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Multisectoral Climate Impact Hotspots in a Warming World

The impacts of global climate change on different aspects of humanity's diverse life-support systems are complex and often difficult to predict. To facilitate policy decisions on mitigation and adaptation strategies, it is necessary to understand, quantify, and synthesize these climate-change impacts, taking into account their uncertainties. Crucial to these decisions is an understanding of how impacts in different sectors overlap, as overlapping impacts increase exposure, lead to interactions of impacts, and are likely to raise adaptation pressure. As a first step we develop herein a framework to study coinciding impacts and identify regional exposure hotspots. This framework can then be used as a starting point for regional case studies on vulnerability and multifaceted adaptation strategies. We consider impacts related to water, agriculture, ecosystems, and malaria at different levels of global warming. Multisectoral overlap starts to be seen robustly at a mean global warming of 3 degC above the 1980-2010 mean, with 11% of the world population subject to severe impacts in at least two of the four impact sectors at 4 degC. Despite these general conclusions, we find that uncertainty arising from the impact models is considerable, and larger than that from the climate models. In a low probability-high impact worst-case assessment, almost the whole inhabited world is at risk for multisectoral pressures. Hence, there is a pressing need for an increased research effort to develop a more comprehensive understanding of impacts, as well as for the development of policy measures under existing uncertainty.

policies↗

High-Capacity, High-Voltage Composite Oxide Cathode Materials

This SBIR project integrates theoretical and experimental work to enable a new generation of high-capacity, high-voltage cathode materials that will lead to high-performance, robust energy storage systems. At low operating temperatures, commercially available electrode materials for lithium-ion (Li-ion) batteries do not meet energy and power requirements for NASA's planned exploration activities. NEI Corporation, in partnership with the University of California, San Diego, has developed layered composite cathode materials that increase power and energy densities at temperatures as low as 0 degC and considerably reduce the overall volume and weight of battery packs. In Phase I of the project, through innovations in the structure and morphology of composite electrode particles, the partners successfully demonstrated an energy density exceeding 1,000 Wh/kg at 4 V at room temperature. In Phase II, the team enhanced the kinetics of Li-ion transport and electronic conductivity at 0 degC. An important feature of the composite cathode is that it has at least two components that are structurally integrated. The layered material is electrochemically inactive; however, upon structural integration with a spinel material, the layered material can be electrochemically activated and deliver a large amount of energy with stable cycling.

Hagh, Nader M.↗

InGaN High-Temperature Photovoltaic Cells

This Phase II project developed Indium-Gallium-Nitride (InGaN) photovoltaic cells for high-temperature and high-radiation environments. The project included theoretical and experimental refinement of device structures produced in Phase I as well as modeling and optimization of solar cell device processing. The devices have been tested under concentrated air mass zero (AM0) sunlight, at temperatures from 100 degC to 250 degC, and after exposure to ionizing radiation. The results are expected to further verify that InGaN can be used for high-temperature and high-radiation solar cells. The large commercial solar cell market could benefit from the hybridization of InGaN materials to existing solar cell technology, which would significantly increase cell efficiency without relying on highly toxic compounds. In addition, further development of this technology to even lower bandgap materials for space applications would extend lifetimes of satellite solar cell arrays due to increased radiation hardness. This could be of importance to the Departmentof Defense (DoD) and commercial satellite manufacturers.

