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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records

Model of carbon fixation in microbial mats from 3,500 Myr ago to the present

Using modern microbial mats as analogs for ancient stromatolites, it is shown that the rate of carbon fixation is higher at the greater levels of atmospheric CO2 that were probably present in the past. It is suggested that carbon fixation in microbial mats was not carbon-limited during the early Precambrian, but became carbon-limited as the supply of inorganic carbon decreased. Carbon limitation led to a lower rate of carbon fixation, especially towards the end of the Precambrian.

Rothschild, Lynn J.↗

Two-Step Resonance-Enhanced Desorption Laser Mass Spectrometry for In Situ Analysis of Organic-Rich Environments

A wide diversity of planetary surfaces in the solar system represent high priority targets for in situ compositional and contextual analysis as part of future missions. The planned mission portfolio will inform our knowledge of the chemistry at play on Mars, icy moons, comets, and primitive asteroids, which can lead to advances in our understanding of the interplay between inorganic and organic building blocks that led to the evolution of habitable environments on Earth and beyond. In many of these environments, the presence of water or aqueously altered mineralogy is an important indicator of habitable environments that are present or may have been present in the past. As a result, the search for complex organic chemistry that may imply the presence of a feedstock, if not an inventory of biosignatures, is naturally aligned with targeted analyses of water-rich surface materials. Here we describe the two-step laser mass spectrometry (L2MS) analytical technique that has seen broad application in the study of organics in meteoritic samples, now demonstrated to be compatible with an in situ investigation with technique improvements to target high priority planetary environments as part of a future scientific payload. An ultraviolet (UV) pulsed laser is used in previous and current embodiments of laser desorption/ionization mass spectrometry (LDMS) to produce ionized species traceable to the mineral and organic composition of a planetary surface sample. L2MS, an advanced technique in laser mass spectrometry, is selective to the aromatic organic fraction of a complex sample, which can provide additional sensitivity and confidence in the detection of specific compound structures. Use of a compact two-step laser mass spectrometer prototype has been previously reported to provide specificity to key aromatic species, such as PAHs, nucleobases, and certain amino acids. Recent improvements in this technique have focused on the interaction between the mineral matrix and the organic analyte. The majority of planetary targets of astrobiological interest are characterized by the presence of water or hydrated mineral phases. Water signatures can indicate a history of available liquid water that may have played an important role in the chemical environment of these planetary surfaces and subsurfaces. The studies we report here investigate the influence of water content on the detectability of organics by L2MS in planetary analog samples.

primitive asteroids↗

Process for Making Single-Domain Magnetite Crystals

A process for making chemically pure, single-domain magnetite crystals substantially free of structural defects has been invented as a byproduct of research into the origin of globules in a meteorite found in Antarctica and believed to have originated on Mars. The globules in the meteorite comprise layers of mixed (Mg, Fe, and Ca) carbonates, magnetite, and iron sulfides. Since the discovery of the meteorite was announced in August 1996, scientists have debated whether the globules are of biological origin or were formed from inorganic materials by processes that could have taken place on Mars. While the research that led to the present invention has not provided a definitive conclusion concerning the origin of the globules, it has shown that globules of a different but related chemically layered structure can be grown from inorganic ingredients in a multistep precipitation process. As described in more detail below, the present invention comprises the multistep precipitation process plus a subsequent heat treatment. The multistep precipitation process was demonstrated in a laboratory experiment on the growth of submicron ankerite crystals, overgrown by submicron siderite and pyrite crystals, overgrown by submicron magnesite crystals, overgrown by submicron siderite and pyrite. In each step, chloride salts of appropriate cations (Ca, Fe, and Mg) were dissolved in deoxygenated, CO2- saturated water. NaHCO3 was added as a pH buffer while CO2 was passed continuously through the solution. A 15-mL aliquot of the resulting solution was transferred into each of several 20 mL, poly(tetrafluoroethylene)-lined hydrothermal pressure vessels. The vessels were closed in a CO2 atmosphere, then transferred into an oven at a temperature of 150 C. After a predetermined time, the hydrothermal vessels were removed from the oven and quenched in a freezer. Supernatant solutions were decanted, and carbonate precipitates were washed free of soluble salts by repeated decantations with deionized water.

