Speciation of rare earth elements in acid mine drainage precipitates by sequential extraction
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Engineering↗
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BSSD Performance Metric report: LLNL Soil Microbiome SFA (Q1 2021)
The LLNL “Microbes Persist” Soil Microbiome Scientific Focus Area (SFA) seeks to determine how microbial soil ecophysiology, population dynamics, and microbe-mineral-organic matter interactions regulate the persistence of microbial residues and the formation of soil carbon. Our SFA research program is now four years old; it evolved and benefited from previously-funded BSSD projects in the Firestone (UCB), Banfield (UCB), Sullivan (OSU) and Hungate (NAU) labs. We use stable isotope probing in combination with ‘omics to measure how changing water regimes shape activity of individual microbial populations and ecophysiological traits that affect the fate of microbial and plant C. Using measures of population dynamics and microbiome-mineral interactions, we are working to synthesize both genomescale and ecosystem-scale models of soil organic matter (SOM) turnover, to predict the long-aspired connection between soil microbiomes and fate of soil C.
54 ENVIRONMENTAL SCIENCES↗
Ion produced cometary organic crust
For several years many experimental results have been obtained on the chemical and physical changes induced by ion and electron irradiation of materials with a view to their Astrophysical relevance. Among the studied effects, one of particular interest is the formation of an organic refractory residue left over after ion irradiation and warming-up at room temperature. We call this residue IPHAC (ion produced hydrogenated amorphous carbon). Although 'in situ' infrared spectroscopy points out the formation of new molecular species during bombardment at low temperature, it is not clear if IPHAC is already formed or if its formation is triggered by temperature increase during warming-up of the irradiated target. Since Raman Spectroscopy is a technique particularly suitable for the analysis of carbonaceous materials, we have thought and build-up an experimental apparatus to obtain Raman Spectra of frozen hydrocarbons during ion irradiation. The present experimental results point out clearly to the formation of IPHAC already at low T and low energy deposition (approximately equal to a few eV/C-atom).
Baratta, G. Antonio↗
Identification of an interstellar oxide grain from the Murchison meteorite by ion imaging
We report here the first use of a new ion-imaging system to locate a rare interstellar aluminum oxide grain in a Murchison acid residue. While several types of carbon-rich interstellar grains, including graphite, diamond, SiC, and TiC, have previously been found, isotopically anomalous interstellar oxide grains have proven more elusive. We have developed an ion imaging system which allows us to map the isotopic composition of large numbers of grains relatively quickly and is, thus, ideally suited to search for isotopically exotic subsets of grains. The system consists of a PHOTOMETRICS CCD camera coupled to the microchannel plate/fluorescent screen of the WU modified CAMECA IMS-3F ion microprobe. Isotopic images of the sample surface are focused on the CCD and digitized. Subsequent image processing identifies individual grains in the images and determines isotopic ratios for each. For the present work, we have imaged in O-16 and O-18; negligible contributions of (17)OH(-) and (16)OH2(-) signals to the O-18 signal allow the use of low mass resolution, simplifying the measurements. Repeated imaging runs on terrestrial corundum particles showed that the system measures isotopic ratios reproducibly to about +/- 40%. Each imaging run took about six minutes to complete, and for this study there were on average 5-15 grains in each image. We have conducted imaging searches in 2-4 micron size separates of both Orgueil and Murchison.
Nittler, L. R.↗
Aqueous cleaning and verification processes for precision cleaning of small parts
The NASA Kennedy Space Center (KSC) Materials Science Laboratory (MSL) has developed a totally aqueous process for precision cleaning and verification of small components. In 1990 the Precision Cleaning Facility at KSC used approximately 228,000 kg (500,000 lbs) of chlorofluorocarbon (CFC) 113 in the cleaning operations. It is estimated that current CFC 113 usage has been reduced by 75 percent and it is projected that a 90 percent reduction will be achieved by the end of calendar year 1994. The cleaning process developed utilizes aqueous degreasers, aqueous surfactants, and ultrasonics in the cleaning operation and an aqueous surfactant, ultrasonics, and Total Organic Carbon Analyzer (TOCA) in the nonvolatile residue (NVR) and particulate analysis for verification of cleanliness. The cleaning and verification process is presented in its entirety, with comparison to the CFC 113 cleaning and verification process, including economic and labor costs/savings.