Starikov, David↗

MSL SAM-Like Evolved Gas Analyses of Si-rich Amorphous Materials

Chemical and mineralogical analyses of several samples from Murray Formation mudstones and Stimson Formation sandstones by the Mars Science Laboratory (MSL) revealed the presence of Si-rich amorphous or poorly ordered materials. It is possible to identify the presence of high-SiO2 vs. lower SiO2 amorphous materials (e.g., basaltic glasses), based on the position of the resulting wide diffraction features in XRD patterns from the Chemistry and Mineralogy (CheMin) instrument, but it is not possible to distinguish between several candidate high-SiO2 amorphous materials such as opal-A or rhyolitic glass. In the Buckskin (BS) sample from the upper Murray Formation, and the Big Sky (BY) and Greenhorn (GH) samples from the Stimson Formation, analyses by the Sample Analysis at Mars (SAM) instrument showed very broad H2O evolutions during sample heating at temperatures >450-500degC which had not been observed from previous samples. BS also had a significant broad evolution <450-500degC. We have undertaken a laboratory study targeted at understanding if the data from SAM can be used to place constraints on the nature of the amorphous phases. SAM-like evolved gas analyses have been performed on several opal and rhyolitic glass samples. Opal-A samples exhibited wide <500degC H2O evolutions, with lesser H2O evolved above ~500degC. H2O evolution traces from rhyolitic glasses varied, having either two broad H2O peaks, <300degC and >500degC, or a broad peak centered around 400degC. For samples that produced two evolutions, the lower temperature peak is more intense than the higher temperature peak, a trend also exhibited by opal-A. This trend is consistent with data from BS, but does not seem consistent with data from BY and GH which evolved most of their H2O >500degC. It may be that dehydration of opal-A and/or rhyolitic glass can result in some preferential loss of lower temperature H2O, to produce traces that more closely resemble BY and GH. This is currently under investigation and results will be reported.

McAdam, Amy↗

Effects of Martian Surface Materials on the Thermal Decomposition of Hydrogen Peroxide

While hydrogen peroxide (H2O2) has been detected in the martian atmosphere, it has not been detected in surface materials. Since the Viking lander mission, we have sent instruments to Mars with the capability to detect H2O2. The Sample Analysis at Mars (SAM) instrument onboard the Curiosity Rover and Thermal and Evolved Gas Analyzer (TEGA) instrument on the Phoenix lander both detected water and oxygen releases from analyzed sediments but whether or not peroxide could be the source of these gases has not been investigated. We are investigating the possible presence of H2O2 in martian materials by analyzing Mars-relevant minerals that have been mixed with hydrogen peroxide using lab instruments configured as analogs to Mars mission instruments. The object of this research is to use lab instruments to find the effects of Mars analog minerals on hydrogen peroxide gas release temperatures, specifically gas releases of water and oxygen and also determine the effect of the peroxide on the minerals. Data that we get from the lab can then be compared to the data collected from Mars. The minerals hematite, siderite, San Carlos olivine, magnetite and nontronite were chosen as our Mars analog minerals. ~20 mg of analog Mars minerals with 5μl of 50% H2O2, and were either run immediately or placed in a sealed tube for 2, 4, or 9 days to look for changes over time with two reps being done at each time step to determine repeatability. Each sample was heated from -60 degC to 500 degC at 20 degC/min and the evolved gases were monitored with a mass spectrometer. Each sample was also analyzed with an X-ray diffraction instrument to look for changes in mineralogy. Preliminary results show three potential outcomes: 1) peroxide has no effect on the sample (e.g., hematite), 2) the mineral is unaffected but catalyzes peroxide decomposition (magnetite, siderite), or 3) peroxide alters the mineral (pyrrhotite, San Carlos olivine).

Archer, P. D., Jr.↗

Radiation Tests of Single Photon Avalanche Diode for Space Applications

Single photon avalanche diodes (SPADs) have been recently studied as photodetectors for applications in space missions. In this presentation we report the results of radiation hardness test on large area SPAD (actual results refer to SPADs having 500 micron diameter). Dark counts rate as low as few kHz at −10 degC has been obtained for the 500 micron devices, before irradiation. We performed bulk damage and total dose radiation tests with protons and gamma-rays in order to evaluate their radiation hardness properties and their suitability for application in a Low Earth Orbit (LEO) space mission. With this aim SPAD devices have been irradiated using up to 20 krad total dose with gamma-rays and 5 krad with protons. The test performed show that large area SPADs are very sensitive to proton doses as low as 2×10(exp 8) (1 MeV eq) n/cm2 with a significant increase in dark counts rate (DCR) as well as in the manifestation of the "random telegraph signal" effect. Annealing studies at room temperature (RT) and at 80 degC have been carried out, showing a high decrease of DCR after 24-48 h at RT. Lower protons doses in the range 1-10×10(exp 7) (1 MeV eq) n/cm(exp 2) result in a lower increase of DCR suggesting that the large-area SPADs tested in this study are well suitable for application in low-inclination LEO, particularly useful for gamma-ray astrophysics.