Golden, D. C.↗

Inorganic separator technology program

Testing and failure analyses of silver zinc cells with largely inorganic separators were performed. The results showed that the wet stand and cycle life objective of the silver-zinc cell development program were essentially accomplished and led to recommendations for cell composition, design, and operation that should yield further improvement in wet and cycle life. A series of advanced inorganic materials was successfully developed and formulated into rigid and semiflexible separator samples. Suitable screening tests for evaluation of largely inorganic separators were selected and modified for application to the separator materials. The results showed that many of these formulations are potentially superior to previously used materials and permitted selection of three promising materials for further evaluation in silver-zinc cells.

Smatko, J. S.↗

Applications of MODIS Fluorescent Line Height Measurements to Monitor Water Quality Trends and Algal Bloom Activity

Recent advances in satellite and airborne remote sensing, such as improvements in sensor and algorithm calibrations, processing techniques and atmospheric correction procedures have provided for increased coverage of remote-sensing, ocean-color products for coastal regions. In particular, for the Moderate Resolution Imaging Spectrometer (MODIS) sensor calibration updates, improved aerosol retrievals and new aerosol models has led to improved atmospheric correction algorithms for turbid waters and have improved the retrieval of ocean color in coastal waters. This has opened the way for studying ocean phenomena and processes at finer spatial scales, such as the interactions at the land-sea interface, trends in coastal water quality and algal blooms. Human population growth and changes in coastal management practices have brought about significant changes in the concentrations of organic and inorganic, particulate and dissolved substances entering the coastal ocean. There is increasing concern that these inputs have led to declines in water quality and have increase local concentrations of phytoplankton, which cause harmful algal blooms. In two case studies we present MODIS observations of fluorescence line height (FLH) to 1) assess trends in water quality for Tampa Bay, Florida and 2) illustrate seasonal and annual variability of algal bloom activity in Monterey Bay, California as well as document estuarine/riverine plume induced red tide events. In a comprehensive analysis of long term (2003-2011) in situ monitoring data and satellite imagery from Tampa Bay we assess the validity of the MODIS FLH product against chlorophyll-a and a suite of water quality parameters taken in a variety of conditions throughout a large optically complex estuarine system. A systematic analysis of sampling sites throughout the bay is undertaken to understand how the relationship between FLH and in situ chlorophyll-a responds to varying conditions and to develop a near decadal trend in water quality changes. In situ monitoring locations that correlated well with satellite imagery were in depths greater than seven meters and were located over five kilometers from shore. Water quality parameter of total nitrogen, phosphorous, turbidity and biological oxygen demand had high correlations with these sites, as well. Satellite FLH estimates show improving water quality from 2003-2007 with a slight decline up through 2011. Dinoflagellate blooms in Monterey Bay, California (USA) have recently increased in frequency and intensity. Nine years of MODIS FLH observations are used to describe the annual and seasonal variability of bloom activity within the Bay. Three classes of MODIS algorithms were correlated against in situ chlorophyll measurements. The FLH algorithm provided the most robust estimate of bloom activity. Elevated concentrations of phytoplankton were evident during the months of August-November, a period during which increased occurrences of dinoflagellate blooms have been observed in situ. Seasonal patterns of FLH show the on- and offshore movement of areas of high phytoplankton biomass between oceanographic seasons. Higher concentrations of phytoplankton are also evident in the vicinity of the land-based nutrient sources and outflows, and the cyclonic bay-wide circulation can transport these nutrients to the northern Bay bloom incubation region. Both of these case studies illustrate the utility MODIS FLH observations in supporting management decisions in coastal and estuarine waters.

