcium magnesium carbonate (ACMC) is a crucial factor for its temporal stabilization, to date little is known about its control on ACMC solubility. Therefore, amorphous CaxMg1−xCO3·nH2O solids with 0 ≤ x ≤ 1 and 0.4 ≤ n ≤ 0.8 were synthesized and dispersed in MgCl2–NaHCO3 buffered solutions at 24.5 ± 0.5 °C. The chemical evolution of the solution and the precipitate clearly shows an instantaneous exchange of ions between ACMC and aqueous solution. The obtained ion activity product for ACMC (IAPACMC = “solubility product”) increases as a function of its Mg content ([Mg]ACMC = (1 − x) × 100 in mol%) according to the expression: log(IAPACMC) = 0.0174 (±0.0013) × [Mg]ACMC − 6.278 (±0.046) (R2 = 0.98), where the log(IAPACMC) shift from Ca (−6.28 ± 0.05) to Mg (−4.54 ± 0.16) ACMC endmember, can be explained by the increasing water content and changes in short-range order, as Ca is substituted by Mg in the ACMC structure. The results of this study shed light on the factors controlling ACMC solubility and its temporal stability in aqueous solutions

Effect of temperature on the transformation of amorphous calcium magnesium carbonate with near-dolomite stoichiometry into high Mg-calcite

International audienceAmorphous calcium magnesium carbonate (ACMC) transformation into high Mg-calcite (HMC) proceeds via dissolution and re-precipitation at the ACMC-solution interface

Control of MgSO40(aq) on the transformation of amorphous calcium carbonate to high-Mg calcite and long-term reactivity of the crystalline solid

International audienceThe Mg and SO 4 content of naturally occurring calcite are routinely used as paleoenvironmental proxies. Yet little is known about the mechanisms governing the presence of these ions in carbonate minerals when their formation proceeds via an amorphous precursor. To address this, the transformation of Mg-free amorphous calcium carbonate (ACC) into nanocrystalline high-Mg calcite (HMC) was experimentally studied in solutions containing 27 mM of Mg and a range of 10-90 mM of SO 4. The obtained results suggest that ACC is stable for several minutes in the experimental solutions and this amorphous phase actively uptakes Mg and SO 4 that are incorporated in its structure. Additionally, the obtained results suggest that the stabilization of ACC is not affected by its Mg content and that the transformation to HMC is effectively controlled by the abundance of the free Mg 2+ (aq) ion. The transformation of ACC to HMC occurs earlier at elevated SO 4 concentrations because SO 4 limits the availability of Mg 2+ (aq) due to the formation of the MgSO 4 0 (aq) complex. The HMC that is formed from ACC appears as aggregates composed of nanocrystallites and exhibits Mg and SO 4 contents up to 8 and 2 mol% depending on the initial SO 4 concentration in the reactive solution. The precipitated HMC was kept in contact with the reactive solution in order to assess its reactivity for up to 1 year of reaction time. Over time, a continuous exchange of Mg and SO 4 between calcite and reactive solution was observed resulting in enrichment of Mg and depletion of SO 4 affecting the total mass of the aggregates with the distribution of these elements to appear homogeneous in the crystalline solid. The high reactivity and the continuous exchange of solutes between the nanocrystalline calcite and the reactive solutions limits the use of Mg and SO 4 content of these HMCs as environmental proxies

Mg-Rich Authigenic Carbonates in Coastal Facies of the Vtoroe Zasechnoe Lake (Southwest Siberia): First Assessment and Possible Mechanisms of Formation

The formation of Mg-rich carbonates in continental lakes throughout the world is highly relevant to irreversible CO2 sequestration and the reconstruction of paleo-sedimentary environments. Here, preliminary results on Mg-rich carbonate formation at the coastal zone of Lake Vtoroe Zasechnoe, representing the Setovskiye group of water bodies located in the forest-steppe zone of Southwest Western Siberia, are reported. The Setovskiye lakes are Cl−–Na+–(SO42−) type, alkaline, and medium or highly saline. The results of microscopic and mineralogical studies of microbialites from shallow coastal waters of Lake Vtoroe Zasechnoe demonstrated that Mg in the studied lake was precipitated in the form of hydrous Mg carbonates, which occur as radially divergent crystals that form clusters in a dumbbell or star shape. It is possible that hydrous Mg carbonate forms due to the mineralization of exopolymeric substances (EPS) around bacterial cells within the algal mats. Therefore, the Vtoroe Zasechnoe Lake represents a rare case of Mg-carbonates formation under contemporary lacustrine conditions. Further research on this, as well as other lakes of Setovskiye group, is needed for a better understanding of the possible role of biomineralization and abiotic mechanisms, such as winter freezing and solute concentration, in the formation of authigenic Mg carbonate in modern aquatic environments