Allen, Gale J.↗
Seeking and Identifying Phyllosilicates on Mars - A Simulation Study
In a simulation of seeking phyllosilicates on Mars, terrestrial ocean sediments were found to provide high quality Raman spectra of clays with low interfering fluorescence because most organic residues had been converted to graphitic carbon. Additional information is contained in the original extended abstract.
Wang, A.↗
Thermal/Mechanical Response of a Polymer Matrix Composite at Cryogenic Temperatures
In order for polymeric-matrix composites to be considered for use as structural materials in the next generation of space transportation systems, the mechanical behavior of these materials at cryogenic temperatures must be investigated. This paper presents experimental data on the residual mechanical properties of a carbon-fiber polymeric composite, IM7/PETI-5, both before and after aging. Both tension and compression modulus and strength were measured at room temperature, -196C, and -269 C on five different laminate configurations. One set of specimens was aged isothermally for 576 hours at -184 C in an unconstrained state. Another set of corresponding specimens was aged under constant uniaxial strain for 576 hours at -184 C. Based on the experimental data presented, it is shown that trends in stiffness and strength that result from changes in temperature are not always smooth and consistent. Moreover, it is shown that loading mode and direction are significant for both stiffness and strength, and aging at cryogenic temperature while under load can alter the mechanical properties of pristine, un-aged laminates made of IM7/PETI-5 material.
Whitley, Karen S.↗
Performance Evaluation of Engineered Structured Sorbents for Atmosphere Revitalization Systems On Board Crewed Space Vehicles and Habitats
Engineered structured (ES) sorbents are being developed to meet the technical challenges of future crewed space exploration missions. ES sorbents offer the inherent performance and safety attributes of zeolite and other physical adsorbents but with greater structural integrity and process control to improve durability and efficiency over packed beds. ES sorbent techniques that are explored include thermally linked and pressure-swing adsorption beds for water-save dehumidification and sorbent-coated metal meshes for residual drying, trace contaminant control, and carbon dioxide control. Results from sub-scale performance evaluations of a thermally linked pressure-swing adsorbent bed and an integrated sub-scale ES sorbent system are discussed.
Howard, David F.↗
Fast Characterization of Magnetic Impurities in Single-Wall Carbon Nanotubes
We have demonstrated that the magnetic susceptibility measurement is a non-destructive, fast and accurate method to determine the residual metal catalysts in a few microgram single-wall carbon nanotube (SWCNT) sample. We have studied magnetic impurities in raw and purified SWCNT by magnetic susceptibility measurements, transmission electron microscopy, and thermogravimetry. The data suggest that the saturation magnetic moment and the effective field, which is caused by the interparticle interactions, decreases and increases respectively with the decrease of the particle size. Methods are suggested to overcome the uncertainty associated.
Chen, Feng↗
Heavy carbon in individual oxide grains from the Murchison meteorite
The carbon isotopic composition of individual oxide grains from Murchison HF-HCl acid residue CFOc has been measured in the ion microprobe. Many grains contain carbon with large C-13 excesses ranging to 7000 per mil. In most cases the carbon is present as micron-sized subgrains. The association of silicon with the anomalous carbon points towards SiC as carrier. If this tentative identification is correct, then the SIC grains most likely originated in the circumstellar atmospheres of red giants. Oxide grains in which the O-18/O-16 ratio has also been measured show variable O-16 excesses which are not correlated with the C-13 excesses. This indicates that the sources of the anomalous carbon and oxygen isotopic compositions of the oxide grains are unrelated.
