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At least 19 records

Spectral reflectance of carbonate minerals in the visible and near infrared (0.35-2.55 microns) - Anhydrous carbonate minerals

Visible and near IR reflectance spectra for anhydrous carbonate minerals are presented, and the use of the spectra to determine the mineralogy and gaining information for the carbonate minerals is examined. Seven strong absorption bands at wavelengths greater than 1.6 microns are observed in all the spectra of anhydrous end-member carbonate minerals. The band position, intensity, and width for the carbonate bands are studied. The iron and maganese bands for the carbonate minerals are analyzed. The potential causes of spectral differences between carbonate minerals are investigated.

Gaffey, Susan J.

Carbonate Mineral Formation on Mars: Clues from Stable Isotope Variation Seen in Cryogenic Laboratory Studies of Carbonate Salts

The geologic history of water on the planet Mars is intimately connected to the formation of carbonate minerals through atmospheric CO2 and its control of the climate history of Mars. Carbonate mineral formation under modern martian atmospheric conditions could be a critical factor in controlling the martian climate in a means similar to the rock weathering cycle on Earth. The combination of evidence for liquid water on the martian surface and cold surface conditions suggest fluid freezing could be very common on the surface of Mars. Cryogenic calcite forms readily when a rise in pH occurs as a result of carbon dioxide degassing quickly from freezing Ca-bicarbonate-rich water solutions. This is a process that has been observed in some terrestrial settings such as arctic permafrost cave deposits, lakebeds of the Dry Valleys of Antarctica, and in aufeis (river icings) from rivers of N.E. Alaska. We report here the results of a series of laboratory experiments that were conducted to simulate potential cryogenic carbonate formation on the planet Mars. These results indicate that carbonates grown under martian conditions (controlled atmospheric pressure and temperature) show enrichments from starting bicarbonate fluids in both carbon and oxygen isotopes beyond equilibrium values with average delta13C(DIC-CARB) values of ~20.5%0 which exceed the expected equilibrium fractionation factor of [10(sup 3) ln alpha = ~13%0] at 0 degC. Oxygen isotopes showed a smaller enrichment with delta18O(H2O-CARB) values of ~35.5%0, slightly exceeding the equilibrium fractionation factor of [10(sup 3) ln alpha = ~34%0 ] at 0degC. Large kinetic carbon isotope effects during carbonate precipitation could substantially affect the carbon isotope evolution of CO2 on Mars allowing for more efficient removal of 13C from the Noachian atmosphere enriched by atmospheric loss. This mechanism would be consistent with the observations of large carbon isotope variations in martian materials despite the relative paucity of carbonate minerals in the martian crust.

Socki, Richard

Bulk and Stable Isotopic Compositions of Carbonate Minerals in Martian Meteorite Allan Hills 84001: No Proof of High Formation Temperature

Understanding the origin of carbonate minerals in the Martian meteorite Allan Hills (ALH) 84001 is crucial to evaluating the hypothesis that they contain traces of ancient Martian life. Using arguments based on chemical equilibria among carbonates and fluids, an origin at greater than 650 C (inimical to life) has been proposed. However, the bulk and stable isotopic compositions of the carbonate minerals are open to multiple interpretations and so lend no particular support to a high-temperature origin. Other methods (possibly less direct) will have to be used to determine the formation temperature of the carbonates in ALH 84001.

Treiman, Allan H.

Spectral reflectance of carbonate minerals and rocks in the visible and near infrared (0.35 - 2.55 microns) and its applications in carbonate petrology

Reflection spectroscopy in the visible and near infrared (0.35 to 2.55 micron) offers a rapid, inexpensive, nondestructive tool for determining the mineralogy and investigating the minor element chemistry of the hard-to-discriminate carbonate minerals, and can, in one step, provide information previously obtainable only by the combined application of two or more analytical techniques. When light interacts with a mineral certain wavelengths are preferentially absorbed. The number, positions, widths and relative intensities of these absorptions are diagnostic of the mineralogy and chemical composition of the sample. At least seven bands due to vibrations of the carbonate radical occur between 1.60 and 2.55 micron. Positions of these bands vary from one carbonae mineral to another and can be used for mineral identification. Cation mass is the primary factor controlling band position; cation radius plays a secondary role.

Gaffey, S. J.

