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NASA NTRS1992

Volcanic recycling of carbonate deposits on Mars

One question of great interest to those who study the evolution of the Martian atmosphere is: if there was an early, dense atmosphere that was removed, is there any mechanism that could restore it? In the case of an atmosphere removed largely by the formation of carbonates, the only obvious means of restoring it is by the thermal decomposition of the carbonates. Decomposition of carbonates under turbulently flowing lava holds great promise as a means of resupplying the atmosphere with CO2. Huppert and colleagues have modeled the emplacement of terrestrial komatiite flows and found that komatiites, even when flowing over previously emplaced and cooled komatiite flows, could melt and erode this rock to a significant depth. Based on this work, I have begun modeling the erosion of Martian carbonate deposits under turbulently flowing, komatiitic lava. Initial results from this modeling indicate that a high-volume lava flow, emerging at a temperature of, say, 1600 degrees, is capable of eroding several meters of carbonate deposits per day. If such a flow is active for a hundred days, several hundreds of meters of carbonate could be decomposed. If this process occurred over a large area, a bar or more of CO2 could be injected back into the atmosphere over an extremely short period of time. The implications of such an occurrence are intriguing. For instance, if a relatively late pulse of volcanism (such as is suggested by Frey) were to cause a large flow of lava over carbonate deposits in the northern lowlands, the resulting pulse of CO2 into the atmosphere could conceivably restore the climate to one in which liquid water could exist on the surface, or ice could flow.

Schaefer, M. W.↗

NASA NTRS1994

Friction and Wear Properties of As-deposited and Carbon Ion-implanted Diamond Films

Recent work on the friction and wear properties of as-deposited and carbon ion-implanted diamond films was reviewed. Diamond films were produced by the microwave plasma chemical vapor deposition (CVD) technique. Diamond films with various grain sizes and surface roughnesses were implanted with carbon ions at 60 ke V ion energy, resulting in a dose of 1.2310(exp 17) carbon ions/cm(exp 2). Various analytical techniques, including Raman spectroscopy, proton recoil analysis, Rutherford backscattering, transmission and scanning electron microscopy, x-ray photoelectron spectroscopy, and x-ray diffraction, were utilized to characterize the diamond films. Sliding friction experiments were conducted with a polished natural diamond pin in contact with diamond films in the three environments: humid air (40 percent relative humidity), dry nitrogen (less than 1 percent relative humidity), and ultrahigh vacuum (10(exp -7) Pa). The CVD diamond films indeed have friction and were properties similar to those of natural diamond in the three environments. The as-deposited, fine-grain diamond films can be effectively used as self-lubricating, wear-resistant coatings that have low coefficients of friction (0.02 to 0.04) and low wear rates (10(exp -7) to 10(exp -8)mm(exp 3)/N-m) in both humid air and dry nitrogen. However, they have high coefficients of friction (1.5 to 1.7) and a high wear rate (10(exp -4)mm(exp 3/N-m) in ultrahigh vacuum. The carbon ion implanation produced a thin surficial layer (less than 0.1 micron thick) of amorphous, nondiamond carbon on the diamond films. In humid air and dry nitrogen, the ion-implanted, fine- and coarse-grain diamond films have a low coefficient of friction (around 0.1) and a low wear rate (10(exp -7)mm(exp 3/N-m). Even in ultrahigh vacuum, the presence of the nondiamond carbon layer reduced the coefficient of friction of fine-grain diamond films to 0.1 or lower and the wear rate to 10(exp -6)mm(exp 3)/N-m. Thus, the carbon ion-implanted, fine-grain diamond films can be effectively used as wear-resistant, self-lubricating coatings not only in air and dry nitrogen, but also in ultrahigh vacuum. The wear mechanism of diamond films is that of small fragments chipping off the surface. The size of wear particles is related to the extent of wear rates.

