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At least 19 records

Calcium carbonate and calcium sulfate in Martian meteorite EETA79001

Chips of glassy Lithology C of EETA79001 were studied by scanning electron microscopy and energy dispersive X-ray spectroscopy to determine the mineralogy and petrogenesis of the glass that was shown by others to contain trapped Mars-like gases. Calcium carbonite was identified as massive to acicular crystals for which Ca, C, and O were the major elements. Calcium sulfate was identified as prismatic-acicular crystals with Ca and S as the major elements.

Gooding, J. L.↗

Evidence for the involvement of carbonic anhydrase and urease in calcium carbonate formation in the gravity-sensing organ of Aplysia californica

To better understand the mechanisms that could modulate the formation of otoconia, calcium carbonate granules in the inner ear of vertebrate species, we examined statoconia formation in the gravity-sensing organ, the statocyst, of the gastropod mollusk Aplysia californica using an in vitro organ culture model. We determined the type of calcium carbonate present in the statoconia and investigated the role of carbonic anhydrase (CA) and urease in regulating statocyst pH as well as the role of protein synthesis and urease in statoconia production and homeostasis in vitro. The type of mineral present in statoconia was found to be aragonitic calcium carbonate. When the CA inhibitor, acetazolamide (AZ), was added to cultures of statocysts, the pH initially (30 min) increased and then decreased. The urease inhibitor, acetohydroxamic acid (AHA), decreased statocyst pH. Simultaneous addition of AZ and AHA caused a decrease in pH. Inhibition of urease activity also reduced total statoconia number, but had no effect on statoconia volume. Inhibition of protein synthesis reduced statoconia production and increased statoconia volume. In a previous study, inhibition of CA was shown to decrease statoconia production. Taken together, these data show that urease and CA play a role in regulating statocyst pH and the formation and maintenance of statoconia. CA produces carbonate ion for calcium carbonate formation and urease neutralizes the acid formed due to CA action, by production of ammonia.

Non-NASA Center↗

Results of the TTF-TCNQ and the calcium carbonate crystallization on the Long Duration Exposure Facility

Experiment A0139A on the Long Duration Exposure Facility (LDEF) carried four large containers into orbit five years with crystal growth solutions for lead sulfide, calcium carbonate, and TTF-TCNQ. Although temperature data was lost, the experimental program had been working since the valves in all containers had been opened. All four experiments produced crystals of varying quality. The calcium carbonate crystals had the best appearance. The TTF-TCNQ crystals were packed together near the valve openings of the container. When taken apart, the single crystals showed some unusual morphological properties. X ray investigations as well as conductivity measurements on long duration space grown TTF-TCNQ crystals will be presented. Comparisons will be made with our previous space solution growth experiments. The TTF-TCNQ crystals are no longer of the highest interest, so this activity has been terminated in favor of calcium carbonate and calcium phosphate crystallizations.

Nielsen, Kjeld Flemming↗

Impregnating Coal With Calcium Carbonate

Relatively inexpensive process proposed for impregnating coal with calcium carbonate to increase rates of gasification and combustion of coal and to reduce emission of sulfur by trapping sulfur in calcium sulfide. Process involves aqueous-phase reactions between carbon dioxide (contained within pore network of coal) and calcium acetate. Coal impregnated with CO2 by exposing it to CO2 at high pressure.

Sharma, Pramod K.↗

Were kinetics of Archean calcium carbonate precipitation related to oxygen concentration?