Fischer, Andrew↗

Causes of Model Biases in Simulating Inorganic Aerosol Composition During KORUS-AQ and Implications for the Estimate of Transboundary Pollution

East Asia is a region of increasing economic growth which has led to severe PM2.5 pollution in urban areas. The joint NASA-NIER Korea-United States Air Quality (KORUS-AQ) field campaign in May-June 2016 provided an extensive dataset of ground, airborne, and remote sensing observations to test model simulations of PM2.5 pollution transport and potential control measures. During KORUS-AQ, a period of haze was observed in which PM2.5 rapidly increased to the highest levels observed during the campaign. This increase is associated with increasing inorganic aerosol. While a portion of this increase is due to long-range transport, there is observational evidence that aerosol formation from local precursors was also enhanced. This suggests that domestic policy measures could have a greater than expected influence on controlling PM2.5. However, models have difficulty reproducing PM2.5 levels, particularly the composition of secondary inorganic aerosol. Models generally underestimate sulfate and overestimate nitrate and fail to represent the peak levels of PM2.5 during haze events. These biases have been chiefly attributed to errors in chemical mechanisms and model meteorology, not issues with underlying emissions inventories. Here, we use observations from KORUS-AQ interpreted by the GEOS-Chem chemical transport model to improve the model’s ability to reproduce secondary inorganic aerosol concentrations during the campaign and explore mechanisms to improve model biases during the haze event. We assess the fraction of inorganic aerosol from the improved model simulation that results from transboundary transport during KORUS-AQ and test the model sensitivity to potential emission reduction measures that could improve air quality in Seoul during different meteorological periods including haze episodes.

Katie Travis↗

New Directions in Biotechnology

The macromolecule crystallization program within NASA is undergoing considerable pressure, particularly budgetary pressure. While it has shown some successes, they have not lived up to the expectations of others, and technological advances may rapidly overtake the natural advantages offered by crystallization in microgravity. Concomitant with the microgravity effort has been a research program to study the macromolecule crystallization process. It was believed that a better understanding of the process would lead to growth of improved crystals for X-ray diffraction studies. The results of the various research efforts have been impressive in improving our understanding of macromolecule crystallization, but have not led to any improved structures. Macromolecule crystallization for structure determination is "one of", the job being unique for every protein and finished once a structure is obtained. However, the knowledge gained is not lost, but instead lays the foundation for developments in new areas of biotechnology and nanotechnology. In this it is highly analogous to studies into small molecule crystallization, the results of which have led to our present day microelectronics-based society. We are conducting preliminary experiments into areas such as designed macromolecule crystals, macromolecule-inorganic hybrid structures, and macromolecule-based nanotechnology. In addition, our protein crystallization studies are now being directed more towards industrial and new approaches to membrane protein crystallization.

Source record↗

An Ensemble Investigation of the Causes for Regional Air-Quality Model Critical Load Exceedances Prediction Variability in European and North American Domains Using Diagnostics From Phase 4 of the Air Quality Model Evaluation International Initiative

We summarize tentative findings from multi air quality model ensembles for the years 2009 and 2010 in Europe (EU), and 2010 and 2016 in North America (NA), under AQMEII-4. The model predictions of sulphur and nitrogen deposition were used to estimate exceedances of critical loads for acidification and eutrophication, to show the extent to which the ensemble members agree in the magnitude and the trend of ecologically meaningful impacts. Model exceedance variability was analyzed using AQMEII-4 diagnostics. Evaluation against concentration and wet deposition observations, coupled with these diagnostics, identified specific process representations as the causes for variability between model predictions and for reduced model performance. All models predicted reductions in ecosystem acidification impacts in North America between the years 2010 and 2016, in accord with SO2 emissions reduction legislation which started in 2010 (SO2 SIP) However, all models in EU and NA domains had net negative biases for wet deposition of sulphur and nitrogen relative to observations. The wet S deposition average mean bias for the NA ensemble was -0.17 eq ha-1 d-1, and for the EU ensemble -1.15 eq ha-1 d-1. The NA daily wet deposition average mean bias for NH4+ was -0.37 eq ha-1d-1; EU -1.19 eq ha-1 d-1. The daily NA wet NO3- deposition average mean bias was -0.24 eq ha-1d-1; EU -0.69 eq ha-1 d-1. The members of the ensemble diverged (factor of 10) in their North American predictions for Ndep and consequently their eutrophication exceedances. The models with the highest eutrophication predictions also predicted the highest levels of gas-phase ammonia dry deposition (standard deviation of ammonia dry deposition flux across ensemble members was larger than the ensemble average). These models also had negative biases of predicted ammonia concentrations; average mean biases of -0.63 (satellite NH3) and -0.85 ppbv (surface NH3) compared to ensemble averages of -0.30 and -0.34 ppbv. Diagnostics showed that these differences resulted from the manner in which bidirectional ammonia fluxes were parameterized within these models. The second largest source of NA eutrophication prediction variability were models with positive biases in particulate ammonium and nitrate concentrations, and higher particle nitrogen deposition levels ( particle ammonium concentration bias +0.35 ug m-3; ensemble bias +0.15 ug m-3). We believe two factors may have led to these latter overestimates: higher levels of fine mode particle nitrate formation compared to other models (due to the use of an inorganic heterogeneous chemistry algorithm which did not take base cation chemistry into account), and updates to particle dry deposition velocities carried out in the absence of concurrent updates to wet scavenging algorithms. The relative importance of dry gas, dry particulate, and wet deposition towards total sulphur and nitrogen deposition totals differed between EU and North American domains, though all models had negative biases in wet deposition as noted above. Parallel and subsequent work suggests that multiphase hydrometeor scavenging may improve model wet deposition performance. An increased research focus is recommended for four model processes: multiphase hydrometeor scavenging, ammonia bidirectional fluxes, base cation chemistry and emissions, and particle dry deposition.