Zinner, Ernst↗
Catalytic Removal of Oxygen and Pollutants in Exhaust Gases from Pressurized Oxy-Combustors
The primary goal of this project was to develop and validate advanced catalytic materials and systems for purifying the flue gas generated from pressurized oxy-combustors in an effort to achieve the purity specifications of carbon dioxide (CO 2 ) streams required by the U.S. Department of Energy (USDOE) for application in enhanced oil recovery. The technology has shown great potential for improving energy efficiency, simplifying process complexity, and lowering costs compared with current state-of-the-art oxy-combustion flue gas purification technologies. Laboratory studies were conducted for the development, characterization, and screening of metal catalysts for residual oxygen (O 2 ) reduction with methane (CH 4 ) and multifunctional carbon catalysts for combined nitrogen oxides (NO x ), sulfur oxides (SO x ), and mercury (Hg) removal. A bench-scale reverse-flow fixed-bed (RFFB) reactor and a trickle-bed direct-contact cooler (DCC) reactor capable of treating 15 standard liters per min of pressurized oxy-combustion flue gas were fabricated and tested with both a simulated flue gas in the laboratory and a slipstream of actual flue gas at a 100 kW th Staged, Pressurized Oxy-Combustion (SPOC) pilot facility. Process simulation and techno-economic studies were performed to evaluate the energy efficiency and cost of the developed catalytic flue gas purification process integrated into a conceptual 550-MWe SPOC power plant. The goal and objectives of the project have been successfully accomplished. A cobalt-manganese (CoMn) oxide catalyst was developed and demonstrated in the bench-scale RFFB reactor in either a reverse-flow or one-direction flow mode of operation that met the success criterion of performance for residual O 2 reduction. A carbon catalyst was developed and demonstrated in the bench-scale DCC reactor that met the success criterion of performance for combined NO x /SO x /Hg removal. Slipstream testing of the integrated DCC-RFFB system at the SPOC pilot facility demonstrated stable operation and verified the superior performance obtained in the laboratory. The techno-economic analysis showed that a 550-MWe SPOC plant integrated with the catalytic flue gas purification process would result in costs of electricity of $\$$96.94/MWh and $\$$80.27/MWh in two assessed cases compared with $\$$91.07/MWh reported for the USDOE’s Current Technology Case, which generated only a partially pure CO 2 stream. On the basis of the results and findings from this project, scale-up studies of materials production and system demonstration and optimization studies of reactors and processes are recommended at the next stage of technology development.
20 FOSSIL-FUELED POWER PLANTS↗
LDEF impact craters formed by carbon-rich impactors: A preliminary report
Two impact craters found in Al from the Long Duration Exposure Facility (LDEF) experiment tray have residues concentrated in the bottoms, along the walls, and on top of overturned rims. Analyses indicate a 'chondritic' compositional signature (Si, S, Ca, Fe, Mg, and Ni) for the bulk residue. In one crater (number 74), round to irregular silicate grains are overlain by carbon. In addition, carbon also partially covers the crater walls, the top of the raised overturned rim, and extends outward from the crater. The second crater (number 31) also contains carbon with similar distribution in and about the crater, although the silicate residue appears to be glassy. Silver, I, K, and F (possibly some of the Ca, S, and Cl) appear to be contaminants as well as analyzed aromatic carbonaceous species associated with the raised rim and the area surrounding the crater. The origin of the impactors is assumed to be extraterrestrial. The existence of impactor residue in two craters implies impact velocities less than or equal to 6 km, based on experimental hypervelocity studies.