radiation hardness↗

Design and Development of a Laboratory-Scale Ice Adhesion Testing Device

When an aircraft traverses through clouds containing supercooled water droplets, in-flight icing can occur that negatively affects vehicle performance by increasing weight and drag leading to loss of lift. Super-cooled water droplets present in clouds that impact vehicle surfaces can lead to inflight icing any time during the year.1 Most events occur at temperatures ranging from 0 to -20degC. Ice generated on the aircraft can vary between clear/glaze, rime, and mixed (Fig. 1) depending on air temperature (-5 to -20degC), liquid water content (0.3-0.6 g/m3), and droplet size (median volumetric diameter of 15-40 μm). Current strategies to remove ice are based on active technologies such as pneumatic boots, heated surfaces, and deicing agents (i.e., ethylene- and propylene-based glycols). The latter have potential environmental concerns. A passive approach to mitigate accreting ice that is actively being investigated are protective coatings. An ice mitigating coating could potentially be used as a stand-alone material, but more likely in combination with an active approach. In the latter scenario, potential reduction in power consumption by the active approach may be realized. To determine the ice adhesion strength of impact ice that is representative of the aircraft environment is not a trivial matter. Test methods utilizing slowly formed ice (i.e., freezer ice) do not accurately simulate this environment. Likewise, some testing methodologies involve sample relocation from the icing environment to the test chamber that can result in thermal shock to the sample, thus affecting the results. The Adverse Environment Rotor Test Stand (AERTS) located at Pennsylvania State University (PSU) has been demonstrated to simulate impact icing conditions within the icing envelope for the determination of ice adhesion shear strength (IASS) without removal/relocation of the sample.2 Due to the confidence in results obtained from AERTS, this instrument is in high demand and requires a significant amount of lead time and capital investment to obtain IASS results. As a solution for quickly and economically screening coatings in a controlled manner under impact icing conditions, a laboratory-scale ice adhesion test and dead blades were then removed from the rotor/blade assembly to obtain the final mass. The IASS of the live blade was determined from the difference in mass (before and after testing) of the live and dead blades, the ice shed area, and the rpm of the shed event. The same live blade sample was tested in triplicate at all three test temperatures. Surface roughness was determined using a Bruker Dektak XT Stylus Profilometer. Measurements were conducted using a 12.5 μm tip at a vertical range of 65.5 μm with an applied force of 3 mg. Data were collected over a 1.0 mm length at a resolution of 0.056 μm/point. Five single line scans at different locations were collected and processed using a two-point leveling subtraction. The resultant Ra (arithmetic roughness) and Rq (root mean square roughness) average values were calculated.

Smith, Joseph G., Jr.↗

Utah FORGE Hydrothermal Friction-Hydraulic Transmissivity Laboratory Experiments

Submission includes data from laboratory slide-hold-slide tests, combined with flow through tests, conducted on Westerly granite with 30 degree sawcut. Tests were conducted with a constant confining pressure of 30 MPa with an average pore pressure of 10 MPa at temperatures of 23 and 200 degC. Three fluid flow conditions were examined (1) no flow, (2) cycled flow, and (3) continuous flow. Data were collected to asses the effect of temperature and pore fluid on frictional healing rates in granite at geothermal conditions. Data is available in XML and JSON data types.

15 GEOTHERMAL ENERGY↗

Ultra-lightweight, Low Scatter, Large Mirror Technology

A technique is being developed to fabricate a prototype lightweight composite mirror one meter in diameter. The mandrel, on which the composite mirror will be laid up, is an ultra low expansion quartz glass, TSG, whose thermal expansion coefficient, 10(exp -7)/ degC or less, is similar to that for the composite material itself. The mandrel surface will be super-polished to 6-8 A rms or better, resulting in ten times less scattered light in the visible region than is found in typical astronomical mirrors. We have shown experimentally that mandrel micro-roughnesses of this order can be successfully replicated on composite faceplates. The faceplate is very tough, and does not fracture like a thin glass faceplate. It will be supported by actuators alone, not by the edge of the mirror mount, to avoid non-uniform or non-symmetric influence functions. BOR developed actuators are designed for atmospheric correction, maintenance of optical figure, and minor tip tilt. They have a throw of a centimeter, can be controlled remotely, and have a response time of 1/2 msec. The piezoelectric part of the actuator operates in the 30-70 V range and the differential screw portion has a linearity of about +/-0.1 microns.