Miyoshi, Kazuhisa↗

NASA NTRS1994

Storage and recycling of water and carbon dioxide in the earth

The stabilities and properties of water- and carbon-bearing phases in the earth have been determined from phase equilibrium measurements, combined with new data on the equations of state of water, carbon dioxide, carbonates and hydrates. The data have then been used to predict the fate of calcite and hydrous phases in subducting oceanic lithosphere. From the compositions of MORB's one can estimate concentrations of water and carbon of around 200 ppm and 80 ppm respectively in the upper mantle. Lower mantle estimates are very uncertain, but 1900 ppm water and 2000 ppm C are plausible concentrations. Measurements of the density of supercritical water to 3 GPa demonstrate that this phase is less compressible than anticipated from the equations of state of Haar et al. or Saul and Wagner and is closer to predictions based on molecular dynamics simulations. Conversely, fugacity measurements on carbon dioxide to 7 GPa show that this fluid is more compressible than predicted from the MRK equation of state. The results imply that hydrates are relatively more stable and carbonates less stable at pressures greater than 5 GPa than would be predicted from simple extrapolation of the low pressure data. Nevertheless, carbonates remain extremely refractory phases within both the upper and lower mantle.

Wood, Bernard J.↗

NASA NTRS1994

Martian carbonates in ALH 84001: Textural, elemental, and stable isotopic compositional evidence on their formation

Martian orthopyroxenite ALH 84001 is unusual compared to other martian meteorites in its abundance of Mg-Fe-Ca carbonites. Becasue textural evidence indicates that these carbonates are undoubtedly of martian origin, we have undertaken stable isotopic studies to elucidate their origin by evaluating whether they represent primordial martian C that was outgassing from the mantle of Mars, or volatile additions to the ALH 84001 protolith that equilibrated with the martian atmosphere. If precipitation occurred in a closed system then the isotopic results are compatible with the observed chemical zonation. A unique temperature of formation can be calculated using the difference in C-13 and O-18 between the Fe and Mg carbonates, assuming that precipitation occurred at a constant temperature. Precipitation of approximately one-half of the CO2 reservoir at 320 C can account for the observed values, with the original CO2 reservoir having a delta C-13 of approximately 45% and delta O-18 of approximately 22%. If carbonate precipitated in equilibrium with a large isotopically homogeneous CO2 reservoir (open system), isotopic differences must be attributed to a change in temperature of at least several hundreds of degrees. This temperature change is compatible with a calculated range of temperatures based on carbonate geothermometry. Clearly, carbonate in ALH 84001 is in delta O-18 disequilibrium with orthopyroxene groundmass. Most likely, the carbonate precipitated from a fluid that equilibrated with the martian atmosphere. The deposits or fluids in equilibrium with these deposits were remobilized in the crust producing the carbonate in ALH 84001. This observation establishes a link for the first time between the atmospheric and lithospheric C and O pools that reside on Mars.

Romanek, C. S.↗

NASA NTRS1997

Lightweight Ceramic Composition of Carbon Silicon Oxygen and Boron

Lightweight, monolithic ceramics resistant to oxidation in air at high temperatures are made by impregnating a porous carbon preform with a sol which contains a mixture of tetraethoxysilane, dimethyldiethoxysilane and trimethyl borate. The sol is gelled and dried on the carbon preform to form a ceramic precursor. The precursor is pyrolyzed in an inert atmosphere to form the ceramic which is made of carbon, silicon, oxygen and boron. The carbon of the preform reacts with the dried gel during the pyrolysis to form a component of the resulting ceramic. The ceramic is of the same size, shape and form as the carbon precursor. Thus, using a porous, fibrous carbon precursor, such as a carbon felt, results in a porous, fibrous ceramic. Ceramics of the invention are useful as lightweight tiles for a reentry spacecraft.

Leiser, Daniel B.↗

NASA NTRS1996

Friction and Wear Properties of As-Deposited and Carbon Ion-Implanted Diamond Films