The Relationship between Bacterial Sulfur Cycling and Ca/Mg Carbonate Precipitation : Old Tales and New Insights from Lagoa Vermelha and Brejo do Espinho, Brazil

Over the few past decades, the concept of microbial sulfur cycling catalyzing the precipitation of CaMg (CO3)2 at low temperatures (<40 °C) has been studied intensely. In this respect, two hypersaline lagoons, Lagoa Vermelha and Brejo do Espinho, in Brazil, have been the subject of numerous studies investigating sedimentary Ca/Mg carbonate formation. Here, we present the sulfur and oxygen isotopic compositions of dissolved sulfate from surface water, as well as sulfate and sulfide from pore-water (δ34SSO4, δ18OSO4, and δ34SH2S), the sulfur isotopic composition of sedimentary pyrite (δ34SCRS), and sulfur and oxygen isotopic compositions of carbonate-associated sulfate (CAS, δ34SCAS and δ18OCAS). The pore-water profiles at Lagoa Vermelha indicate ongoing bacterial sulfate reduction by increasing δ34SSO4, δ18OSO4 and δ34SCRS values downcore. At Brejo do Espinho, the pore-water profiles displayed no depth-dependent isotope trends; the Ca/Mg ratio was, on average, lower, and the δ18OSO4 values in both surface and pore-water were strongly enriched in 18O. There was an overall mismatch between δ34SSO4 and the significantly higher δ34SCAS values. A negative correlation was observed between the Ca/Mg ratio and higher δ34SCAS values. The results show that the size difference between the two lagoons induces differences in the intensity of evaporation, which leads to the increased secretion of extrapolymeric substances (EPSs) by microbes in the smaller Brejo do Espinho. EPS provides the microenvironment where Ca/Mg carbonate can nucleate and preserve increased δ34SCAS values. Apart from EPS, increased sulfur oxidation is proposed to be a second factor causing relative enrichment of Ca/Mg carbonates at Brejo do Espinho. Our results emphasize the role of evaporative processes on Ca/Mg carbonate formation, and indicate that the respective δ34SCAS values reflect microenvironments rather than preserving an open marine δ34SSO4 signature

Late Holocene to recent aragonite-cemented transgressive lag deposits in the Abu Dhabi lagoon and intertidal sabkha

Modern cemented intervals (beachrock, firmgrounds to hardgrounds and concretionary layers) form in the lagoon and intertidal sabkha of Abu Dhabi. Seafloor lithification actively occurs in open, current-swept channels in low-lying areas between ooid shoals, in the intertidal zone of the middle lagoon, some centimetres beneath the inner lagoonal seafloor (i.e. within the sediment column) and at the sediment surface the intertidal sabkha. The concept of "concretionary sub-hardgrounds", i.e. laminar cementation of sediments formed within the sediment column beneath the shallow redox boundary, is introduced and discussed. Based on calibrated radiocarbon ages, seafloor lithification commenced during the Middle to Late Holocene ($\it {ca}$ 9000 cal yr $\tiny {BP})$, and proceeds to the present-day. Lithification occurs in the context of the actualistic relative sea-level rise shifting the coastline landward across the extremely low-angle carbonate ramp. The cemented intervals are interpreted as parasequence boundaries in the sense of "marine flooding surfaces", but in most cases the sedimentary cover overlying the transgressive surface has not yet been deposited. Aragonite, (micritic) calcite and, less commonly, gypsum cements lithify the firmground/hardground intervals. Cements are described and placed into context with their depositional and marine diagenetic environments and characterized by means of scanning electron microscope petrography, cathodoluminescence microscopy and Raman spectroscopy. The morphology of aragonitic cements changes from needle-shaped forms in lithified decapod burrows of the outer lagoon ooidal shoals to complex columnar, lath and platy crystals in the inner lagoon. Precipitation experiments provide first tentative evidence for the parameters that induce changes in aragonite cement morphology. Data shown here shed light on ancient, formerly aragonite-cemented seafloors, now altered to diagenetic calcites, but also document the complexity of highly dynamic near coastal depositional environments