regional air-quality model↗

Self-Cleaning Coatings and Materials for Decontaminating Field-Deployable Land and Water-Based Optical Systems

This technology exploits the organic decomposition capability and hydrophilic properties of the photocatalytic material titanium dioxide (TiO2), a nontoxic and non-hazardous substance, to address contamination and biofouling issues in field-deployed optical sensor systems. Specifically, this technology incorporates TiO2 coatings and materials applied to, or integrated as a part of, the optical surfaces of sensors and calibration sources, including lenses, windows, and mirrors that are used in remote, unattended, ground-based (land or maritime) optical sensor systems. Current methods used to address contamination or biofouling of these optical surfaces in deployed systems are costly, toxic, labor intensive, and non-preventative. By implementing this novel technology, many of these negative aspects can be reduced. The functionality of this innovative self-cleaning solution to address the problem of contamination or biofouling depends on the availability of a sufficient light source with the appropriate spectral properties, which can be attained naturally via sunlight or supplemented using artificial illumination such as UV LEDs (light emitting diodes). In land-based or above-water systems, the TiO2 optical surface is exposed to sunlight, which catalyzes the photocatalytic reaction, facilitating both the decomposition of inorganic and organic compounds, and the activation of superhydrophilic properties. Since underwater optical surfaces are submerged and have limited sunlight exposure, supplementary UV light sources would be required to activate the TiO2 on these optical surfaces. Nighttime operation of land-based or above-water systems would require this addition as well. For most superhydrophilic self-cleaning purposes, a rainwater wash will suffice; however, for some applications an attached rainwater collector/ dispenser or other fresh water dispensing system may be required to wash the optical surface and initiate the removal of contaminates. Deployment of this non-toxic,non-hazardous-technology will take advantage of environmental elements (i.e. rain and sunlight), increase the longevity of unattended optical systems, increase the amount of time between required maintenance, and improve the long-term accuracy of sensor measurements.

Ryan, Robert↗

Scientific need for a cometary mission

Known facts about comets are reviewed including their organic and inorganic content. Photographs are used to show the differences in the physical appearances of the three types of comets. Space missions will provide the opportunity to determine the sequence of events that led to their formation and that of the solar system; how volatiles arrived on earth; and the basis for the existence of life on earth; and the source of the outer planetary system.