Recent work on the friction and wear properties of as-deposited and carbon ion-implanted diamond films was reviewed. Diamond films were produced by the microwave plasma chemical vapor deposition (CVD) technique. Diamond films with various grain sizes and surface roughnesses were implanted with carbon ions at 60 keV ion energy, resulting in a dose of 1.2 x 10(exp 17) carbon ions per cm(exp 2). Various analytical techniques, including Raman spectroscopy, proton recoil analysis, Rutherford backscattering, transmission and scanning electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction, were utilized to characterize the diamond films. Sliding friction experiments were conducted with a polished natural diamond pin in contact with diamond films in the three environments: humid air (40% relative humidity), dry nitrogen (less than 1 percent relative humidity), and ultrahigh vacuum (10(exp -7) Pa). The CVD diamond films indeed have friction and wear properties similar to those of natural diamond in the three environments. The as-deposited, fine-grain diamond films can be effectively used as self-lubricating, wear-resistant coatings that have low coefficients of friction (0.02 to 0.04) and low wear rates (10(exp -7) to lO(exp -8) mm(exp 3) N(exp -1) m(exp -1)) in both humid air and dry nitrogen. However, they have high coefficients of friction (1.5 to 1.7) and a high wear rate (10(exp -4) mm(exp 7) N(exp -1) m(exp -1)) in ultrahigh vacuum. The carbon ion implantation produced a thin surficial layer (less than 0.1 micron thick) of amorphous, non-diamond carbon on the diamond films. In humid air and dry nitrogen, the ion-implanted, fine and coarse-grain diamond films have a low coefficient of friction (around 0.1) and a low wear rate (10(exp -7) mm(exp 3) N(exp -1) m(exp-1)). Even in ultrahigh vacuum, the presence of the non-diamond carbon layer reduced the coefficient of friction of fine-grain diamond films to 0.1 or lower and the wear rate to 10(exp -6) mm(exp 3) N(exp -1) m(exp -1). Thus, the carbon ion-implanted, fine-grain diamond films can be effectively used as wear-resistant, self-lubricating coatings not only in air and dry nitrogen, but also in ultrahigh vacuum.

Miyoshi, Kazuhisa↗

NASA NTRS1997

The effects of atmospheric [CO2] on carbon isotope fractionation and magnesium incorporation into biogenic marine calcite

The influences of atmospheric carbon dioxide on the fractionation of carbon isotopes and the magnesium incorporation into biogenic marine calcite were investigated using samples of the calcareous alga Amphiroa and benthic foraminifer Sorites grown in the Biosphere 2 Ocean system under variable atmospheric CO2 concentrations (approximately 500 to 1200 ppm). Carbon isotope fractionation was studied in both the organic matter and the skeletal carbonate. Magnesium analysis was to be performed on the carbonate removed during decalcification. These data have not been collected due to technical problems. Carbon isotope data from Amphiroa yields a linear relation between [CO2] and Delta(sup 13)C(sub Corg)values suggesting that the fractionation of carbon isotopes during photosynthesis is positively correlated with atmospheric [CO2]. [CO2] and Delta(sup 13)C(sub Corg) values for Sorites produce a relation that is best described by a hyperbolic function where Delta(sup 13)C(sub Corg) values increase between 300 and 700 ppm and decrease from 700 to 1200 ppm. Further investigation of this relation and Sorites physiology is needed.

Vieira, Veronica↗

NASA NTRS1996

Modelling Temporal Variability in the Carbon Balance of a Spruce/Moss Boreal Forest

A model of the daily carbon balance of a black spruce/feathermoss boreal forest ecosystem was developed and results compared to preliminary data from the 1994 BOREAS field campaign in northern Manitoba, Canada. The model, driven by daily weather conditions, simulated daily soil climate status (temperature and moisture profiles), spruce photosynthesis and respiration, moss photosynthesis and respiration, and litter decomposition. Model agreement with preliminary field data was good for net ecosystem exchange (NEE), capturing both the asymmetrical seasonality and short-term variability. During the growing season simulated daily NEE ranged from -4 g C m(exp -2) d(exp -1) (carbon uptake by ecosystem) to + 2 g C m(exp -2) d(exp -1) (carbon flux to atmosphere), with fluctuations from day to day. In the early winter simulated NEE values were + 0.5 g C m(exp -2) d(exp -1), dropping to + 0.2 g C m(exp -2) d(exp -1) in mid-winter. Simulated soil respiration during the growing season (+ 1 to + 5 g C m(exp -2) d(exp -1)) was dominated by metabolic respiration of the live moss, with litter decomposition usually contributing less than 30% and live spruce root respiration less than 10% of the total. Both spruce and moss net primary productivity (NPP) rates were higher in early summer than late summer. Simulated annual NEE for 1994 was -51 g C m(exp -2) y(exp -1), with 83% going into tree growth and 17% into the soil carbon accumulation. Moss NPP (58 g C m(exp -2) d(exp -1)) was considered to be litter (i.e. soil carbon input; no net increase in live moss biomass). Ecosystem respiration during the snow-covered season (84 g Cm(exp -2)) was 58% of the growing season net carbon uptake. A simulation of the same site for 1968-1989 showed about 10-20% year-to-year variability in heterotrophic respiration (mean of + 113 g C m-2 y@1). Moss NPP ranged from 19 to 114 g C m(exp -2) y(exp -1); spruce NPP from 81 to 150 g C nt-2 y,@l; spruce growth (NPP minus litterfall) from 34 to 103 g C m(exp -2) y(exp -1); NEE ranged from +37 to -142 g C m(exp -2) y(exp -1). Values for these carbon balance terms in 1994 were slightly smaller than the 1969 - 89 means. Higher ecosystem productivity years (more negative NEE) generally had early springs and relatively wet summers; lower productivity years had late springs and relatively dry summers.

