On the quantitative thermogravimetric analysis of calcite content in hydrated cementitious systems

Calcite is a compound that is present in hydrated cementitious materials when carbonation of portlandite occurs or when limestone constituents are used. The quantification of its content in cementitious systems is then frequently necessary. Thermogravimetry (TG) measures the change in mass of a material (as a function of time) over a temperature range using a predetermined heating rate. It can be applied to estimate calcite content in the hydrated cement system, considering the temperature range at which it decomposes and releases carbon dioxide. However, the quantification is not easy because the onset of this decomposition is a function of many variables. The tangential method over the TG signal or the integration method over the derivative TG curve (DTG) are usually used to discount the background over the temperature range at which calcite decomposes. However, consistent underestimation of compounds is frequently described. The reasons for this are unclear and some hypothesis are discussed in this paper. Additionally, experimental quantitative TG of cement paste and aggregate containing calcite and diluted with low contents of analytical calcite are compared with the expected contents, as a calibration method regarding calcite content in the samples is given to improve the reliability of the results

Fluid evolution in CM carbonaceous chondrites tracked through the oxygen isotopic compositions of carbonates

The oxygen isotopic compositions of calcite grains in four CM carbonaceous chondrites have been determined by NanoSIMS, and results reveal that aqueous solutions evolved in a similar manner between parent body regions with different intensities of aqueous alteration. Two types of calcite were identified in Murchison, Mighei, Cold Bokkeveld and LaPaz Icefield 031166 by differences in their petrographic properties and oxygen isotope values. Type 1 calcite occurs as small equant grains that formed by filling of pore spaces in meteorite matrices during the earliest stages of alteration. On average, the type 1 grains have a δ18O of ∼32–36‰ (VSMOW), and Δ17O of between ∼2‰ and −1‰. Most grains of type 2 calcite precipitated after type 1. They contain micropores and inclusions, and have replaced ferromagnesian silicate minerals. Type 2 calcite has an average δ18O of ∼21–24‰ (VSMOW) and a Δ17O of between ∼−1‰ and −3‰. Such consistent isotopic differences between the two calcite types show that they formed in discrete episodes and from solutions whose δ18O and δ17O values had changed by reaction with parent body silicates, as predicted by the closed-system model for aqueous alteration. Temperatures are likely to have increased over the timespan of calcite precipitation, possibly owing to exothermic serpentinisation. The most highly altered CM chondrites commonly contain dolomite in addition to calcite. Dolomite grains in two previously studied CM chondrites have a narrow range in δ18O (∼25–29‰ VSMOW), with Δ17O ∼−1‰ to −3‰. These grains are likely to have precipitated between types 1 and 2 calcite, and in response to a transient heating event and/or a brief increase in fluid magnesium/calcium ratios. In spite of this evidence for localised excursions in temperature and/or solution chemistry, the carbonate oxygen isotope record shows that fluid evolution was comparable between many parent body regions. The CM carbonaceous chondrites studied here therefore sample either several parent bodies with a very similar initial composition and evolution or, more probably, a single C-type asteroid

Refining the interpretation of lacustrine carbonate isotope records: Implications of a mineralogy-specific Lake Van case study

Oxygen and carbon isotope (δ18O and δ13C) data from bulk carbonates are widely applied proxies for temperature, the precipitation/evaporation ratio and productivity in lacustrine palaeohydrology and palaeoclimatology. In case of the terminal and alkaline Lake Van, however, previous studies have shown that bulk oxygen isotope compositions are in disagreement with other proxies when interpreted in a conventional manner. Similarly, the reports on the nature and the timing and site of carbonate precipitation in Lake Van are inconsistent. This study provides evidence on the mineralogy (X-ray powder diffraction analysis, scanning electron microscope imaging, confocal Raman microscopy, electron microprobe analysis) and isotope composition (δ18O and δ13C) of non-skeletal carbonate minerals in a Lake Van sedimentary profile spanning the last ca. 150 kyr. Carbonate phases present in the sediment include aragonite, low-Mg calcite, and calcian dolomite. Dolomite forms as an early diagenetic phase and occurs episodically in high concentrations driving the bulk isotope record towards the higher dolomite δ18O and varying δ13C values. Aragonite and low-Mg calcite precipitate in the surface water and are present in the sediments in varying amounts (relative aragonite to calcite content for dolomite-poor samples Ar/(Ar + Cc) of 93 to 41 wt%). In an attempt to explain this variation, we revised a precipitation model based on annually laminated sediments containing both aragonite and calcite spatially separated in light and dark coloured laminae, respectively. According to our model, spring calcite precipitation, under close-to-freshwater conditions, is followed by evapoconcentration-driven aragonite precipitation in late summer. The precipitation of these carbonate polymorphs from chemically differing surface waters (i.e. freshwater-influenced and evapoconcentrated) leads to distinctly different oxygen and carbon isotope signatures between sedimentary penecontemporaneous aragonite and calcite. The δ18O and δ13C values of aragonite relative to calcite are significantly higher by several per mille than inferred from aragonite-calcite fractionation factors alone, suggesting that the generalised assumption of sedimentary coeval calcite and aragonite precipitating from water with the same isotopic composition is flawed. The here proposed revised hydrologically-separated carbonate precipitation model is not only taking (i) differences in the isotopic fractionation between carbonate minerals into account, but also (ii) considering the hydrological conditions and the processes favouring the precipitation of a given mineral and ultimately controlling its isotopic composition. If mixed mineralogies are present, this mineralogy-specific approach has the potential of refining environmental reconstructions and reconciling apparently equivocal interpretations of different proxy records

