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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Precipitation of low-temperature disordered dolomite induced by extracellular polymeric substances of methanogenic Archaea Methanosarcina barkeri : Implications for sedimentary dolomite formation

Abstract A correlation between methanogenesis and dolomite formation has been reported; however, the mechanism underlying this association is not fully understood. In this study, we conducted forced carbonate precipitation experiments at room temperature in calcite-seeded Ca/Mg carbonate solutions containing either purified non-living biomass or bound extracellular polymeric substances (EPS) of the methanogen Methanosarcina barkeri. Purified non-living biomass and bound EPS was used so as to avoid the possible influence of the complex components of the growing microbial culture on carbonate crystallization. Our results demonstrated that non-living biomass of M. Barkeri can enhance the Mg incorporation into calcitic structure and induce the crystallization of disordered dolomite. In the presence of ~113 mg L–1 of non-living biomass, disordered dolomite with ~41 and 45 mol% of MgCO3 was precipitated in solutions with initial Mg:Ca ratios of 5:1 and 8:1, respectively. A systematic increase in the MgCO3 contents of the precipitated Ca-Mg carbonates was also observed with the increased non-living biomass concentration. Bound EPS was shown to be the component of non-living biomass that catalyzed the precipitation of disordered dolomite. At only ~25 mg L–1 of bound EPS, disordered dolomite with ~47 and 48 mol% of MgCO3 was precipitated in solutions with initial Mg:Ca ratios of 5:1 and 8:1, respectively. We propose that adsorption of bound EPS to growing carbonate surfaces through hydrogen bonding is the key to catalyzing disordered dolomite crystallization, and that this mechanism is also applicable to natural EPS-induced dolomite formation. This study provides significant insight into the formation mechanism of microbial-induced dolomite with high δ13C values.

Geochemistry & Geophysics↗
DOE OSTI2020

Massive formation of early diagenetic dolomite in the Ediacaran ocean: Constraints on the “dolomite problem”

Paleozoic and Precambrian sedimentary successions frequently contain massive dolomicrite [CaMg(CO 3 ) 2 ] units despite kinetic inhibitions to nucleation and precipitation of dolomite at Earth surface temperatures (<60 °C). This paradoxical observation is known as the “dolomite problem.” Accordingly, the genesis of these dolostones is usually attributed to burial–hydrothermal dolomitization of primary limestones (CaCO 3 ) at temperatures of >100 °C, thus raising doubt about the validity of these deposits as archives of Earth surface environments. We present a high-resolution, >63-My-long clumped-isotope temperature (T Δ47 ) record of shallow-marine dolomicrites from two drillcores of the Ediacaran (635 to 541 Ma) Doushantuo Formation in South China. Our T ∆47 record indicates that a majority (87%) of these dolostones formed at temperatures of <100 °C. When considering the regional thermal history, modeling of the influence of solid-state reordering on our T Δ47 record further suggests that most of the studied dolostones formed at temperatures of <60 °C, providing direct evidence of a low-temperature origin of these dolostones. Furthermore, calculated δ 18 O values of diagenetic fluids, rare earth element plus yttrium compositions, and petrographic observations of these dolostones are consistent with an early diagenetic origin in a rock-buffered environment. We thus propose that a precursor precipitate from seawater was subsequently dolomitized during early diagenesis in a near-surface setting to produce the large volume of dolostones in the Doushantuo Formation. Our findings suggest that the preponderance of dolomite in Paleozoic and Precambrian deposits likely reflects oceanic conditions specific to those eras and that dolostones can be faithful recorders of environmental conditions in the early oceans.

58 GEOSCIENCES↗
NASA NTRS2020

Preservation of Organic Carbon in Dolomitized Cambrian Stromatolites and Implications for Microbial Biosignatures in Diagenetically Replaced Carbonate Rock