Archean carbonates commonly contain decimetre- to metre-thick beds consisting entirely of fibrous calcite and neomorphosed fibrous aragonite that precipitated in situ on the sea floor. The fact that such thick accumulations of precipitated carbonate are rare in younger marine carbonates suggests an important change in the modes of calcium carbonate precipitation through time. Kinetics of carbonate precipitation depend on the concentration of inhibitors to precipitation that reduce crystallization rates and crystal nuclei formation, leading to kinetic maintenance of supersaturated solutions. Inhibitors also affect carbonate textures by limiting micrite precipitation and promoting growth of older carbonate crystals on the sea floor. Fe2+, a strong calcite-precipitation inhibitor, is thought to have been present at relatively high concentrations in Archean seawater because oxygen concentrations were low. The rise in oxygen concentration at 2.2-1.9 Ga led to the removal of Fe2+ from seawater and resulted in a shift from Archean facies, which commonly include precipitated beds, to Proterozoic facies, which contain more micritic sediment and only rare precipitated beds.

Non-NASA Center↗

Sulfur Cycling Mediates Calcium Carbonate Geochemistry in Modern Marine Stromatolites

Modem marine stromatolites forming in Highborne Cay, Exumas (Bahamas), contain microbial mats dominated by Schizothrix. Although saturating concentrations of Ca2+ and CO32- exist, microbes mediate CaCO3 precipitation. Cyanobacterial photosynthesis in these stromatolites aids calcium carbonate precipitation by removal of HS+ through CO2 use. Photorespiration and exopolymer production predominantly by oxygenic phototrophs fuel heterotrophic activity: aerobic respiration (approximately 60 umol/sq cm.h) and sulfate reduction (SR; 1.2 umol SO42-/sq cm.h) are the dominant C- consuming processes. Aerobic microbial respiration and the combination of SR and H2S oxidation both facilitate CaCO3 dissolution through H+ production. Aerobic respiration consumes much more C on an hourly basis, but duel fluctuating O2 and H2 depth profiles indicate that overall, SR consumes only slightly less (0.2-0.5) of the primary production. Moreover, due to low O2 concentrations when SR rates are peaking, reoxidation of the H2S formed is incomplete: both thiosulfate and polythionates are formed. The process of complete H2S oxidation yields H+. However, due to a low O2 concentration late in the day and relatively high O2 concentrations early in the following morning, a two-stage oxidation takes place: first, polythionates are formed from H2S, creating alkalinity which coincides with CaCO3 precipitation; secondly, oxidation of polythionates to sulfate yields acidity, resulting in dissolution, etc. Vertical profiles confirmed that the pH peaked late in the afternoon (greater than 8.8) and had the lowest values (less than 7.4) early in the morning. Thus, the effect of this S-cycling through alkalinity production, followed by acidification during H2S oxidation, results in a six times stronger fluctuation in acidity than photosynthesis plus aerobic respiration accomplish. This implies that anaerobic processes play a pivotal role in stromatolite formation.

Visscher, P. T.↗

Lab-Scale Study of the Calcium Carbonate Dissolution and Deposition by Marine Cyanobacterium Phormidium subcapitatum