Bennett, H. E.↗

Advanced Embedded Active Assemblies for Extreme Space Applications

This work describes the development and evaluation of advanced technologies for the integration of electronic die within membrane polymers. Specifically, investigators thinned silicon die, electrically connecting them with circuits on flexible liquid crystal polymer (LCP), using gold thermo-compression flip chip bonding, and embedding them within the material. Daisy chain LCP assemblies were thermal cycled from -135 to +85degC (Mars surface conditions for motor control electronics). The LCP assembly method was further utilized to embed an operational amplifier designed for operation within the Mars surface ambient. The embedded op-amp assembly was evaluated with respect to the influence of temperature on the operational characteristics of the device. Applications for this technology range from multifunctional, large area, flexible membrane structures to small-scale, flexible circuits that can be fit into tight spaces for flex to fit applications.

lead bonding↗

Do We Already have Samples of CERES H Chondrite Haliites and the CERES-HEBE Link

We investigate the hypothesis that halite grains in the brecciated H chondrites Zag and Monahans originate from Ceres. Evidence includes mineralogy of the halites consistent with formation on a large, carbonaceous, aqueously active body close to the H chondrite parent body >4 Ga ago. Evidence also includes orbital simularities between 1 Ceres and the purported H chondrite parent body (HPB) 6 Hebe, possibly facilitating a gentle transfer between the bodies. Halite grains in the Monahans and Zag Hchondrites are exogenous to the H chondrite parent body and were transported to the HPB >4 Ga ago. Examination of minerals and carboanceous materials entrained within the halites shows that the halite parent body (HaPB) is consistent with a carbonaceous body [1]. It is probably a large body due to the variety of entrained carbonaceous materials which probably accreted from multiple sources. The halite grains contain intact, HaPB-origin, ancient fluid inclusions indicating that transfer between the HaPB and the HPB was a gentle process resulting in a ΔT of <25 degC. Ejection from the HaPB may have been via cryovolcanic processes similar to those on modern-day Enceladus, which have been interpreted to include halite from spectroscopic observations. The ΔTmax to preserve the brinebearing halite restricts the impact velocity to the HPB at less than ≈350-700 m/s, depending upon the fraction of kinetic energy used heat the sample. [2-6]. Therefore the HaPB and HPB must have shared nearby orbits at the time of the HaPB-HPB transfer. Evidence presented elsewhere indicates asteroid 6 Hebe is a favored candidate for the HPB based on reflectance spectrum similarity with H chondrites and dynamical arguments [7,8]. The modern orbits of Ceres and Hebe are reasonably similar, with aphelion/perihelion of Ceres and Hebe of 2.99/2.55 and 2.91/1.94 AU, respectively. Initial calculations indicate an approximate mean infall velocity of 1.20 to 1.38 km/s. While higher than 350- 700 m/s, the orbits may have been more favorable >4 Ga ago. Additional dynamical factors need to be investigated. A combination of factors suggests Ceres as the HaPB. It is a carbonaceous body with suggestions of past aqueous activity [9], which is consistent with the mineral species found in H chondrite halites. Ceres is also a large body capable of accreting the range of carbonaceous materials noted [5]. It is relatively near to purported HPB Hebe, which is required to preserve halite fluid inclusions. The above evidence defines a hypothesized scenario featuring ejection of halite grains from Ceres onto Hebe. Halite was then entrained in H-chondrite near-surface breccias and ejected from Hebe for transport to Earth.