Bunch, T. E.↗
Quantification of carbon phases in detonation soot
Soot is a powdery substance composed of solid residues that results from the incomplete combustion of hydrocarbons. Soot holds valuable information because its chemical makeup can provide answers for condensed carbon kinetics in HE detonations by quantitively identifying what carbon species remain. For carbon-rich explosives, this is particularly important because carbon kinetics is a major pathway for energy release. Current efforts have been able to qualitatively identify the carbons and confirm their presence, but we haven’t been able to successfully quantify them. For example, small angle x-ray diffraction has been fielded to qualitatively identify carbon phases as a function of time during a detonation (work by Trevor Willey and Mike Nielson). Other work (ice experiments) has focused on measuring the “effective” static cold curve equation of state (EOS) of the recovered carbon soots.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Distribution of inorganic species in two Antarctic cryptoendolithic microbial communities
Chemical differences were noted between two Antarctic cryptoendolithic (hidden within rock) microenvironments colonized by different microbial communities. Microenvironments dominated by cyanobacteria (BPC) had a higher pH (pH 7-8) than those dominated by lichen (LTL) (pH 4.5-5.5). In order to understand the interactions between the microbiota and the inorganic environment, the inorganic environment was characterized. Water-soluble, carbonate-bound, metal-oxide, organically bound, and residual inorganic species were sequentially extracted from rock samples by chemical means. Each fraction was then quantified using inductively coupled plasma atomic emission spectrometry. BPC contained much more water-soluble and carbonate-bound Ca and Mg than LTL. Metal-oxide species of Al, Fe, and Mn were more abundant in LTL than BPC. Metal oxides appeared to be mobilized (in the order Mn > Fe > Al) from the LTL lichen zone but remained immobile in BPC sandstone. The distribution of K and P bound to metal oxide reflected the distribution of iron oxide in LTL, an indication of the importance of iron in controlling the availability of nutrients in this ecosystem. Metal oxides in turn were likely controlled or influenced by organic matter associated with the lichen community. Despite overall depletion of Fe, Al, and K in the lichen zone, SEM X-ray analysis showed that they were enriched in fungal hyphae. Water-soluble P was present despite the presence of metal oxides, which sequester phosphate. This has biological relevance since P is an essential nutrient.
NASA Program Exobiology↗
Recovery of resources for advanced life support space applications: effect of retention time on biodegradation of two crop residues in a fed-batch, continuous stirred tank reactor
Bioreactor retention time is a key process variable that will influence costs that are relevant to long distance space travel or long duration space habitation. However. little is known about the effects of this parameter on the microbiological treatment options that are being proposed for Advanced Life Support (ALS) systems. Two bioreactor studies were designed to examine this variable. In the first one, six retention times ranging from 1.3 to 21.3 days--were run in duplicate, 81 working-volume continuous stirred tank reactors (CSTR) that were fed ALS wheat residues. Ash-free dry weight loss, carbon mineralization, soluble TOC reduction, changes in fiber content (cellulose, hemicellulose, and lignin), bacterial numbers, and mineral recoveries were monitored. At short retention times--1.33 days--biodegradation was poor (total: 16-20%, cellulose - 12%, hemicellulose - 28%) but soluble TOC was decreased by 75-80% and recovery of major crop inorganic nutrients was adequate, except for phosphorus. A high proportion of the total bacteria (ca. 83%) was actively respiring. At the longest retention time tested, 21.3 days, biodegradation was good (total: 55-60%, cellulose ca. 70%, hemicellulose - ca. 55%) and soluble TOC was decreased by 80%. Recovery of major nutrients, except phosphorus, remained adequate. A very low proportion of total bacteria was actively respiring (ca. 16%). The second bioreactor study used potato residue to determine if even shorter retention times could be used (range 0.25-2.0 days). Although overall biodegradation deteriorated, the degradation of soluble TOC continued to be ca. 75%. We conclude that if the goal of ALS bioprocessing is maximal degradation of crop residues, including cellulose, then retention times of 10 days or longer will be needed. If the goal is to provide inorganic nutrients with the smallest volume/weight bioreactor possible, then a retention time of 1 day (or less) is sufficient.