Stromatolites have been a major focus in the search for ancient microbial life, however, the organic carbon biosignatures of dolomitized stromatolites have not yet been fully characterized or correlated with their dolomitizing conditions. Although dolomitization rarely preserves microbial morphology, the presence of organic carbon can provide valuable information for characterization of fossils’ biogenicity, syngenicity, and indigeneity to their host rock. The Cambrian Allentown Formation in New Jersey, USA, is an excellent example of dolomitized stromatolites and thrombolites containing diagenetically modified microbial biosignatures. Based on XRD and EPMA data, the dolomite composition is typically stoichiometric, with varying degrees of cationic ordering. The outcrop underwent early dolomitization in a marginal-marine setting and later burial diagenesis resulting in multi-generational dolomite formation: (1) 2 microspar dolomite formed by early diagenetic replacement at or near the surface, (2) zoned dolomite formed penecontemporaneously with the microspar phase as rhombohedral crystals by infilling primary pore spaces within the microspar matrix. The rhombic crystals continued to grow outward in alternating stages of Fe-enriched and -depleted fluids, which were preserved in zoned rims and revealed by cathodoluminescence, and (3) saddle dolomite formed during late stage deep burial with Fe- and Mn-rich fluids, and occurs as a void-filling, high-temperature phase. Organic carbon, characterized using confocal Raman microscopy, has an exclusive distribution within the microspar dolomite, and the D and G bands’ characteristics reveal similar thermal alteration to the host rock, indicating that the mapped organic carbon is indigenous and syngenetic with the Cambrian carbonates. The findings presented in this study reveal organic matter found within microspar of various dolomitized facies deriving from different source pools of organic carbon. This study sheds light on biosignatures in secondary dolostones and may aid biosignature detection in older carbonate rocks on Earth and Mars.

Dolomitization↗
DOE OSTI2020

Investigation and Analysis of Dolomite Dissolution in Variable Strength Systems Relevant to the WIPP

The Waste Isolation Pilot Plant (WIPP) was opened in 1999 as a solution to the long-term disposal of the nation's nuclear defense-generated transuranic (TRU) waste. The salt beds were recommended as the ideal location because they are free from flowing fresh water, easily mined, impermeable, and geologically stable. However, for performance assessment modeling, release scenarios must be considered. The most likely release scenario was determined to be human intrusion leading to direct and/or long-term brine release (US DOE 1995, US DOE 1996, Perkins et al., 1999). The focus of this research is the Rustler formation because it is located above the WIPP and is the most transmissive layer (Perkins et al., 1999). Objective: To determine the effect of chelating ligands ( e.g. EDTA) on dissolution of dolomite in high ionic strength systems. Do brines impact dolomite dissolution and how is it affected by EDTA binding with cations? By varying the ionic strengths, different brine conditions can be simulated similar to those in and around the Culebra member and evaluate trends of dissolved Ca and Mg in the aqueous phase from the quantified data. Conclusions: <2% of dolomite dissolved over one week at pH 8.5. Greater dissolution occurred at higher ionic strength and in the presence of NaCl with approximately 0.4 vs. 0.9% of Mg removed from dolomite in 0.1 and 1.0 M Na. Further, 0.3 vs. 0.9% of Mg was removed from dolomite in 1.0 M IS CaCl{sub 2} versus NaCl. EDTA increased dissolution of dolomite at low ionic strength due to its strong complexation affinity for Ca/Mg with slightly greater removal of Ca than Mg. Significant differences were not observed at high ionic strength due to the presence of large concentrations of competing cations (Na, Ca, Mg). Slightly higher concentrations of Ca were removed from dolomite than Mg after one week, suggesting either incongruent dissolution or release through ion exchange of Ca from trace mineral impurities. Further, when EDTA was present, it may have increased Ca removal due to its greater complexation for Ca than Mg. Environmental Implications: High ionic strength brines and low ionic strength solutions with organic ligands increase dissolution of dolomite. Due to the long half-lives of radionuclides in the TRU waste, it may be important to consider the long term impact of dolomite dissolution for potential release scenarios.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Wabash CarbonSAFE. Geologic Analysis of the Potosi Dolomite Reservoir Interval and Potential Confining Units, at the Wabash #1 Well, Vigo Co., Indiana, Subtask 7.2, Technical Report