Fries, Marc D.↗

The Mechanical Properties of Candidate Superalloys for a Hybrid Turbine Disk

The mechanical properties of several cast blade superalloys and one powder metallurgy disk superalloy were assessed for potential use in a dual alloy hybrid disk concept of joined dissimilar bore and web materials. Grain size was varied for each superalloy class. Tensile, creep, fatigue, and notch fatigue tests were performed at 704 to 815 degC. Typical microstructures and failure modes were determined. Preferred materials were then selected for future study as the bore and rim alloys in this hybrid disk concept. Powder metallurgy superalloy LSHR at 15 micron grain size and single crystal superalloy LDS-1101+Hf were selected for further study, and future work is recommended to develop the hybrid disk concept.

Gabb, Timothy P.↗

No Need to Wait for the Clean Air Dividend

Controlling smog and soot is the classic win-win situation, so it's great that the world is finally waking up to the idea. WHAT if there was a way to simultaneously slow down climate change, save millions of lives, improve crop yields and contribute to sustainable development and energy security? It sounds too good to be true, but it is possible. It won't be free or easy, but with some effort and moderate investment, it can be done. The way to do it is to reduce emissions leading to two types of pollution: black carbon and ozone. These are the only pollutants that we know contribute to both global warming and poor air quality. Black carbon is essentially soot, emitted from incomplete combustion of fossil fuels and biomass. It warms the climate in two ways: by absorbing heat in the atmosphere - similar to the greenhouse effect - and by reducing Earth's albedo, or ability to reflect sunlight. Inhaled into the lungs, it leads to cancer and cardiovascular disease. Ozone in the atmosphere also acts as a greenhouse gas, while ground-level ozone is toxic to humans and plants, so leads to both premature death and reduced crop yields. Ozone is not emitted directly but is produced by the action of sunlight on other pollutants, which are known as ozone precursors. Since black carbon and ozone are important components of soot and smog, a great deal of effort has already been put into developing methods to reduce emissions. So effective technology is available, but needs wider implementation. The recommended control measures for black carbon include widespread and tight emission standards on diesel cars and trucks; improved solid fuel cooking stoves, brick kilns and coke ovens in the developing world; and a ban on the open burning of agricultural waste. Implementation of these measures would have a rapid impact on the climate and human health, and also have the added benefit of greatly reducing emissions of carbon monoxide, an important ozone precursor. A second key ozone precursor is methane, which is also a powerful greenhouse gas in its own right. Control measures include reducing leaks from natural gas pipelines and storage tanks, and capturing it from coal, gas and oil extraction, landfills and wastewater treatment plants. Aeration of rice paddies and manure management can also reduce methane releases. Captured methane can often be sold or turned into power. In Monterrey, Mexico, for example, electricity generated from methane collected from the city landfill powers the public transportation system. So such measures can be beneficial even when ignoring the health and climate effects, as they can contribute to energy security and often pay for themselves. According to calculations by me and my colleagues, phasing in all these measures over the next 20 years would reduce global warming by about 0.5 degC in 2050, half of the projected increase between now and then (Science, vol 335, p 183). Regional benefits would be even greater, as black carbon disrupts rainfall patterns and magnifies warming and melting of snow and ice in parts of the world including the Arctic and the Himalayas. On top of the climate benefits, cutting black carbon and ozone would prevent over 3 million premature deaths from air pollution, and increase yields of staple crops by roughly 50 million tonnes a year. Improved cooking stoves would also decrease the demand for firewood in the developing world, reducing deforestation and freeing up time for those who collect wood - primarily women and children - to pursue other activities such as education. Similarly, improved brick kilns now being used in parts of Latin America and Asia require half as much fuel as traditional ones and are less time-intensive for the operators. This means that in addition to their environmental benefits, these measures can contribute to sustainable and human development. Tackling black carbon and methane is clearly a great idea, so why hasn't it been done already? There are many barriers. The upfront costs of some measures can be prohibitive even when they eventually pay for themselves. But this can be overcome by mechanisms such as international financing of capital costs. For other measures, the costs are typically borne by a few while the benefits accrue to everybody. In such cases civil society and governments must get involved. Governments are starting to act. In February, the US, Canada, Sweden, Bangladesh, Ghana and Mexico launched the Climate and Clean Air Coalition to support implementation of measures like these. This coalition will hopefully expand and achieve rapid, widespread adoption of measures to cut black carbon and ozone. While the climate benefits will be substantial, it is important to note that these measures cannot substitute for cuts in carbon dioxide. Black carbon, ozone, carbon monoxide and methane stay in the atmosphere for a fairly short time - a few days for black carbon and about a decade for methane. They thus respond quickly to emissions changes and give us substantial leverage over near-term climate change. In contrast, carbon dioxide is very long-lived and so responds slowly to emissions changes. This means that cuts have little immediate impact, but it also means they must be made now to avoid disastrous changes later on. Controlling short-lived climate pollutants is thus an issue of fairness. Much as failure to reduce carbon dioxide emissions soon would condemn future generations to disastrous change, failure to reduce near-term climate change condemns those alive today to suffer worsening effects of the sort already seen. Some wonder if we really can do both. We can, and we must.