Frolking, S.↗

NASA NTRS1999

Durability, Performance, and Emission of Diesel Engines Using Carbon Fiber Piston and Liner

This report summarizes the research conducted by NC State University in investigating the durability, performance and emission of a carbon fiber piston and liner in our single cylinder research Diesel engine. Both the piston and liner were supplied to NC State University by NASA LaRC and manufactured by C-CAT under a separate contract to NASA LaRC. The carbon-carbon material used to manufacture the piston and liner has significantly lower thermal conductivity, coefficient of thermal expansion, and superior strength characteristics at elevated temperatures when compared to conventional piston materials such as aluminum. The results of the carbon-carbon fiber piston testing were compared to a baseline configuration, which used a conventional aluminum piston in a steel liner. The parameters measured were the brake specific fuel consumption, ignition delay, frictional horsepower, volumetric efficiency, and durability characteristics of the two pistons. Testing was performed using a naturally aspirated Labeco Direct Injection single cylinder diesel engine. Two test cases were performed over a range of loads and speeds. The fixed test condition between the aluminum and carbon-carbon piston configurations was the brake mean effective pressure. The measured data was the fuel consumption rate, volumetric efficiency, load, speed, cylinder pressure, needle lift, and exhaust gas temperature. The cylinder pressure, and fuel consumption, exhaust gas temperature, and needle lift were recorded using a National Instruments DAQ board and a PC. All test cases used Diesel no. 2 for fuel.

Afify, E. M.↗

NASA NTRS1998

Laboratory Studies of Carbon Emission from Biomass Burning for use in Remote Sensing

Biomass burning is a significant source of many trace gases in the atmosphere. Up to 25% of the total anthropogenic carbon dioxide added to the atmosphere annually is from biomass burning. However, this gaseous emission from fires is not directly detectable from satellite. Infrared radiance from the fires is. In order to see if infrared radiance can be used as a tracer for these emitted gases, we made laboratory measurements to determine the correlation of emitted carbon dioxide, carbon monoxide and total burned biomass with emitted infrared radiance. If the measured correlations among these quantities hold in the field, then satellite-observed infrared radiance can be used to estimate gaseous emission and total burned biomass on a global, daily basis. To this end, several types of biomass fuels were burned under controlled conditions in a large-scale combustion laboratory. Simultaneous measurements of emitted spectral infrared radiance, emitted carbon dioxide, carbon monoxide, and total mass loss were made. In addition measurements of fuel moisture content and fuel elemental abundance were made. We found that for a given fire, the quantity of carbon burned can be estimated from 11 (micro)m radiance measurements only within a factor of five. This variation arises from three sources, 1) errors in our measurements, 2) the subpixel nature of the fires, and 3) inherent differences in combustion of different fuel types. Despite this large range, these measurements can still be used for large-scale satellite estimates of biomass burned. This is because of the very large possible spread of fire sizes that will be subpixel as seen by Moderate Resolution Imaging Spectroradiometer (MODIS). Due to this large spread, even relatively low-precision correlations can still be useful for large-scale estimates of emitted carbon. Furthermore, such estimates using the MODIS 3.9 (micro)m channel should be even more accurate than our estimates based on 11 (micro)m radiance.