Suggestions that calcification in marine organisms changes in response to global variations in seawater chemistry continue to be advanced (Wilkinson, 1979; Degens et al. 1985; Kazmierczak et al. 1986; R. Riding 1992). However, the effect of [Na+] on calcification in marine cyanobacteria has not been discussed in detail although [Na+] fluctuations reflect both temperature and sea-level fluctuations. The goal of these lab-scale studies therefore was to study the effect of environmental pH and [Na+] on CaCO3 deposition and dissolution by marine cyanobacterium Phormidium subcapitatum. Marine cyanobacterium P. subcapitatum has been cultivated in ASN-III medium. [Ca2+] fluctuations were monitored with Ca(2+) probe. Na(+) concentrations were determined by the initial solution chemistry. It was found that the balance between CaCO3 dissolution and precipitation induced by P. subcapitatum grown in neutral ASN III medium is very close to zero. No CaCO3 precipitation induced by cyanobacterial growth occurred. Growth of P. subcapitatum in alkaline ASN III medium, however, was accompanied by significant oscillations in free Ca(2+) concentration within a Na(+) concentration range of 50-400 mM. Calcium carbonate precipitation occurred during the log phase of P. subcapitatum growth while carbonate dissolution was typical for the stationary phase of P. subcapitatum growth. The highest CaCO3 deposition was observed in the range of Na(+) concentrations between 200-400 mM. Alkaline pH also induced the clamping of P. subcapitatum filaments, which appeared to have a strong affinity to envelop particles of chemically deposited CaCO3 followed by enlargement of those particles size. EDS analysis revealed the presence of Mg-rich carbonate (or magnesium calcite) in the solution containing 10-100 mM Na(+); calcite in the solution containing 200 mM Na(+); and aragonite in the solution containing with 400 mM Na(+). Typical present-day seawater contains xxmM Na(+). Early (Archean) seawater was likely less saline. The division of marine cyanobacterium P. subcapitatum is associated with periodic deposition and dissolution of CaCO3, the rhythms and intensity of which are dependent on concentrations of both OH(-) and Na(+). Thus, the role of present-day marine cyanobacteria in the global carbonate cycle might be reduced to aggregation and recrystallization of available CaCO3 particles in marine water rather than long-term precipitation and accumulation of CaCO3 deposits. For lower Na(+) concentrations, precipitation of carbonates by cyanobacteria would be even less significant. These results suggest that the lack of calcified cyanobacteria in stromatalite-bearing Precambrian sequences can be explained not only by high dissolved inorganic carbon concentrations but also by lower salinity, as well as possible lower pH compared to present-day oceans.

Karakis, S. G.↗

Calcium carbonate and sulfate of possible extraterrestrial origin in the EETA 79001 meteorite

Two varieties of Ca-carbonate were found in a total of three interior (greater than 2-cm depth) samples of glass inclusions from the shergottite meteorite, Elephant Moraine, Antarctica, A79001. Two of the samples, including the largest deposit around a vug near the center of the meteorite (8-cm depth), contained veins of granular calcite with significant Mg and P, either as Mg-calcite with dissolved P or as calcite with very finely intergrown Mg-bearing phosphate. The second variety, which occurred in a third sample with a previously documented high concentration of trapped gases, consisted of disseminated 10-20-micron anhedral grains of nearly pure CaCO3 and was intimately associated with laths and needles of Ca-sulfate (possibly gypsum). All evidence considered, it is probable that both varieties of Ca-carbonate (and the Ca-sulfate) formed on a planetary body (probably Mars) before the meteorite fell on earth.

Gooding, James L.↗

Evidence for Calcium Carbonate at the Phoenix Landing Site

The Phoenix mission has recently finished its study of the north polar environment of Mars with the aim to help understand both the current climate and to put constraints on past climate. An important part of understanding the past climate is the study of secondary minerals, those formed by reaction with volatile compounds such as H2O and CO2. This work describes observations made by the Thermal and Evolved-Gas Analyzer (TEGA) on the Phoenix Lander related to carbonate minerals. Carbonates are generally considered to be products of aqueous processes. A wet and warmer climate during the early history of Mars coupled with a much denser CO2 atmosphere are ideal conditions for the aqueous alteration of basaltic materials and the subsequent formation of carbonates. Carbonates (Mg- and Ca-rich) are predicted to be thermodynamically stable minerals in the present martian environment, however, there have been only a few indications of carbonates on the surface by a host of orbiting and landed missions to Mars. Carbonates (Mg-rich) have been suggested to be a component (2-5 wt %) of the martian global dust based upon orbital thermal emission spectroscopy. The identifications, based on the presence of a 1480 cm-1 absorption feature, are consistent with Mgcarbonates. A similar feature is observed in brighter, undisturbed soils by Mini-TES on the Gusev plains. Recently, Mg-rich carbonates have been identified in the Nili Fossae region by the CRISM instrument onboard the Mars Reconnaissance Orbiter. Carbonates have also been confirmed as aqueous alteration phases in martian meteorites so it is puzzling why there have not been more discoveries of carbonates by landers, rovers, and orbiters. Carbonates may hold important clues about the history of liquid water and aqueous processes on the surface of Mars.