Shindell, Drew↗

Quasi-Linear Circuit

This work involved developing spacequalifiable switch mode DC/DC power supplies that improve performance with fewer components, and result in elimination of digital components and reduction in magnetics. This design is for missions where systems may be operating under extreme conditions, especially at elevated temperature levels from 200 to 300 degC. Prior art for radiation-tolerant DC/DC converters has been accomplished utilizing classical magnetic-based switch mode converter topologies; however, this requires specific shielding and component de-rating to meet the high-reliability specifications. It requires complex measurement and feedback components, and will not enable automatic re-optimization for larger changes in voltage supply or electrical loading condition. The innovation is a switch mode DC/DC power supply that eliminates the need for processors and most magnetics. It can provide a well-regulated voltage supply with a gain of 1:100 step-up to 8:1 step down, tolerating an up to 30% fluctuation of the voltage supply parameters. The circuit incorporates a ceramic core transformer in a manner that enables it to provide a well-regulated voltage output without use of any processor components or magnetic transformers. The circuit adjusts its internal parameters to re-optimize its performance for changes in supply voltage, environmental conditions, or electrical loading at the output

Bradley, William↗

Detection of Only Viable Bacterial Spores Using a Live/Dead Indicator in Mixed Populations

This method uses a photoaffinity label that recognizes DNA and can be used to distinguish populations of bacterial cells from bacterial spores without the use of heat shocking during conventional culture, and live from dead bacterial spores using molecular-based methods. Biological validation of commercial sterility using traditional and alternative technologies remains challenging. Recovery of viable spores is cumbersome, as the process requires substantial incubation time, and the extended time to results limits the ability to quickly evaluate the efficacy of existing technologies. Nucleic acid amplification approaches such as PCR (polymerase chain reaction) have shown promise for improving time to detection for a wide range of applications. Recent real-time PCR methods are particularly promising, as these methods can be made at least semi-quantitative by correspondence to a standard curve. Nonetheless, PCR-based methods are rarely used for process validation, largely because the DNA from dead bacterial cells is highly stable and hence, DNA-based amplification methods fail to discriminate between live and inactivated microorganisms. Currently, no published method has been shown to effectively distinguish between live and dead bacterial spores. This technology uses a DNA binding photoaffinity label that can be used to distinguish between live and dead bacterial spores with detection limits ranging from 109 to 102 spores/mL. An environmental sample suspected of containing a mixture of live and dead vegetative cells and bacterial endospores is treated with a photoaffinity label. This step will eliminate any vegetative cells (live or dead) and dead endospores present in the sample. To further determine the bacterial spore viability, DNA is extracted from the spores and total population is quantified by real-time PCR. The current NASA standard assay takes 72 hours for results. Part of this procedure requires a heat shock step at 80 degC for 15 minutes before the sample can be plated. Using a photoaffinity label would remove this step from the current assay as the label readily penetrates both live and dead bacterial cells. Secondly, the photoaffinity label can only penetrate dead bacterial spores, leaving behind the viable spore population. This would allow for rapid bacterial spore detection in a matter of hours compared to the several days that it takes for the NASA standard assay.