The Wabash CarbonSAFE project drilled the Wabash #1 stratigraphic test well (ID# 168045) at the Wabash Valley Resources (WVR) IGCC facility in Vigo County, Indiana, to evaluate the feasibility of commercial-scale CO 2 storage near the site. The Mt. Simon Sandstone was the initial target for storage evaluation and was found to have generally poor reservoir qualities in the Wabash #1 well. Focus was then placed on the secondary target, the Potosi Dolomite. For storage and containment evaluation an extensive suite of geophysical logs was collected throughout the borehole, and whole cores were obtained from the Mt. Simon Sandstone, Eau Claire Formation, and Maquoketa Group. The Maquoketa Group is identified as a regionally extensive secondary sealing interval above the Mt. Simon Sandstone and as a primary seal for the Potosi Dolomite storage complex. Due to concerns over potential lost circulation zones in the Potosi Dolomite during drilling, no core samples or Formation Micro Imager (FMI) logs were acquired in the Potosi Dolomite. However, cased hole well testing was performed over a 20 feet (6 m) interval within the Potosi Dolomite during which a fluid swab sample was obtained. Approximately 35 miles of 2D seismic information was acquired in the project area near Wabash #1 to aid in reservoir and caprock characterization. The highly porous and permeable zones in the Potosi Dolomite and lower Oneota Dolomite observed within the Wabash #1 well are, for the purpose of this report, considered the same reservoir package and referred to as the Potosi reservoir interval. This report presents a regional depositional context for the Potosi reservoir interval, the overlying confining zones in the Knox Group, and Maquoketa Group primary seal. This context is developed through detailed information obtained from the Wabash #1 well such as lithologic data collected from cuttings and core, geophysical logging, geomechanical analysis of core samples, and well testing and fluid sampling within the Potosi reservoir interval. Information discussed in this report was compiled as a basis for the development of static and dynamic geologic models of the Potosi Dolomite storage complex. The static and dynamic modeling of CO 2 injection in the Potosi reservoir interval are discussed in a separate report (Dessenberger et al., 2022) under the Wabash CarbonSAFE project.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2021

Seismic fault weakening via CO 2 pressurization enhanced by mechanical deformation of dolomite fault gouges

Carbon dioxide emissions from dolomite decarbonation play an essential role in the weakening of carbonate faults by lowering the effective normal stress, which is thermally activated at temperatures above 600–700 °C. However, the mechanochemical effect of low-crystalline ultrafine fault gouge on the decarbonation and slip behavior of dolomite-bearing faults remains unclear. In this study, we obtained a series of artificial dolomite fault gouges with systematically varying particle sizes and dolomite crystallinities using a high-energy ball mill. The laboratory-scale pulverization of dolomite yielded MgO at temperatures below 50 °C, indicating that mechanical decarbonation without significant heating occurred due to the collapse of the crystalline structure, as revealed by X-ray diffraction and solid-state nuclear magnetic resonance results. Furthermore, the onset temperature of thermal decarbonation decreased to ~400 °C. Numerical modeling reproduced this two-stage decarbonation, where the pore pressure increased due to low-temperature thermal decarbonation, leading to slip weakening on the fault plane even at 400–500 °C; i.e., 200–300 °C lower than previously reported temperatures. Thus, the presence of small amounts of low-crystalline dolomite in a fault plane may lead to a severely reduced shear strength due to thermal decomposition at ~400 °C with a small slip weakening distance.

58 GEOSCIENCES↗
NASA NTRS1991

Coastal lithofacies and biofacies associated with syndepositional dolomitization and silicification (Draken Formation, Upper Riphean, Svalbard)