Boynton, W. V.↗

A Structural and Molecular Approach for the Study Biomarkers

Investigation of the nucleation and growth of crystals in both abiotic and biotic systems is critical to seemingly diverse disciplines of geology, biology, environmental science, and astrobiology. While there are abundant studies devoted to the determination of the structure and composition of inorganic crystals, as well as to the development of thermodynamic and kinetic models, it is only recently that research efforts have been directed towards understanding mineralization in biological systems (i.e., biomineralization). Biomineralization refers to the processes by which living organisms form inorganic solids. Studies of the processes of biomineralization under low temperature aqueous conditions have focused primarily on magnetite forming bacteria and shell forming marine organisms. Many of the biological building materials consist of inorganic minerals (calcium carbonate, calcium phosphate, silica or iron oxide) intricately combined with organic polymers (like proteins). More recently, efforts have been undertaken to explore the nature of biological activities in ancient rocks. In the absence of well-preserved microorganisms or genetic material required for the polmerase chain reaction (PCR) method in molecular phylogenetic studies, using biominerals as biomarkers offers an alternative approach for the recognition of biogenic activity in both terrestrial and extraterrestrial environments. The primary driving force in biomineralization is the interaction between organic and inorganic phases. Thus, the investigation of the ultrastructure and the nature of reactions at the molecular level occurring at the interface between inorganic and organic phases is essential to understanding the processes leading to the nucleation and growth of crystals. It is recognized that crystal surfaces can serve as the substrate for the organization of organic molecules that lead to the formation of polymers and other complex organic molecules, and in discussions of the origins of life, is referred to as organic synthesis on mineral surfaces. Furthermore, it is suggested that the interaction between mineral surfaces and simple organic molecules resulted in the formation of amino acids, RNA, and perhaps other more complex molecules such as proteins. On the other hand, in natural systems, it is recognized that functional groups on cell walls or membranes of microorganisms serve as sites of nucleation and crystallization. The precise replication of biominerals with controlled structure, morphology, size and texture is not confined to higher organisms as it also occurs in primitive prokaryotic cells such as magnetotactic bacteria and cyanobacteria. This suggests that the principal strategies of biomineralization were established early on in the evolutionary history of organisms. It is critical, therefore, to search for common mechanisms within diverse biological systems. One such common factor is the capability for organization and self-assembly. Organic macromolecules such as proteins and lipids can aggregate and polymerize forming membranes or extracellular matrix. At the organic-inorganic interface, several factors such as lattice geometry, polarity, stereochemistry and topography may act in concert to control nucleation and growth of crystals. Although several models have been proposed that discuss the significance of these factors for biomineralization, no comprehensive experimental data are available. In contrast to crystallization in exclusively inorganic systems, the kinetics of reaction and structural relationships between organic and inorganic phases in biominerals or biomimetic material is poorly understood. For example, it is not clear if the concept of epitactic growth (geometrical matching of unit cells at the interface of a secondary crystal growing on a primary crystal) applies to organic-inorganic systems. In contrast to inorganic templates that often have a smooth and rigid surface that promotes epitactic growth, biological substrates are usually rough and result in a large degree of mismatch. It is apparent that factors controlling the reaction at the crystal-matrix interface are strongly dependent upon the nature of the substrate. Therefore, characterization of the assembled organic surface and surface structure of the inorganic phase is crucial to understanding the processes of biomineralization. The focus of our research is the investigation of the processes leading to the nucleation and growth of crystals on both natural and synthetic systems through an interdisciplinary approach that integrates molecular biology, morphology and mineralogy using advanced preparation and analytical techniques. We have studied run-products, particularly magnetite, siderite and other carbonates, that resulted from extracellular biomineralization by extremophiles isolated from a variety of extreme environments ranging from permafrost to hydrothermal vent systems. The results of this study are critical to recognizing biomarkers in terrestrial and extraterrestrial environments.