Behar, Alberto E.↗

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

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

Socki, Richard↗

Oxygen Permeability and Grain-Boundary Diffusion Applied to Alumina Scales

High-temperature oxygen permeability measurements had determined grain-boundary diffusivities (deltaD(sub gb)) in bulk polycrystalline alumina (Wada, Matsudaira, and Kitaoka). They predict that oxygen deltaD(sub gb,O) varies with oxygen pressure as P(O2)(sup -1/6) at low pressure whereas aluminum deltaD(sub gb),Al varies with P(O2)(sup +3/16) at high pressure. These relations were used to evaluate alumina scale growth in terms of diffusivity and grain size. A modified Wagner treatment for dominant inward oxygen growth produces the concise solution: П(sub i) = k(sub p,i)×G(sub i) = 12 deltaD(sub gb,O,int), where П(sub i) is a constant and k(sub p,i) and G(sub i) refer to instantaneous values of the scale parabolic growth constant and grain size, respectively. A commercial FeCrAl(Zr) alloy was oxidized at 1100 to 1400 degC to determine k(sub p,i), interfacial grain size, П, and thus deltaD(sub gb,O,int). The deltaD(sub gb,O,int) values predicted from oxidation at (375 kJ/mole) were about 20 times less than those obtained above (at 298 kJ/mole), but closer than extrapolations from high-temperature bulk measurements. The experimental oxidation results agree with similar FeCrAl(X) studies, especially where both k(sub p,i) and G(sub i) were characterized. This complete approach accounts for temperature-sensitive oxidation effects of grain enlargement, equilibrium interface pressure variation, and grain-boundary diffusivity.

Smialek, James L.↗

The First X-ray Diffraction Patterns of Clay Minerals from Gale Crater

The Mars Science Laboratory (MSL) Rover, Curiosity spent approx 150 sols at Yellowknife Bay (YKB) studying a section of fluvio-lacustrine sedimentary rocks (with potential indications of volcanic influence), informally known as the Yellowknife Bay formation. YKB lies in a distal region of the Peace Vallis alluvial fan, which extends from the northern rim of Gale Crater toward the dune field at the base of Mt Sharp. Sedimentological and stratigraphic observations are consistent with the Yellowknife Bay formation being part of a distal fan deposit, which could be as young as middle Hesperian to even early Amazonian in age (approx 3.5 to 2.5 Ga). The Yellowknife Bay formation hosts a unit of mudstone called the Sheepbed member. Curiosity obtained powdered rock samples from two drill holes in the Sheepbed Member, named John Klein and Cumberland, and delivered them to instruments in Curiosity. Data from CheMin, a combined X-ray diffraction (XRD)/X-ray fluorescence instrument (XRF), has allowed detailed mineralogical analysis of mudstone powders revealing a clay mineral component of approx 20 wt.% in each sample. The clay minerals are important indicators of paleoenvironmental conditions and sensitive recorders of post-depositional alteration processes. The XRD pattern of John Klein reveals a 021 band consistent with a trioctahedral phyllosilicate. A broad peak at approx 10A with a slight inflexion at approx 12A indicates the presence of 2:1 type clay minerals in the John Klein sample. The trioctahedral nature of the clay minerals, breadth of the basal reflection, and presence of a minor component with larger basal spacing suggests that John Klein contains a trioctahedral smectite (probably saponite), whose interlayer is largely collapsed because of the low-humidity conditions. The XRD patterns show no evidence of corrensite (mixed-layer chlorite/smectite) or chlorite, which are typical diagenetic products of trioctahedral smectites when subjected to burial and heating >60degC in the presence of water. Given estimated geothermal gradients on Mars temperatures <60 degC might still be consistent with (but do not require) moderate burial. However, our ability to identify interstratified minerals is greatly limited by the lack of access to traditional treatments methods used in the lab (e.g., ethylene glycol solvation). Our preferred explanation for the origin of trioctahedral smectites in Sheepbed mudstone is in situ production via reaction of olivine, water and Si-bearing amorphous material, an important mudstone component detected by XRD. Elevated levels of magnetite in the Sheepbed and the trioctahedral monomineralic nature of the clay minerals support this model. These observations, combined with previous studies of olivine stability, support the persistence of circum-neutral hydrous conditions for thousands of years at YKB.

Bristow, Thomas↗