The Draken Formation (120-250 m) of northeast Spitsbergen (Svalbard) forms part of a thick Upper Proterozoic carbonate platform succession. It consists predominantly of intraformational dolomitic conglomerates, with excellent textural preservation. Six main lithofacies were recognized in the field: quartz sandstones, stromatolitic mats, conglomerates with silicified intraclasts, dolostone conglomerates with desiccated mudrocks, oolitic/pisolitic grainstones and fenestral dolostones. A series of five main gradational biofacies were recognized from silicified (and rare calcified) microfossils. Biofacies 1 represents low-energy subtidal benthos (erect filaments) and plankton (acritarchs and vase-shaped microfossils) whereas biofacies 2 to 5 are microbial mat assemblages (with filamentous mat-builders, and associated dwellers and washed-in plankton) ranging from basal intertidal to high intertidal/supratidal. Colour values (a measure of the lightness of the colour shade) of sawn rock samples were quantified using a Munsell chart, and exhibit a pronounced variation (means of major groups varying from 4.0 to 5.95) across the spectrum of subtidal to supratidal sediments as inferred from other criteria. The lightening in progressively more exposed sediments is related to lowering of organic carbon contents, probably mainly by oxidation. Six types of early cement have been recognized. Calcite microspar (type 1) is common as a subtidal cement in many Proterozoic formations, whereas types 2 (subtidal isopachous fringes), 3 (subtidal hardground dolomicrite) and 4 (intertidal meniscus dolomicrite) are very similar to Phanerozoic examples except for their dolomitic mineralogy. Types 5 and 6 are complex and variable dolomite growths associated with expansion and replacive phenomena. They characterize the fenestral lithofacies and compare with modern supratidal cements. Consideration of diagenetic fabrics and truncation textures of intraclasts indicates that leaching, dolomitization, silicification were all significant syndepositional processes altering the original metastable carbonates. The data set provides evidence for a spectrum of peritidal environments including ooid shoals, protected subtidal, tidal sandflats and protected carbonate mudflats. Different sections show a preponderance of particular facies. The coastal lithofacies continuum was completely dolomitized, unlike offshore to ooid shoal facies of adjacent formations. Dolomitization thus bears a relationship to depositional bathymetry. Although hydrodynamics clearly have a role, the potential importance of whiting precipitation in raising Mg/Ca in marginal marine environments is also stressed.

Non-NASA Center↗
NASA NTRS2003

Common Ion Effects In Zeoponic Substrates: Dissolution And Cation Exchange Variations Due to Additions of Calcite, Dolomite and Wollastonite

c1inoptilolite-rich tuff-hydroxyapatite mixture (zeoponic substrate) has the potential to serve as a synthetic soil-additive for plant growth. Essential plant macro-nutrients such as calcium, phosphorous, magnesium, ammonium and potassium are released into solution via dissolution of the hydroxyapatite and cation exchange on zeolite charged sites. Plant growth experiments resulting in low yield for wheat have been attributed to a Ca deficiency caused by a high degree of cation exchange by the zeolite. Batch-equilibration experiments were performed in order to determine if the Ca deficiency can be remedied by the addition of a second Ca-bearing, soluble, mineral such as calcite, dolomite or wollastonite. Variations in the amount of calcite, dolomite or wollastonite resulted in systematic changes in the concentrations of Ca and P. The addition of calcite, dolomite or wollastonite to the zeoponic substrate resulted in an exponential decrease in the phosphorous concentration in solution. The exponential rate of decay was greatest for calcite (5.60 wt. % -I), intermediate for wollastonite (2.85 wt.% -I) and least for dolomite (1.58 wt.% -I). Additions of the three minerals resulted in linear increases in the calcium concentration in solution. The rate of increase was greatest for calcite (3.64), intermediate for wollastonite (2.41) and least for dolomite (0.61). The observed changes in P and Ca concentration are consistent with the solubilities of calcite, dolomite and wollastonite and with changes expected from a common ion effect with Ca. Keywords: zeolite, zeoponics, common-ion effect, clinoptilolite, hydroxyapatite

Beiersdorfer, R. E.↗
DOE OSTI2023

Dissolution enables dolomite crystal growth near ambient conditions

Crystals grow in supersaturated solutions. A mysterious counterexample is dolomite CaMg(CO 3 ) 2 , a geologically abundant sedimentary mineral that does not readily grow at ambient conditions, not even under highly supersaturated solutions. Using atomistic simulations, we show that dolomite initially precipitates a cation-disordered surface, where high surface strains inhibit further crystal growth. However, mild undersaturation will preferentially dissolve these disordered regions, enabling increased order upon reprecipitation. Furthermore, our simulations predict that frequent cycling of a solution between supersaturation and undersaturation can accelerate dolomite growth by up to seven orders of magnitude. We validated our theory with in situ liquid cell transmission electron microscopy, directly observing bulk dolomite growth after pulses of dissolution. This mechanism explains why modern dolomite is primarily found in natural environments with pH or salinity fluctuations. More generally, it reveals that the growth and ripening of defect-free crystals can be facilitated by deliberate periods of mild dissolution.