Whipple, F. L.↗

ELM: Europa Luminescence Microscope

The Europa Luminescence Microscope (ELM) is an automated fluorescence and bright-field microscope designed to meet key objectives defined in the 2016 NASA Europa Lander Study Report, including the identification and characterization of morphological biosignatures. ELM’s heritage stems from a 2U cubesat fluorescence microscope, the Fluorescence Analysis for In situ Research imager, designed and built at NASA Ames Research Center, for the autonomous study of microbial biology in low Earth orbit. For ELM implementation, a sample is autonomously manipulated with a microfluidic system using in-line 10, 1.0, and 0.2 μm pore-size filters to capture successively smaller particles for imaging. For bright-field imaging, ELM uses deep-ultraviolet, ultraviolet and visible light to image organic and inorganic structures with submicron resolution. The ability to detect biosignatures as small as 0.2 μm in size is achieved by imaging native fluorescence and using fluorescence microscopy stains to identify key structural and functional indicators of microbial life (proteins, lipids, nucleic acids). For fluorescence imaging, ELM uses 265, 370, 470, and 530 nm LEDs with five emission bands. The use of multiple excitation and emission wavelengths for native fluorescence imaging enables the detection of a wide range of molecular species and their rough classification. Excitation at 265 nm allows for the detection of smaller polycyclic aromatic hydrocarbons (PAH), aromatic amino acids, and proteins with little to no interference from mineral fluorescence, given proper emission band selection. 370 and 470 nm light excites increasingly larger PAH structures and larger aromatic biomolecules that may be present (e.g., protective pigments). Similarly, inorganic fluorescence can be characterized and separated from organic fluorescence, allowing the recognition and in some cases classification, of minerals and other abiotic particles. ELM is based upon work supported by the NASA COLDTech and ICEE-2 programs.

Richard C Quinn↗

Europa Luminescence Microscope

The Europa Luminescence Microscope (ELM) is an automated fluorescence and dark-field mi-croscope designed to meet key objectives defined in the NASA Europa Lander Study Report, includ-ing the identification and characterization of morphological biosignatures. ELM’s heritage stems from a 2U cubesat fluorescence microscope, the Fluorescence Analysis for In-situ Research (FLAIR) im-ager, designed and built at NASA Ames Research Center, for the autonomous study of microbial bi-ology in low Earth orbit. For the ELM implementation, a sample is autonomously manipulated with a microfluidic system using in-line filter sets to capture successively smaller particles on 10, 1.0, and 0.1 µm pore-size filters for imaging. For darkfield imaging, ELM uses ultraviolet and visible light to image organic and inorganic structures with submicron resolution. The ability to detect structural and chemical biosignatures as small as 0.2 µm in size is achieved by imaging native fluorescence and us-ing fluorescence microscopy stains to identify key molecular and structural indicators of microbial life (proteins, lipids, nucleic acids). To excite fluorescence, ELM uses LEDs with wavelengths centered near 265, 370, 470, and 530 nm and five emission bands. The use of multiple excitation and emission wavelengths for native fluorescence imaging not only enables the detection of different molecular species, but also their rough classification. Excitation at 265 nm allows for the detection of smaller polyaromatic hydrocarbons (PAHs; 1-5 rings), aromatic amino acids, and proteins with little to no interference from mineral fluorescence, given proper emission band selection. 370 and 470 nm light excites increasingly larger PAH structures (e.g., coronene) and larger aromatic biomolecules that may be present (e.g., protective pigments). Similarly, inorganic fluorescence can be characterized and sep-arated from organic fluorescence, allowing the recognition and in some cases classification, of miner-als and other abiotic particles. ELM is based upon work supported by the NASA COLDTech and ICEE-2 programs.

Microscope↗

Secondary Inorganic Aerosol Chemistry and Its Impact on Atmospheric Visibility Over an Ammonia-Rich Urban Area in Central Taiwan