Wald, Andrew E.↗

NASA NTRS1997

New Potential Sources for Black Onaping Carbon

One intriguing and important issue of the Sudbury Structure concerns the source of the relatively large amount of C in the Onaping Formation Black member. This dilemma was recently addressed, and the conclusion was reached that an impactor could not have delivered all of the requisite C. Becker et al. have suggested that much of the C came from the impactor and reported the presence of interstellar He "caged" inside some fullerenes that may have survived the impact. So, conceivably, the C inventory in the Sudbury Structure comes from both target and impactor materials, although the known target rocks have little C. We discuss here the possibility of two terrestrial sources for at least some of the C: (1) impact evaporation/dissociation of C from carbonate target rocks and (2) the presence of heretofore-unrecognized C-rich (up to 26 wt%) siliceous "shale," fragments, which are found in the upper, reworked Black member. Experimental: Hypervelocity impact of a 0.635-diameter Al projectile into dolomite at 5.03 km/s (performed at the Ames Research Center vertical gun range) produced a thin, black layer (= 0.05 mm thick) that partially lined the crater and coated impactor remnants. Scanning electronic microscope (SEM) imagery shows this layer to be spongelike on a submicron scale and Auger spectroscopic analyses yield: 33% C, 22% Mg, 19% 0, and 9% Al (from the projectile). Elemental mapping shows that all of the available 0 is combined with Ca and Mg, Al is not oxidized, and C is in elemental form. Dissociation efficiency of C from CO2 is estimated to be <10% of crater volume. Raman spectroscopy indicates that the C is highly disorganized graphite. Another impact experiment [4] also produced highly disordered graphite from a limestone target (reducing collector), in addition to small amounts of diamond/lonsdaleite/chaoite (oxidizing collector). These experiments confirm the reduction of C from carbonates in impact vapor plumes. Observational: SEM observations and microprobe analyses of small, black shalelike inclusions in the upper Black Onaping indicate high C contents (7-26 wt% avg. = 16%). They contain mostly quartz and carbonaceous matter with small amounts of altered K-feldspar, clays, Fe oxide, and a sulfide. No evidence of shock is seen in quartz, and overall characteristics indicate a natural, lightly metamorphosed carbonaceous shale or mudstone that probably existed as a preimpact rock in the target region and distal fragments washed in during early crater filling. Fragments range in size from tens of microns to cm and increase in abundance in the upper Black toward the Onwatin contact, although their distribution is highly irregular. This increase corresponds to an increase in "organic" C with increasingly negative delta-13 C values and S, together with a decrease in fullerene abundance. In addition, we have found soot in acid-demineralized residues of the Onwatin but not in the Onaping samples. These data could be consistent with impact plume and atmospheric chemical processes, with possible diageneric ovedays. We are analyzing carbonaceous fractions of the Onaping and Onwatin to determine diagnostic C isotopic signatures Analyses by Whitehead et al. on bulk samples revealed no definitive source or processes, although delta-13 C values for "organic" C overlapped those for some meteorites. Discussion: If impact evaporation of Sudbury target carbonates did occur, then where are the carbonates? Distal carbonate (limestone/dolostone) exposures of the Espanola Formation (Huronian Supergroup) are generally thin-bedded, although remnants that partially encompass the Sudbury Crater are variable in thickness and may locally reach 250 m . If a carbonate thickness of 100-200 in existed at the target site, then copious amounts of C could have been reduced by impact processing of carbonates and also C-shale, depending on the efficiency of the processing and the amount of postimpact oxidation. Conclusion: The Sudbury crater offers a unique opportunity to study preserved characteristics of immediate carbonaceous fallback matter and particles of short-term residency in the impact plume as well as dust/aerosols from postimpact atmospheric processing.