Exploring Carbon Mineral Systems: Recent Advances in C Mineral Evolution, Mineral Ecology, and Network Analysis

Large and growing data resources on the spatial and temporal diversity and distribution of the more than 400 carbon-bearing mineral species reveal patterns of mineral evolution and ecology. Recent advances in analytical and visualization techniques leverage these data and are propelling mineralogy from a largely descriptive field into one of prediction within complex, integrated, multidimensional systems. These discoveries include: (1) systematic changes in the character of carbon minerals and their networks of coexisting species through deep time; (2) improved statistical predictions of the number and types of carbon minerals that occur on Earth but are yet to be discovered and described; and (3) a range of proposed and ongoing studies related to the quantification of network structures and trends, relation of mineral “natural kinds” to their genetic environments, prediction of the location of mineral species across the globe, examination of the tectonic drivers of mineralization through deep time, quantification of preservational and sampling bias in the mineralogical record, and characterization of feedback relationships between minerals and geochemical environments with microbial populations. These aspects of Earth’s carbon mineralogy underscore the complex coevolution of the geosphere and biosphere and highlight the possibility for scientific discovery in Earth and planetary systems.

Carbon

Carbon Limited Soils of Iceland: Analogs for Identifying Carbon-Mineral Interactions in Gale Crater, Mars Surface Materials

The Mars Science Laboratory’s Curiosity rover mission to Gale Crater, Mars has a goal to search for organic carbon and corresponding evidence of ancient microbiology preserved in clay mineral-rich sedimentary deposits [1]. No clear correlation of clay mineral (smectite) abundances with the Sample Analysis at Mars (SAM) carbon detections (up to 2000 ppm C) [2] has been established, suggesting other phases may preserve organic C in martian sediments. Terrestrial volcanic glass soils can accumulate C due to the C-complexing abilities of poorly crystalline Al- and Fe-oxyhydroxides [3]. The Xray amorphous component (20 to 73 wt. %) in Gale Crater materials [4,5] has received little consideration regarding organic C preservation in Gale Crater. The objectives of this work are to 1) Evaluate C content and level of soil development of basaltic glass-bearing Icelandic soils to determine the role that poorly crystalline phases have in complexing organic C in carbon limited soils and 2) Determine if evolved gas analysis (EGA) of well-characterized Mars analog basaltic materials from Iceland can be used to interpret SAM data to understand the nature of organic-C mineral/geochemical associations in Gale materials.

B. Sutter

Trace-Element Analyses of Carbonate Minerals in the Gunflint Banded Iron Formation

We report on the petrography, mineralogy and trace-element abundances of individual carbonate grains in the Early Proterozoic Gunflint BIF (Banded Iron Formation). Trace-element data may be used as environmental recorders of the fluid evolution from which the various carbonate phases precipitated. Additional information is contained in the original extended abstract.

Pun, Aurora

Formation of Smectite and Carbonate Minerals From Basaltic Glass on Early Mars

Intense aqueous alteration occurred on early Mars and left behind various secondary minerals. Physicochemical characteristics of ancient aquatic systems are still largely unknown, including why widespread smectite but limited carbonate deposits formed. Acidic events caused by sulfuric acid could permit smectite but inhibit carbonate formation on Mars. Gradual acid neutralization by basalts, however, develops conditions favorable for carbonate precipitation, leading to the coexistence of smectite and carbonates. The objectives of our work were to identify pH conditions and mineralogy of smectite and carbonate formed together from Mars analog basaltic glass.

T. S. Peretyazhko

Method and apparatus for instantaneous band ratioing in a reflectance radiometer

A hand-held instrument is provided to compare information from selected infrared and visible bands in the 0.4 to 2.5 micrometer range, to perform ratioing via a dividing circuit (17) and to directly read out, via a display system (18), ratio values in a continuous digital display. The dual-beam, ratioing radiometer contains two optical trains (10, 12), each having two repeater lenses (L1a, L1b and L2a, L2b) and a cooled lead sulfide detector (D1, D2). One of the trains (10) is pivotal to facilitate measurements at distances ranging from about 1 meter to infinity. The optical trains are intersected by a set of two coaxially-mounted filter wheels (F1, F2), each containing up to five interference filters and slits to pass radiation filtered by the other. Filters with band passes as narrow as 0.01 micrometer are used in the region 0.4 to 2.5 micrometers. The total time for a calibration and measurement is only a few seconds. It is known from previous field studies using prior art devices, that materials, e.g., clay minerals, and carbonate minerals such as limestone, have unique spectral properties in the 2.0 to 2.5 micrometer region. Using properly chosen spectral filters, and ratioing the signals to remove the effect of topography on the brightness measured, the instrument can be used for real-time analysis of reflecting materials in the field. Other materials in the broader range of 0.4 to 2.5 micrometers (and even beyond) could be similarly identified once the reflectance spectrum of the material is established by any means.

Goetz, Alexander F. H.