This study investigated the hourly inorganic aerosol chemistry and its impact on atmospheric visibility over an urban area in Central Taiwan, by relying on measurements of aerosol light extinction, inorganic gases, and PM 2.5 water-soluble ions (WSIs), and simulations from a thermodynamic equilibrium model. On average, the sulfate (SO 4 2− ), nitrate (NO 3 − ), and ammonium (NH 4 + ) components (SNA) contributed ∼90% of WSI concentrations, which in turn made up about 50% of the PM 2.5 mass. During the entire observation period, PM 2.5 and SNA concentrations, aerosol pH, aerosol liquid water content (ALWC), and sulfur and nitrogen conversion ratios all increased with decreasing visibility. In particular, the NO 3 − contribution to PM 2.5 increased, whereas the SO 4 2− contribution decreased, with decreasing visibility. The diurnal variations of the above parameters indicate that the interaction and likely mutual promotion between NO 3 − and ALWC enhanced the hygroscopicity and aqueous-phase reactions conducive for NO 3 − formation, thus led to severely impaired visibility. The high relative humidity (RH) at the study area (average 70.7%) was a necessary but not sole factor leading to enhanced NO 3 − formation, which was more directly associated with elevated ALWC and aerosol pH. Simulations from the thermodynamic model depict that the inorganic aerosol system in the study area was characterized by fully neutralized SO 4 2− (i.e. a saturated factor in visibility reduction) and excess NH 4 + amidst a NH 3 -rich environment. As a result, PM 2.5 composition was most sensitive to gas-phase HNO 3 , and hence NOx, and relatively insensitive to NH 3 . Consequently, a reduction of NOx would result in instantaneous cuts of NO 3 − , PM 2.5 , and ALWC, and hence improved visibility. On the other hand, a substantial amount of NH 3 reduction (>70%) would be required to lower the aerosol pH, driving more than 50% of the particulate phase NO 3 − to the gas phase, thereby making NH 3 a limiting factor in shifting PM 2.5 composition.

aerosol chemistry↗

Thermal performance of a catalytic/oxidizer for the Space Station Freedom

Thermal analysis and testing have been performed for the High Temperature Catalytic/Oxidizer (HTCO) for the Space Station Freedom (SSF) Trace Contaminant Control Subassembly (TCCS). The HTCO consists of a counterflow, plate-fin heat exchanger, a resistance heater, and a charcoal catalytic oxidizer bed. The unit removes various inorganics and hydrocarbons from the SSF cabin air. A thermal model of the unit was developed which was used to design the HEX and catalytic bed. The model has been used to predict both steady state and transient results. Accurate predictions of ground test data have led to confidence in proper operation of the unit in the SSF.

Wedel, R. K.↗

Vitamin C-sulfate inhibits mineralization in chondrocyte cultures: a caveat

Differentiating chick limb-bud mesenchymal cell micro-mass cultures routinely mineralize in the presence of 10% fetal calf serum, antibiotics, 4 mM inorganic phosphate (or 2.5 mM beta-glycerophosphate), 0.3 mg/ml glutamine and either 25 microg/ml vitamin C or 5-12 microg/ml vitamin C-sulfate. The failure of these cultures to produce a mineralized matrix (assessed by electron microscopy, 45Ca uptake and Fourier transform infrared microscopy) led to the evaluation of each of these additives. We report here that the "stable" vitamin C-sulfate (ascorbic acid-2-sulfate) causes increased sulfate incorporation into the cartilage matrix. Furthermore, the release of sulfate from the vitamin C derivative appears to be responsible for the inhibition of mineral deposition, as demonstrated in cultures with equimolar amounts of vitamin C and sodium sulfate.

NASA Discipline Musculoskeletal↗

Isomeric Trisaryloxycyclotriphosphazene Polymer Precursors

Substances useful for making heat-and fire-resistant polymers. Cyclotriphosphazene-based monomers and polymer precursors led to development of high-temperature materials. Cyclotriphosphazene-derived monomers, polymer precursors, and polymers becoming important from both industrial and scientific points of view. Presence of phosphazene moiety in cyclotriphosphazene-based monomers and polymer precursors expected to impact special properties in desired high-performance materials containing inorganic backbones for aerospace applications. Useful for obtaining heat-and fire-resistant polymers for composites, adhesives, molding powders, and coating laminates. Also used in structures (e.g. secondary structures in aircraft), in construction of spacecraft, and in electronics and computer industries.