Kim, Joonsoo↗
DOE OSTI2021

Influence of microstructure on replacement and porosity generation during experimental dolomitization of limestones

Replacement reactions commonly alter the multiscale pore structures of rocks during fluid-rock interactions. Analysis of these processes in various model fluid-rock systems during controlled laboratory experiments provides insights into the origins of microstructures found in natural materials. This study focused on understanding the effects of initial starting material permeability and resultant differences in transport pathways on porosity and mineralogical changes during limestone dolomitization.A series of replacement experiments (32–317 days in duration) have been conducted in which 1.59 cm (5/8 in.) diameter cores of two different limestones were reacted with saturated MgCl2 solutions at 200 °C. The Texas Cream (Austin Chalk) is a high-porosity, high-permeability limestone, whereas both the porosity and permeability of the Carthage Marble (Burlington Limestone) are relatively low. Altered limestones were imaged using scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX), Time-of-Flight Secondary Ion Mass Spectrometry (ToF–SIMS) and electron microprobe analysis (EMPA). A representative grain boundary of the low-porosity limestone was targeted for a focused ion beam (FIB) lift-out and characterized using transmission electron microscopy (TEM). These results were coupled with analyses of radial changes in the porosity distribution of the core derived from X-ray and neutron small- and ultra-small angle scattering ((U)SANS/(U)SAXS).The high-porosity/permeability limestone showed a four times faster bulk replacement rate than the lower-porosity/permeability material, and a different mechanism of porosity development. For the low-porosity limestone, a two-stage replacement occurred, with the reacted region of the core consisting of an inner rim in which the limestone was replaced by two calcite-dolomite solid solutions, and an outer rim in which the dolomite was replaced by magnesite. Elongated pores formed along grain boundaries at the initial limestone/dolomite reaction interface, and additional nanometer-scale porosity was formed at the secondary magnesite replacement rim. Grain boundaries were identified as preferential pathways for transport leading to dolomitization and a grain boundary diffusion rate was calculated based on microstructural characterization. In contrast, replacement in the high-porosity limestone was accompanied by porosity generation through replacement of individual grains by dolomite throughout the sample and, in longer runs, magnesite in outer parts of the core. These observations emphasize that both the mechanisms of the replacement reaction and the microstructure and chemistry of the replaced product are contingent on the initial structure of the starting material.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Radiation-Induced Changes in Single Crystal Calcite and Dolomite: Mineral Analogues of Light Water Reactor, Nuclear Power Plant Concrete Aggregates

Two analogues of aggregates (calcite and dolomite) found in nuclear power plant (NPP) concrete have been neutron irradiated to fluences up to 2 × 10 20 n/cm 2 at 52 °C and 4 × 10 19 n/cm 2 at 95 °C (E > 0.1 MeV). X-ray diffraction studies showed that these aging conditions affected crystallography of both calcite and dolomite, with both showing a growth in their unit cells compared to that of the unirradiated samples. Only dolomite samples showed a continuous increase of its lattice parameters with the increase in irradiation. In calcites, the lattice growth with irradiation dissipated after a fluence of 5 × 10 18 n/cm 2 . Radiation-induced disordering of the crystal structure was observed in both materials, while a healing effect of irradiation temperature was mainly observed in calcites. Dislocation densities calculated by using XRD data also supported these observations. Insights made into the unit cells of both minerals by using Fourier synthesis showed that the Mg sites are more prone to the neutron irradiation than the Ca sites, resulting in larger radiation effects and higher disruption in the crystal structure of dolomite than that of calcite. Furthermore, other than the polycrystalline characteristics observed by using TEM, these minerals did not show complete amorphization or significant structural decomposition at the studied irradiation fluences.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Equation of state and structural evolution of manganese dolomite (kutnohorite) under high pressures

Abstract Understanding the structural evolution of carbonate minerals with increasing pressure is essential to decoding the role of Earth’s mantle in the global carbon cycle and long-term climate change. Here, we carried out synchrotron single-crystal X-ray diffraction measurements on a natural sample of manganese dolomite [kutnohorite, Ca1.11Mn0.89(CO3)2] in a diamond-anvil cell up to 51.2 GPa at room temperature with neon as the pressure-transmitting medium. The manganese dolomite sample remains stable in the rhombohedral structure from 1 bar to ~13.3 GPa. The equation of state of Ca1.11Mn0.89(CO3)2 was determined: V0 = 334.06 ± 0.29 Å3, K0 = 99.9 ± 4.7 GPa, and K0′ = 4.3 ± 0.9; when K0′ is fixed at 4.0, V0 = 334.04 ± 0.24 Å3, and K0 = 101.4 ± 1.5 GPa. Upon further compression at room temperature, the split and disappearance of diffraction spots were observed. That is, the rhombohedral structure of manganese dolomite becomes highly distorted to lose its long-range order at 13.3–51.2 GPa at room temperature. Moreover, our single-crystal X-ray diffraction results reveal the mechanisms of the reported lattice and internal Raman mode splits of the same manganese dolomite sample approximately at 13 and 24 GPa, respectively. These results suggest manganese-bearing carbonates may play a distinct role in the deep carbon cycle.