Global geochemical cycles of carbon, sulfur and oxygen

Time resolved data on the carbon isotopic composition of carbonate minerals and the sulfur isotopic composition or sulfate minerals show a strong negative correlation during the Cretaceous. Carbonate minerals are isotopically heavy during this period while sulfate minerals are isotopically light. The implication is that carbon is being transferred from the oxidized, carbonate reservoir to the reservoir of isotopically light reduced organic carbon in sedimentary rocks while sulfur is being transferred from the reservoir of isotopically light sedimentary sulfide to the oxidized, sulfate reservoir. These apparently oppositely directed changes in the oxidation state of average sedimentary carbon and sulfur are surprising because of a well-established and easy to understand correlation between the concentrations of reduced organic carbon and sulfide minerals in sedimentary rocks. Rocks rich in reduced carbon are also rich in reduced sulfur. The isotopic and concentration data can be reconciled by a model which invokes a significant flux of hydrothermal sulfide to the deep sea, at least during the Cretaceous.

Non-NASA Center

A New Method for Evaluating the Carbon Isotope Characteristics of Carbonate Formed Under Cryogenic Conditions Analogous to Mars

The two upcoming robotic missions to Mars, Phoenix and MSL, will both have the capability of measuring the carbon isotopic composition of CO2 in the martian atmosphere, as well as possible CO2 trapped in carbonate minerals in the Martian soil. Results from orbital and landed missions now clearly indicate that no large scale deposits of carbonate materials exist at the surface. However, some results from orbital remote sensing have been interpreted to indicate that carbonate minerals are present as fine particles interspersed at low concentrations (approx. 2%) in the martian dust. One likely mechanism for the production of these carbonates is during the freezing of transient water near the surface. Large deposits of near surface ice and photographic evidence for flowing water on the surface suggest that transient melting and refreezing of H2O is an active process on Mars. Any exposure of these fluids to the CO2 rich atmosphere should al-low the production of HCO3- solutions. Carbonates are likely precipitates from these solutions during freezing as extensive CO2 degassing, driven by the fluid s decreasing volume, drives CO2 out. This rapid CO2 degassing increases the pH of the solution and drives carbonate precipitation. It has been shown in previous studies that this rapid CO2 degassing also results in a kinetic isotopic fractionation where the CO2 gas has a much lighter isotopic composition causing a large isotope enrichment of C-13 in the precipitated carbonate. This kinetic isotope enrichment may be very common in the current martian environment, and may be a very important factor in understanding the very high deltaC-13 values of carbonates found in the martian meteorites. However, while previous studies have succeeded in generally quantifying the magnitude of this effect, detailed studies of the consistency of this effect, and the freezing rates needed to produce it are needed to understand any carbon isotope analyses from carbonate minerals in the martian soil or dust. This study demonstrates an innovative new method for measuring the isotopic composition of gas evolved from the freezing of carbonate solutions in real time, which allows for a much clearer view of the chemical processes involved. This method now sets the stage for detailed analysis of the chemical and isotopic mechanisms that produce cryogenic carbonates.

Niles, P. B.

Isotope Variations in Terrestrial Carbonates and Thermal Springs as Biomarkers: Analogs for Martian Processes

Stable isotope measurements of carbonate minerals contained within ALH84001 [1] suggest that fluids were present at 3.9 Gy on Mars [2, 3, 4, 5]. Both oxygen and carbon isotopes provide independent means of deciphering paleoenvironmental conditions at the time of carbonate mineral precipitation. In terrestrial carbonate rocks oxygen isotopes not only indicate the paleotemperature of the precipitating fluid, but also provide clues to environmental conditions that affected the fluid chemistry. Carbon isotopes, on the other hand, can indicate the presence or absence of organic compounds during precipitation (i.e. biogenically vs. thermogenically-generated methane), thus serving as a potential biomarker. We have undertaken a study of micro scale stable isotope variations measured in some terrestrial carbonates and the influence of organic compounds associated with the formation of these carbonates. Preliminary results indicate that isotope variations occur within narrow and discrete intervals, providing clues to paleoenvironmental conditions that include both biological and non-biological activity. These results carry implications for deciphering Martian isotope data and therefore potential biological prospecting on the planet Mars. Recently, Fourier Transform Spectrometer observations have detected methane occurring in the Martian atmosphere [6] that could be attributed to a possible biogenic source. Indeed, Mars Express has detected the presence of methane in the Martian atmosphere [7], with evidence indicating that methane abundances are greatest above those basins with high water concentrations.

Socki, Richard A.

Infrared airborne spectroradiometer survey results in the western Nevada area

The Mark II airborne spectroradiometer system was flown over several geologic test sites in western Nevada. The infrared mineral absorption bands were observed and recorded for the first time using an airborne system with high spectral resolution in the 2.0 to 2.5 micron region. The data show that the hydrothermal alteration zone minerals, carbonates, and other minerals are clearly visible in the airborne survey mode. The finer spectral features that distinguish the various minerals with infrared bands are also clearly visible in the airborne survey data. Using specialized computer pattern recognition methods, it is possible to identify mineralogy and map alteration zones and lithologies by airborne spectroradiometer survey techniques.