St. Clair, Terry L.↗

Contamination monitoring of the OSIRIS-REx ISO5 asteroid sample cleanroom

The OSIRIS-REx mission to asteroid Bennu successfully collected hundreds of grams of asteroid regolith in October 2020 [1]. The spacecraft departed Bennu in May 2021 for Earth return and will release the sample canister to be recovered in Utah in September 2023 [2]. Samples will be transported to the curation facility at NASA Johnson Space Center, where an ISO5 equivalent cleanroom has been designed in 2017 and completed in 2021. Aspects of the design and material selection for the cleanroom and its supporting facilities (air handling system, cleanroom floors and walls, filters, paints, etc.) were optimized to minimize effects of organic and inorganic contaminants and offgassing [3]. Since its completion, the lab has been carefully monitored to understand and establish a baseline with respect to multiple environmental aspects – measurement of particle counts, deploying Si wafer witness plates for organic and inorganic contaminants, deploying aluminum foils for a focus on organics with JSC in-house expertise, gas samples, and regular microbial and fungal measurements on selected surfaces and air samples in the cleanroom. This contribution will report on nearly one year of monitoring and highlight several specific aspects that have led to a better understanding of the new cleanroom environment.

carbonaceous asteroid↗

Carbonate petrography, kerogen distribution, and carbon and oxygen isotope variations in an early Proterozoic transition from limestone to iron-formation deposition, Transvaal Supergroup, South Africa

The transition zone comprises Campbellrand microbialaminated (replacing "cryptalgalaminate") limestone and shale, with minor dolomite, conformably overlain by the Kuruman Iron Formation of which the basal part is characterized by siderite-rich microbanded iron-formation with minor magnetite and some hematite-containing units. The iron-formation contains subordinate intraclastic and microbialaminated siderite mesobands and was deposited in deeper water than the limestones. The sequence is virtually unaltered with diagenetic mineral assemblages reflecting a temperature interval of about 110 degrees to 170 degrees C and pressures of 2 kbars. Carbonate minerals in the different rock types are represented by primary micritic precipitates (now recrystallized to microsparite), early precompactional sparry cements and concretions, deep burial limpid euhedral sparites, and spar cements precipitated from metamorphic fluids in close contact with diabase sills. Paragenetic pathways of the carbonate minerals are broadly similar in all lithofacies with kerogen intimately associated with them. Kerogen occurs as pigmentation in carbonate crystals, as reworked organic detritus in clastic-textured carbonate units, and as segregations of kerogen pigment around late diagenetic carbonate crystals. Locally kerogen may also be replaced by carbonate spar. Carbon isotope compositions of the carbonate minerals and kerogen are dependent on their mode of occurrence and on the composition of the dominant carbonate species in a specific lithofacies. Integration of sedimentary, petrographic, geochemical, and isotopic results makes it possible to distinguish between depositional, early diagenetic, deep burial, and metamorphic effects on the isotopic compositions of the carbonate minerals and the kerogen in the sequence. Major conclusions are that deep burial thermal decarboxylation led to 13C depletion in euhedral ferroan sparites and 13C enrichment in kerogen (organic carbon). Metamorphic sparites are most depleted in 13C. Carbonates in oxide-rich iron-formations are more depleted in 13C than those in siderite-rich iron-formation whereas the kerogens in oxide banded iron-formations (BIF) are more enriched. This implies that the siderite-rich iron-formations were not derived from oxide-rich iron-formation through reduction of ferric iron by organic matter. Organic matter oxidation by ferric iron did, however, decrease the abundance of kerogen in oxide-rich iron-formation and led to the formation of isotopically very light sparry carbonates. Siderite and calcmicrosparite both represent recrystallized primary micritic precipitates but differ in their 13C composition, with the siderites depleted in 13C by 4.6 per mil on average relative to calcmicrosparite. This means that the siderites were precipitated from water with dissolved inorganic carbon depleted in 13C by about 9 per mil relative to that from which the limestones precipitated. This implies an ocean system stratified with regard to total carbonate, with the deeper water, from which siderite-rich iron-formation formed, depleted in 13C. Iron-formations were deposited in areas of very low organic matter supply. Depletion of 13C may, therefore, derive not from degradation of organic matter but from hydrothermal activity, a conclusion which is supported by 18O composition of the carbonate minerals and trace element and rare earth element (REE) compositions of the iron-formations.

NASA Discipline Number 52-30↗