Geochemistry & Geophysics↗
NASA NTRS2000

Mineralogical Studies of Experimentally Shocked Dolomite: Implications for the Outgassing of Carbonates

Common rock-forming rhombohedral carbonates - calcite and dolomite - constitute a considerable fraction of terrestrial sediments that may be shocked during hypervelocity impacts, such as during the Cretaceous-Tertiary (K/T) event or at the Haughton structure. The relatively modest temperatures needed to decompose carbonates and to release their CO2 are easily attained during such impacts. However, detailed and quantitative understanding of the CO2 release of carbonates as a function of shock stress is still the subject of controversy, as are a number of other reactions and phase transitions that were suggested for carbonates. The first devolatilization studies of carbonates in the early 1980s suggested that incipient devolatilization of calcite and/or dolomite commences at modest pressures, in the range < 10-18 GPa (amounting to 0.03-0.3% CO2 loss), with massive decarbonation (30-40% CO2 loss) occurring at shock pressure of 20 GPa and above. However, most later studies revealed that both calcite and dolomite are unexpectedly stable under shock conditions and no significant outgassing has been observed at pressures as high as 40 GPa for calcite and 60 GPa for dolomite. Despite these uncertainties, the calculations of O'Keefe and Ahrens (and others) serve to illustrate that the K/T bolide liberated sufficient CO2 that a substantial temperature increase of the global atmosphere is possible due to CO2-triggered greenhouse effects. The quantitative understanding of the devolatilization of carbonates as a function of shock stress is obviously critical to refine such calculations. Additional information is contained in the original extended abstract.

Skala, R.↗
DOE OSTI2022

Determining Infrared Optical Constants for Dolomite using Single Angle Reflectance and Spectroscopic Ellipsometry

The optical constants, namely the real (n) and imaginary (k) parts of the complex refractive index, are of particular interest to generate the infrared (IR) spectra of liquid and solid materials in different morphologies. To obtain n/k, however, most materials are typically not found in the monolithic forms necessary to easily measure n/k, and thus require the use of other methods such as pressing powders to form planar, specularly-reflective pellets. In this work dolomite crystals are measured using fixed-angle IR reflectance spectroscopy in both 1) a monolithic form with the crystal fixed in epoxy and polished, but data are also recorded from 2) pressed-pellet forms of powders of the same mineral using the same spectroscopic protocols. First results for the two methods are compared. It was found that the measured reflectance can vary by as much as a factor of two between the dolomite crystals and the pressed powder forms. For the two-sample preparation approaches the preliminary spectra are compared and the implications and limitations of each method for determining the optical constants of given materials are discussed. Comparison to literature data suggest that polarization effects likely account for the differing amplitude results for reflectance (and hence the k -vectors): Dolomite is known to be biaxial with significantly differing ordinary and extraordinary rays; the pressed pellet method measures an ensemble of microcrystals in randomly oriented positions, whereas the single crystal maintains just one orientation relative to the optical axis.

ellipsometry, dolomite, complex refractive index, ↗
NASA NTRS1991

Carbonate stability in the earth's mantle - A vibrational spectroscopic study of aragonite and dolomite at high pressures and temperatures

The structural changes of aragonite and dolomite taking place at high pressures and temperatures were investigated by measuring the Raman spectra of these materials to pressures of 23 and 28 GPa (generated in a diamond anvil cell), respectively; in addition, the IR spectra of aragonite were measured to 40 GPa. The spectroscopic data demonstrated that, at 300 K, dolomite and aragonite samples were stable to pressures of 28 and 41 GPa, respectively. No phase transitions were observed following heating of aragonite and dolomite to temperatures of 2000 K and 800 K, respectively. The mode Grueneisen parameters indicate that the carbonate group in these two minerals is relatively insensitive to pressure, with the dominant compaction mechanism being the compression of the Ca and Mg polyhedra.