Collins, W.

Kinetic Fractionation of Stable Isotopes in Carbonates on Mars: Terrestrial Analogs

An ancient Martian hydrosphere consisting of an alkali-rich ocean would likely produce solid carbonate minerals through the processes of evaporation and/or freezing. We postulate that both (or either) of these kinetically-driven processes would produce carbonate minerals whose stable isotopic compositions are highly fractionated (enriched) with respect to the source carbon. Various scenarios have been proposed for carbonate formation on Mars, including high temperature formation, hydrothermal alteration, precipitation from evaporating brines, and cryogenic formation. 13C and 18O -fractionated carbonates have previously been shown to form kinetically under some of these conditions, ie.: 1) alteration by hydrothermal processes, 2) low temperature precipitation (sedimentary) from evaporating bicarbonate (brine) solutions, and 3) precipitation during the process of cryogenic freezing of bicarbonate-rich fluids. Here we examine several terrestrial field settings within the context of kinetically controlled carbonate precipitation where stable isotope enrichments have been observed.

Socki, Richard A.

Pathways of organic carbon oxidation in three continental margin sediments

We have combined several different methodologies to quantify rates of organic carbon mineralization by the various electron acceptors in sediments from the coast of Denmark and Norway. Rates of NH4+ and Sigma CO2 liberation sediment incubations were used with O2 penetration depths to conclude that O2 respiration accounted for only between 3.6-17.4% of the total organic carbon oxidation. Dentrification was limited to a narrow zone just below the depth of O2 penetration, and was not a major carbon oxidation pathway. The processes of Fe reduction, Mn reduction and sulfate reduction dominated organic carbon mineralization, but their relative significance varied depending on the sediment. Where high concentrations of Mn-oxide were found (3-4 wt% Mn), only Mn reduction occurred. With lower Mn oxide concentrations more typical of coastal sediments, Fe reduction and sulfate reduction were most important and of a similar magnitude. Overall, most of the measured O2 flux into the sediment was used to oxidized reduced inorganic species and not organic carbon. We suspect that the importance of O2 respiration in many coastal sediments has been overestimated, whereas metal oxide reduction (both Fe and Mn reduction) has probably been well underestimated.

NASA Discipline Exobiology

Contribution of Organic Material to the Stable Isotope Composition of Some Terrestrial Carbonates as Analogs for Martian Processes

Understanding the isotopic geochemistry of terrestrial carbonate formation is essential to understanding the evolution of the Martian atmosphere, hydrosphere, and potential biosphere. Carbonate minerals, in particular, are important secondary minerals for interpreting past aqueous environments, as illustrated by the carbonates present in ALH84001 [1]. Models for the history of Mars suggest that the planet was warmer, wetter, and possessed a greater atmospheric pressure within the first billion years as compared to present conditions [2],[3],[4], and likely had an active hydrologic cycle. Morse and Marion [5] point out that associated with this hydrologic cycle would be the active chemical weathering of silicate minerals and thus consumption of atmospheric CO2 and deposition of carbonate and silica. It is during this warmer and wetter period of Martian history that surface and/or near-surface conditions would be most favorable for harboring possible microbiological life. Carbonates within ALH84001 offer evidence that fluids were present at 3.9 Gy on Mars [6]. A more through understanding of the effects of aqueous weathering and the potential contribution of organic compounds on the isotopic composition of Martian carbonate minerals can be gained by studying some terrestrial occurrences of carbonate rocks.

Socki, Richard A.

Carbon Tracers of Aqueous Processes: Isotopic Analysis of Cr Carbonate Grains With Implications for Bennu Samples

Carbonate grains in carbonaceous chondrites record aqueous alteration events on the asteroidal parent bodies, including evidence for episodic alteration, timing of alteration, and time and temperature evolution of volatiles. Spectral features in the 3.4 μm region at asteroid Bennu have been interpreted as coming from carbonate minerals. Coordinated analysis of carbonate grains will be a valuable tool for analysis of Bennu samples, and related analysis of analog materials provides important context for understanding aqueous alteration of carbonaceous asteroids more broadly. To that end, our team is analyzing carbonates in Bennu analog materials, using Raman spectroscopy to identify carbonates and assess the maturity of related organic materials, vacuum reflectance spectroscopy from the ultraviolet through thermal infrared range to constrain contributions from carbonates and organics, X-ray microtomography and electron probe microanalysis (EPMA) to assess the distribution of void space, transmission electron microscopy to characterize space weathering effects, and EPMA and secondary ion mass spectrometry (SIMS) to measure composition and isotopic ratios. Here, we describe in situ analysis of carbon and oxygen isotopes from carbonates in Grosvenor Mountains (GRO) 95577.

K E Miller