Bunch, T. E.↗

NASA NTRS2000

Growth of Carbon Nanostructure Materials Using Laser Vaporization

Since the potential applications of carbon nanotubes (CNT) was discovered in many fields, such as non-structure electronics, lightweight composite structure, and drug delivery, CNT has been grown by many techniques in which high yield single wall CNT has been produced by physical processes including arc vaporization and laser vaporization. In this presentation, the growth mechanism of the carbon nanostructure materials by laser vaporization is to be discussed. Carbon nanoparticles and nanotubes have been synthesized using pulsed laser vaporization on Si substrates in various temperatures and pressures. Two kinds of targets were used to grow the nanostructure materials. One was a pure graphite target and the other one contained Ni and Co catalysts. The growth temperatures were 600-1000 C and the pressures varied from several torr to 500 torr. Carbon nanoparticles were observed when a graphite target was used, although catalysts were deposited on substrates before growing carbon films. When the target contains catalysts, carbon nanotubes (CNT) are obtained. The CNT were characterized by scanning electron microscopy, x-ray diffraction, optical absorption and transmission, and Raman spectroscopy. The temperature-and pressure-dependencies of carbon nanotubes' growth rate and size were investigated.

Zhu, Shen↗

NASA NTRS1999

Production and Characterization of Carbon Nanotubes and Nanotube-Based Composites

The Nobel Prize winning discovery of the Buckuball (C60) in 1985 at Rice University by a group including Dr. Richard Smalley led to the whole new class of carbon allotropes including fullerenes and nanotubes. Especially interesting from many viewpoints are single-walled carbon nanotubes, which structurally are like a single graphitic sheet wrapped around a cylinder and capped at the ends. This cylinders have diameter as small as 0.5 - 2 nm (1/100,000th the diameter of a human hair) and are as long as 0.1 - 1 mm. Nanotubes are really individual molecules and believed to be defect-free, leading to high tensile strength despite their low density. Additionally, these fibers exhibit electrical conductivity as high as copper, thermal conductivity as high as diamond, strength 100 times higher than steel at one-sixth the weight, and high strain to failure. Thus it is believed that developments in the field of nanotechnology will lead to stronger and lighter composite materials for next generation spacecraft. Lack of a bulk method of production is the primary reason nanotubes are not used widely today. Toward this goal JSC nanotube team is exploring three distinct production techniques: laser ablation, arc discharge and chemical vapor deposition (CVD, in collaboration with Rice University). In laser ablation technique high-power laser impinges on the piece of carbon containing small amount of catalyst, and nanotubes self-assemble from the resulting carbon vapor. In arc generator similar vapor is created in arc discharge between carbon electrodes with catalyst. In CVD method nanotubes grow at much lower temperature on small catalyst particles from carbon-containing feedstock gas (methane or carbon monoxide). As of now, laser ablation produces cleanest material, but mass yield is rather small. Arc discharge produces grams of material, but purity is low. CVD technique is still in baby steps, but preliminary results look promising, as well as perspective of scaling the process up. We are also working on necessary purification of nanotubes. Applications of nanotubes are in such various fields as lightweight composites, molecular electronics, energy storage (electrodes in Li ion batteries), flat panel displays, conductive polymers, etc. JSC nanotube team is focused on development of lightweight materials. We work on the injection thermoset epoxies reinforced with nanotubes. Early results show good wetting of nanotube surface with epoxy, which is very important. More research will be possible as more nanotubes become available.

Nikolaev, Pavel↗

NASA NTRS2001

Formation of Carbon Nanotubes in a Microgravity Environment

Even though nanotube science has become one of the worlds most rapidly advancing areas of research, very little is known about the processes involved in nanotube synthesis. To study the formation of carbon nanotubes in an environment unhindered by the buoyancy induced flows generated by the high temperatures necessary to vaporize carbon and grow nanotubes, we have designed a miniature carbon arc apparatus that can produce carbon nanotubes under microgravity conditions. During the first phase of this project, we designed, built, and successfully tested the mini carbon arc in both 1g and 2.2 sec drop tower microgravity conditions. We have demonstrated that microgravity can eliminate the strong convective flows from the carbon arc and we have successfully produced single-walled carbon nanotubes in microgravity. We believe that microgravity processing will allow us to better understand the nanotube formation process and eventually allow us to grow nanotubes that are superior to ground-based production.