Kraft, Susan↗
NASA NTRS2019

Estimated Refractive Indices of Calcite, Dolomite, and Magnesite: ~0.3-500 M.

Carbonate minerals are germane to questions involving volatile and climate history on Mars [e.g., 1-2]. In particular, the abundance of carbonate-bearing minerals can provide broad useful bounds on the amount of CO2 out-gassed into the atmosphere over its history and their spatial distribution and mineralogy can yield constraints on the environments in which they were produced. Earth-based, orbital, and landed spectral observations provide evidence for the presence of carbonates in the Martian environment [3-6]. Infrared observations made from spacecraft near Mars were interpreted to indicate the presence of carbonates. [6] associated the carbonates with the surface dust and interpreted the mineralogy as being consistent with magnesite (MgCO3). Near- infrared observations from Mars orbit have been interpreted to suggest magnesite outcrops in restricted locations [7-9]. Quantitative estimates of the abundance of carbonates on Mars range from 0-3% [3], 2-5% [6], less than a few percent [10], and <10% [8]. With the growing evidence for magnesite on Mars additional quantitative estimates can be provided via theoretical modeling of the reflectance from the Martian surface. Calcite (CaCO3) and dolomite ((Ca,Mg)CO3) are identified in Asian dust [2-17%], [10] and calcite in Saharan dust [~8-10% [12-15]. The importance of op- tical constants at visible and near-infrared wavelengths as proxies for estimating the effects at infrared wave- lengths, has been investigated [15]. The growing evidence for Mg-carbonates on Mars, the presence of calcite and dolomite in terrestrial aero- sols, and general lack of optical constants for these materials in the visible- to mid-infrared (VMIR, ~0.3-6 ❍m) has motivated the current effort to estimate the optical constants of calcite, dolomite, and magnesite in the VMIR.

Roush, T. L.↗
DOE OSTI2020

High-pressure elastic properties of dolomite melt supporting carbonate-induced melting in deep upper mantle

Deeply subducted carbonates likely cause low-degree melting of the upper mantle and thus play an important role in the deep carbon cycle. However, direct seismic detection of carbonate-induced partial melts in the Earth’s interior is hindered by our poor knowledge on the elastic properties of carbonate melts. Here we report the first experimentally determined sound velocity and density data on dolomite melt up to 5.9 GPa and 2046 K by in-situ ultrasonic and sink-float techniques, respectively, as well as first-principles molecular dynamics simulations of dolomite melt up to 16 GPa and 3000 K. Using our new elasticity data, the calculated V P /V S ratio of the deep upper mantle (~180–330 km) with a small amount of carbonate-rich melt provides a natural explanation for the elevated V P /V S ratio of the upper mantle from global seismic observations, supporting the pervasive presence of a low-degree carbonate-rich partial melt (~0.05%) that is consistent with the volatile-induced or redox-regulated initial melting in the upper mantle as argued by petrologic studies. This carbonate-rich partial melt region implies a global average carbon (C) concentration of 80–140 ppm. by weight in the deep upper mantle source region, consistent with the mantle carbon content determined from geochemical studies.

58 GEOSCIENCES↗
NASA NTRS1970

Multispectral analysis of limestone, dolomite, and granite, Mill Creek, Oklahoma

Spectral reflectance and thermal emission data were collected at the Mill Creek, Oklahoma test site during NASA missions 132 and 133 in June 1970. The data were collected by three aircraft flown several times during the diurnal cycle at altitudes of 150 to 17,000 m above mean terrain. Reflectance of the main rock types (limestone, dolomite, and granite) was determined from the data collected using a 12-channel multispectral scanner during mission 133 and from thermal infrared images recorded during mission 132 on an RS-7 scanner from 17,000 m above terrain. A preliminary rock recognition map was generated automatically using data collected from 900 m above terrain. The discrimination provided by the map is reasonably accurate. Misidentification occurred in areas of unusually high dolomite reflectivity. High altitude thermal infrared (10 to 12 micrometers) images show regional folds and faults distinguished by the presence of thermally contrasting materials. Linear and curvilinear structural features two to three times smaller than the nominal 17 m resolution could be detected.

Rowan, L. C.↗