Testing the impact of diagenesis on the delta O-18 and delta C-13 of benthic foraminiferal calcite from a sediment burial depth transect in the equatorial Pacific

Stable oxygen and carbon isotope (δ18O and δ13C) values measured in foraminiferal calcite are one of the primary tools used in paleoceanography. Diagenetic recrystallisation of foraminiferal calcite can act to reset primary isotopic values but its effects are typically poorly quantified. Here we test the impact of early stage diagenesis on stable isotope records generated from a suite of drill sites in the equatorial Pacific Ocean recovered during Ocean Drilling Program (ODP) Leg 199 and Integrated Ocean Drilling Program (IODP) Expedition 320. Our selected sites form paleowater- and burial-depth transects, with excellent stratigraphic control allowing us to confidently correlate our records. We observe large inter-site differences in the preservation state of benthic foraminiferal calcite, implying very different recrystallisation histories, but negligible inter-site offsets in benthic δ18O and δ13C values. We infer that diagenetic alteration of benthic foraminiferal calcite (in sedimentary oozes) must predominantly occur at shallow burial depths (<100 m) where offsets in both the temperature and isotopic composition of waters in which the foraminifera calcified and pore-waters in which diagenesis occurs are small. Our results suggest that even extensive recrystallisation of benthic foraminiferal calcite results in minimal shifts from primary δ18O and δ13C values. This finding supports the long-held suspicion that diagenetic alteration of foraminiferal calcite is less problematic in benthic than in planktic foraminifera and that in deep–sea sediments routinely employed for palaeoceanographic studies benthic foraminifera are robust recorders of stable isotope values in the fossil record

The oxygen isotope evolution of parent body aqueous solutions as recorded by multiple carbonate generations in the Lonewolf Nunataks 94101 CM2 carbonaceous chondrite

The CM2 carbonaceous chondrite LON 94101 contains aragonite and two generations of calcite that provide snapshots of the chemical and isotopic evolution of aqueous solutions during parent body alteration. Aragonite was the first carbonate to crystallize. It is rare, heterogeneously distributed within the meteorite matrix, and its mean oxygen isotope values are δ18O 39.9±0.6‰, Δ17O -0.3±1.0‰ (1σ). Calcite precipitated very soon afterwards, and following a fall in solution Mg/Ca ratios, to produce small equant grains with a mean oxygen isotope value of δ18O 37.5±0.7‰, Δ17O 1.4±1.1‰ (1σ). These grains were partially or completely replaced by serpentine and tochilinite prior to precipitation of the second generation of calcite, which occluded an open fracture to form a millimeter-sized vein, and replaced anhydrous silicates within chondrules and the matrix. The vein calcite has a mean composition of δ18O 18.4±0.3‰, Δ17O -0.5±0.5‰ (1σ). Petrographic and isotopic results therefore reveal two discrete episodes of mineralization that produced Ca-carbonates with contrasting δ18O, but whose Δ17O values are indistinguishable within error. The aragonite and equant calcite crystallized over a relatively brief period early in the aqueous alteration history of the parent body, and from static fluids that were evolving chemically in response to mineral dissolution and precipitation. The second calcite generation crystallized from solutions of a lower Δ17O, and a lower δ18O and/or higher temperature, which entered LON 9410 via a fracture network. As two generations of calcite whose petrographic characteristics and oxygen isotopic compositions are similar to those in LON 94101 occur in at least one other CM2, multiphase carbonate mineralization could be the typical outcome of the sequence of chemical reactions during parent body aqueous alteration. It is equally possible however that the second generation of calcite in formed in response to an event such as impact fracturing and concomitant fluid mobilisation that affected a large region of the common parent body of several CM2 meteorites. These findings show that integrated petrographic, chemical and isotopic studies can provide new insights into the mechanisms of parent body alteration including the spatial and temporal dynamics of the aqueous system

Shock temperatures in calcite (CaCO3): Implication for shock induced decomposition