Alford, J. M.↗

NASA NTRS2001

Carbon Storage in Wetlands and Lakes of the Eastern US

Carbon stored underground may participate in a positive feedback with climate warming, as higher temperatures accelerate decomposition reactions and hence CO2 release. Assessing how below-ground carbon storage varies with modern climate and paleoclimate will advance understanding of this feedback in two ways. First, it will estimate the sensitivity of carbon storage to temperature and precipitation changes. Second, it will help quantify the size of carbon stocks available for the feedback, by indicating how current regional climate differences affect carbon storage. Whereas many studies of below-ground carbon storage concentrate on soils, this investigation focuses on the saturated and primarily organic material stored in wetlands and lake sediments. This study surveys research done on organic sediment depth and organic content at 50-100 sites in the eastern U.S., integrating our own research with the work of others. Storage depth is evaluated for sediments from the past 10,000 years, a date reflected in pollen profiles. Organic content is measured chiefly by loss-on-ignition (101). These variables are compared to characteristics of the sites such as latitude, altitude, and vegetation as well as local climate. Preliminary results suggest a strong relationship between latitude and depth of organic material stored over the last 10,000 years, with more accumulation in the northeastern US than the southeastern US. Linking the percent organic matter to actual carbon content is in progress with wetlands from Black Rock Forest and Alpine Swamp.

Renik, Byrdie↗

NASA NTRS2002

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↗

NASA NTRS2003

Carbonate Platform Development and Stromatolite Morphogenesis: Constraints on Environmental and Biological Evolution

Work has been completed on the digital mapping of a terminal Proterozoic reef complex in Namibia. This complex formed an isolated carbonate platform developed downdip on a carbonate ramp of the Nama Group. The stratigraphic evolution of the platform was digitally reconstructed from an extensive dataset that was compiled by using digital surveying technologies. The platform comprises three accommodation cycles in which each subsequent cycle experienced progressively greater influence of a long-term accommodation increase. Aggradation and progradation during the first cycle resulted in a flat, uniform, sheet-like platform. The coarsening and shallowing-upward sequence representing the first cycle is dominated by columnar stromatolitic thrombolites and massive dolostones with interbedded mudstone-grainstone at the base of the sequence grading into cross-bedded dolostones. The second cycle features aggradation, formation of a distinct margin containing thrombolite mounds and domes, and the development of a bucket geometry. Columnar stromatolitic thrombolites dominate the platform interior. The final stage of platform development shows a deepening trend with initial aggradation and formation of well-bedded, thin deposits in the interior and mound development at the margins. While the interior drowned, the platform margin kept up with rising sea level and a complex pinnacle reef formed containing fused and coalesced thrombolite mounds flanked by bioclastic grainstones (containing Cloudina and Namacalathus fossils) and collapse breccias. A set of isolated large thrombolite mounds flanked by shales indicate the final stage of the carbonate platform. During a progressive increase in accommodation, a flat-topped isolated carbonate platform becomes aerially less extensive by either backstepping or formation of smaller pinnacles or a combination of both. The overall geometric evolution of the studied platform from flat-topped to bucket with elevated margins is recorded in many Proterozoic and Phanerozoic isolated carbonate platforms with similar dimensions. The terminal Proterozoic, microbial-dominated, isolated carbonate platform of this study clearly illustrates that the answer to accommodation changes was already familiar among carbonate platforms before the dawn of metazoan-dominated platforms.

Grotzinger, John P.↗

NASA NTRS2003

Black Carbon in Estuarine (Coastal) High-molecular-weight Dissolved Organic Matter

Dissolved organic matter (DOM) in the ocean constitutes one of the largest pools of organic carbon in the biosphere, yet much of its composition is uncharacterized. Observations of black carbon (BC) particles (by-products of fossil fuel combustion and biomass burning) in the atmosphere, ice, rivers, soils and marine sediments suggest that this material is ubiquitous, yet the contribution of BC to the ocean s DOM pool remains unknown. Analysis of high-molecular-weight DOM isolated from surface waters of two estuaries in the northwest Atlantic Ocean finds that BC is a significant component of DOM, suggesting that river-estuary systems are important exporters of BC to the ocean through DOM. We show that BC comprises 4-7% of the dissolved organic carbon (DOC) at coastal ocean sites, which supports the hypothesis that the DOC pool is the intermediate reservoir in which BC ages prior to sedimentary deposition. Flux calculations suggest that BC could be as important as vascular plant-derived lignin in terms of carbon inputs to the ocean. Production of BC sequesters fossil fuel- and biomass-derived carbon into a refractory carbon pool. Hence, BC may represent a significant sink for carbon to the ocean.

Mannino, Antonio↗