Thomas-Keprta, Kathie↗

Results of the TTF-TCNQ- and the calcium carbonate-crystallization on the Long Duration Exposure Facility

Experiment AO139A on the Long Duration Exposure Facility (LDEF) carried four large containers into orbit for five years with crystal growth solutions for lead sulfide, calcium carbonate, and tetra thiafulvalene- tetra cyanoquino methane (TTF-TCNQ). The LDEF was in excellent condition after the long orbital stay, and although the temperature data was lost, the experiment program had been working since the valves in all containers were opened. All four experiments produced crystals; however, they were of varying quality. The calcium carbonate crystals had the best appearance. The TTF-TCNQ crystals were packed together near the valve openings of the container. When taken apart, the single crystals showed some unusual morphological properties. X-ray investigations as well as conductivity measurements on the long duration space grown TTF-TCNQ crystals are presented, and pictures of the calcium carbonate are shown. Comparisons are made with previous space solution growth experiments on the European Spacelab Mission and the Apollo-Soyuz Test Project.

Nielsen, Kjeld Flemming↗

High-temperature ''hydrostatic'' extrusion

Quasi-fluids permit hydrostatic extrusion of solid materials. The use of sodium chloride, calcium fluoride, or glasses as quasi-fluids reduces handling, corrosion, and sealing problems, these materials successfully extrude steel, molybdenum, ceramics, calcium carbonate, and calcium oxide. This technique also permits fluid-to-fluid extrusion.

Hunt, J. G.↗

Ex Vivo Growth of Bioengineered Ligaments and Other Tissues

A method of growing bioengineered tissues for use in surgical replacement of damaged anterior cruciate ligaments has been invented. An anterior cruciate ligament is one of two ligaments (the other being the posterior cruciate ligament) that cross in the middle of a knee joint and act to prevent the bones in the knee from sliding forward and backward relative to each other. Anterior cruciate ligaments are frequently torn in sports injuries and traffic accidents, resulting in pain and severe limitations on mobility. By making it possible to grow replacement anterior cruciate ligaments that structurally and functionally resemble natural ones more closely than do totally synthetic replacements, the method could create new opportunities for full or nearly full restoration of functionality in injured knees. The method is also adaptable to the growth of bioengineered replacements for other ligaments (e.g., other knee ligaments as well as those in the hands, wrists, and elbows) and to the production of tissues other than ligaments, including cartilage, bones, muscles, and blood vessels. The method is based on the finding that the histomorphological properties of a bioengineered tissue grown in vitro from pluripotent cells within a matrix are affected by the direct application of mechanical force to the matrix during growth generation. This finding provides important new insights into the relationships among mechanical stress, biochemical and cell-immobilization methods, and cell differentiation, and is applicable to the production of the variety of tissues mentioned above. Moreover, this finding can be generalized to nonmechanical (e.g., chemical and electromagnetic) stimuli that are experienced in vivo by tissues of interest and, hence, the method can be modified to incorporate such stimuli in the ex vivo growth of replacements for the various tissues mentioned above. In this method, a three-dimensional matrix made of a suitable material is seeded with pluripotent stem cells. The patient s bone-marrow stromal cells are preferably used as the pluripotent cells in this method. Suitable matrix materials are materials to which cells can adhere for example, collagen type I. The seeded matrix is attached to anchors at opposite ends and then the cells in the matrix are cultured under conditions appropriate for the growth and regeneration of cells. Suitable anchor materials are materials to which the matrix can attach; examples include demineralized bone and Goinopra coral that has been treated to convert its calcium carbonate to calcium phosphate.