The temperatures induced in crystalline calcite upon planar shock compression (95–160 GPa) are reported from two-stage light gas-gun experiments. The temperatures are obtained fitting 6-channel optical pyrometer radiances in the 450 to 900 nm range, to a Planck radiation law temperature varied from 3300 to 5400 K. Calculations demonstrate that the temperatures are some 400 to 1350 K lower than if either shock-induced melting and/or disproportionation of calcite behind the shock front was not occurring. Here calcite is modeled as disproportionating into a molecular liquid, or a solid CaO plus CO2 gas. For temperature calculations, specific heat at constant volume for one mole of CO2 is taken to be 6.7R as compared to 9R in the solid state; whereas calcite and CaO have their solid state values (15R and 6R). Calculations also suggest that the onset of decomposition in calcite to CaO and CO2 during loading occurs at ~75±10 GPa, along the Hugoniot whereas decomposition begins upon unloading from 18 GPa. The 18 GPa value is based on comparison of VISAR measurements of particle velocity profiles induced upon isentropic expansion with one-dimensional numerical simulation

Carbonates in space - The challenge of low temperature data

Carbonates have repeatedly been discussed as possible carriers of stardust emission bands. However, the band assignments proposed so far were mainly based on room temperature powder transmission spectra of the respective minerals. Since very cold calcite grains have been claimed to be present in protostars and in Planetary Nebulae such as NGC 6302, the changes of their dielectric functions at low temperatures are relevant from an astronomical point of view. We have derived the IR optical constants of calcite and dolomite from reflectance spectra - measured at 300, 200, 100 and 10K - and calculated small particle spectra for different grain shapes, with the following results: i) The absorption efficiency factors both of calcite and dolomite are extremely dependent on the particle shapes. This is due to the high peak values of the optical constants of CaCO3 and CaMg[CO3]2. ii) The far infrared properties of calcite and dolomite depend also very significantly on the temperature. Below 200K, a pronounced sharpening and increase in the band strengths of the FIR resonances occurs. iii) In view of the intrinsic strength and sharpening of the 44 mum band of calcite at 200-100K, the absence of this band -- inferred from Infrared Space Observatory data -- in PNe requires dust temperatures below 45K. iv) Calcite grains at such low temperatures can account for the '92' mum band, while our data rule out dolomite as the carrier of the 60-65 mum band. The optical constants here presented are publicly available in the electronic database http://www.astro.uni-jena.de/Laboratory/OCDBComment: 20 pages, 10 figures, accepted by ApJ, corrected typo

Assessment of crystallographic influence on material properties of calcite brachiopods

Calcium carbonate biominerals are frequently analysed in materials science due to their abundance, diversity and unique material properties. Aragonite nacre is intensively studied, but less information is available about the material properties of biogenic calcite, despite its occurrence in a wide range of structures in different organisms. In particular, there is insufficient knowledge about how preferential crystallographic orientations influence these material properties. Here, we study the influence of crystallography on material properties in calcite semi-nacre and fibres of brachiopod shells using nano-indentation and electron backscatter diffraction (EBSD). The nano-indentation results show that calcite semi-nacre is a harder and stiffer (H {approx} 3–5 GPa; E = 50–85 GPa) biomineral structure than calcite fibres (H = 0.4–3 GPa; E = 30–60 GPa). The integration of EBSD to these studies has revealed a relationship between the crystallography and material properties at high spatial resolution for calcite semi-nacre. The presence of crystals with the c-axis perpendicular to the plane-of-view in longitudinal section increases hardness and stiffness. The present study determines how nano-indentation and EBSD can be combined to provide a detailed understanding of biomineral structures and their analysis for application in materials science

Arsenite sorption and co-precipitation with calcite

Sorption of As(III) by calcite was investigated as a function of As(III) concentration, time and pH. The sorption isotherm, i.e. the log As(III) vs. log [As(OH)3 degrees / Assat] plot is S-shaped and has been modelled on an extended version of the surface precipitation model. At low concentrations, As(OH)3 degrees is adsorbed by complexation to surface Ca surface sites, as previously described by the X-ray standing wave technique. The inflexion point of the isotherm, where As(OH)3 degrees is limited by the amount of surface sites (ST), yields 6 sites nm-2 in good agreement with crystallographic data. Beyond this value, the amount of sorbed arsenic increases linearly with solution concentration, up to the saturation of arsenic with respect to the precipitation of CaHAsO3(s). The solid solutions formed in this concentration range were examined by X-ray and neutron diffraction. The doped calcite lattice parameters increase with arsenic content while c/a ratio remains constant. Our results made on bulk calcite on the atomic displacement of As atoms along [0001] direction extend those published by Cheng et al., (1999) on calcite surface. This study provides a molecular-level explanation for why As(III) is trapped by calcite in industrial treatments.Comment: 9 page