Non-NASA Center↗
Interaction of Soil pH and Mineralogy Controls Soil Organic Matter Persistence through Changes in the Composition and Amount of Microbial Necromass
Microbial necromass–mineral associations are key to long-term soil organic matter (SOM) persistence. However, how soil pH and mineralogy interact to regulate SOM stability remains poorly understood. Here, we used artificial soils to test how three clay minerals (bentonite, kaolinite, and goethite), adjusted to four pH levels (5–8), affect microbial activity (respiration), microbial physiology (carbon use efficiency, CUE), microbial-derived residue material (necromass), and the formation and stability of mineral-associated organic matter (MAOM). Artificial soils were inoculated with a rhizosphere-derived microbial community cultured under the same pH conditions and on two representative simulated exudate types (organic acids and carbohydrates) and incubated for 6 weeks. In two complementary experiments, we added necromass from known microbial taxa to the same minerals across pH levels to isolate the role of necromass chemistry and loading. We found that soil pH shaped MAOM chemistry by altering microbial activity and necromass composition. In interaction with mineral type, pH also controlled MAOM thermal stability. Higher necromass loading weakened mineral-organic bonding, reducing MAOM stability, consistent with zonal mineral–organic interaction models. Our results demonstrate that microbial activity, rather than carbon use efficiency, better predicts MAOM formation and that pH-dependent necromass composition and loading govern MAOM persistence. These findings advance mechanistic understanding of SOM stabilization and have implications for predicting soil carbon dynamics under shifting environmental conditions.
carbon use efficiency↗
Affordable Fiber-Reinforced Ceramic Composites Win 1995 R and D 100 Award
Affordable fiber-reinforced ceramic matrix composites (AFReCC) with high strength and toughness, good thermal conductivity, thermal shock resistance, and oxidation resistance are needed for high-temperature structural applications. AFReCC materials will have various applications in advanced high-efficiency and high-performance engines: that is, the High Speed Civil Transport (HSCT), space propulsion components, and land-based systems. For example, silicon-carbide-fiber-reinforced silicon carbide matrix composites show promise for meeting the criteria of high strength, thermal conductivity, and toughness required for the HSCT combustor liner. AFReCC received R&D Magazine's prestigious R&D 100 Award in 1995. The fabrication process for these composites has three steps. In the first step, fiber preforms are made and chemical vapor infiltration is used to apply the desired interface coating on the fibers. This step also rigidizes the preform. The second step consists of resin infiltration, which after pyrolysis, yields an interconnected network of porous carbon as the matrix. In the final step of the process, the carbon-containing preform is infiltrated with molten silicon or silicon alloys in a furnace. This converts the carbon to silicon carbide leaving as little as 5 percent residual free silicon or refractory disilicide phase. This process is suitable for any type of small-diameter fiber (e.g., carbon, alumina, or silicon carbide) woven into a two- or three-dimensional architecture. This processing approach leads to dense composites where matrix microstructure and composition can be tailored for optimum properties. It has much lower processing cost (less than 50 percent) in comparison to other approaches to fabricating silicon-carbide-based composites. The photograph shows the various AFReCC components. Thermomechanical and thermochemical characterization of these composites under the hostile environments that will be encountered in engine applications is underway.
Source record↗
Carbon Dioxide Collection and Purification System for Mars
One of the most abundant resources available on Mars is the atmosphere. The primary constituent, carbon dioxide, can be used to produce a wide variety of consumables including propellants and breathing air. The residual gases can be used for additional pressurization tasks including supplementing the oxygen partial pressure in human habitats. A system is presented that supplies pure, high-pressure carbon dioxide and a separate stream of residual gases ready for further processing. This power-efficient method freezes the carbon dioxide directly from the atmosphere using a pulse-tube cryocooler. The resulting CO2 mass is later thawed in a closed pressure vessel, resulting in a compact source of liquefied gas at the vapor pressure of the bulk fluid. Results from a demonstration system are presented along with analysis and system scaling factors for implementation at larger scales. Trace gases in the Martian atmosphere challenge the system designer for all carbon dioxide acquisitions concepts. The approximately five percent of other gases build up as local concentrations of CO2 are removed, resulting in diminished performance of the collection process. The presented system takes advantage of this fact and draws the concentrated residual gases away as a useful byproduct. The presented system represents an excelient volume and mass solution for collecting and compressing this valuable Martian resource. Recent advances in pulse-tube cryocooler technology have enabled this concept to be realized in a reliable, low power implementation.
Clark, D. Larry↗