Altman, Gregory↗

Limits on the UV Photodecomposition of Carbonates on Mars

The effect of UV (ultraviolet) light on the stability of calcium carbonate in a simulated martian atmosphere was experimentally investigated. Sample cells containing C-13 labeled calcite were irradiated with a Xe arc lamp in 10 mbar of simulated martian atmosphere and a quadrupole mass spectrometer was used to monitor the headspace gases for the production of (13)CO2. We found no experimental evidence of the UV photodecomposition of calcium carbonate in a simulated martian atmosphere. Extrapolating the lower limit of detection of our experimental system to an upper limit of carbonate decomposition on Mars yields a quantum efficiency of 3.5 x 10(exp -8) molecules/photon over the wavelength interval of 190-390 nm and a maximum UV photodecomposition rate of 1.2 x 10(exp -13) kg m(exp -2) s(exp -1) from a calcite surface. The maximum loss of bulk calcite due to this process would be 2.5 nm yr(exp -1). However, calcite is expected to be thermodynamically stable on the surface of Mars and potential UV photodecomposition reaction mechanisms indicate that while calcium carbonate may decompose under vacuum, it would be stable in a CO2 atmosphere. Given the expected stability of carbonate on Mars and our inability to detect carbonate decomposition, we conclude that it is unlikely that the apparent absence of carbonate on the martian surface is due to UV photo decomposition of calcite in the current environment.

Quinn, Richard↗

Strangelove Ocean and Deposition of Unusual Shallow-Water Carbonates After the End-Permian Mass Extinction

The severe mass extinction of marine and terrestrial organisms at the end of the Permian Period (approx. 251 Ma) was accompanied by a rapid negative excursion of approx. 3 to 4 per mil in the carbon-isotope ratio of the global surface oceans and atmosphere that persisted for some 500,000 into the Early Triassic. Simulations with an ocean-atmosphere/carbon-cycle model suggest that the isotope excursion can be explained by collapse of ocean primary productivity (a Strangelove Ocean) and changes in the delivery and cycling of carbon in the ocean and on land. Model results also suggest that perturbations of the global carbon cycle resulting from the extinctions led to short-term fluctuations in atmospheric pCO2 and ocean carbonate deposition, and to a long-term (>1 Ma) decrease in sedimentary burial of organic carbon in the Triassic. Deposition of calcium carbonate is a major sink of river-derived ocean alkalinity and for CO2 from the ocean/atmosphere system. The end of the Permian was marked by extinction of most calcium carbonate secreting organisms. Therefore, the reduction of carbonate accumulation made the oceans vulnerable to a build-up of alkalinity and related fluctuations in atmospheric CO2. Our model results suggest that an increase in ocean carbonate-ion concentration should cause increased carbonate accumulation rates in shallow-water settings. After the end-Permian extinctions, early Triassic shallow-water sediments show an abundance of abiogenic and microbial carbonates that removed CaCO3 from the ocean and may have prevented a full 'ocean-alkalinity crisis' from developing.

Rampino, Michael R.↗

Microbial Diversity Analysis of the Bacterial and Archaeal Population in Present Day Stromatolites

Stromatolites are layered sedimentary structures resulting from microbial mat communities that remove carbon dioxide from their environment and biomineralize it as calcium carbonate. Although prevalent in the fossil record, stromatolites are rare in the modem world and are only found in a few locations including Highbome Cay in the Bahamas. The stromatolites found at this shallow marine site are analogs to ancient microbial mat ecosystems abundant in the Precambrian period on ancient Earth. To understand how stromatolites form and develop, it is important to identify what microorganisms are present in these mats, and how these microbes contribute to geological structure. These results will provide insight into the molecular and geochemical processes of microbial communities that prevailed on ancient Earth. Since stromatolites are formed by lithifying microbial mats that are able to mineralize calcium carbonate, understanding the biological mechanisms involved may lead to the development of carbon sequestration technologies that will be applicable in human spaceflight, as well as improve our understanding of global climate and its sustainability. The objective of my project was to analyze the archaeal and bacterial dIversity in stromatolites from Highborn Cay in the Bahamas. The first step in studying the molecular processes that the microorganisms carry out is to ascertain the microbial complexity within the mats, which includes identifying and estimating the numbers of different microbes that comprise these mats.

Ortega, Maya C.↗