Structural, chemical, and isotopic microanalytical investigations of graphite from supernovae

We report the results of coordinated ion microprobe and transmission electron microscope (TEM) studies of presolar graphites from the KE3 separate (1.65-1.72 g/cm³) of the Murchison CM2 meteorite. Isotopic analysis of individual graphites (1-12 μm) with the ion microprobe shows many to have large ¹⁸O excesses combined with large silicon isotopic anomalies, indicative of a supernova (SN) origin. Transmission electron microscopy (TEM) of ultramicrotome slices of these SN graphites revealed a high abundance (25-2400 ppm) of internal titanium carbides (TiCs), with a single graphite in some cases containing hundreds of TiCs. Isotopic compositions of individual TiCs by nanoscale resolution secondary ion mass spectrometry (NanoSIMS) confirmed their presolar origin. In addition to TiCs, composite TiC/Fe grains (TiCs with attached iron-nickel subgrains) and solitary kamacite internal grains were found. In the composite grains, the attached iron phase (kamacite [0-24 at. % Ni] or taenite [up to 60 at. % Ni]) was epitaxially grown onto one or more TiC faces. In contrast to the denser Murchison KFC1 graphites, no Zr-Ti-Mo carbides were observed. The average TiC diameters were quite variable among the SN graphites, from 30 to 232 nm, and were generally independent of the host graphite size. TiC grain morphologies ranged from euhedral to anhedral, with the grain surfaces exhibiting variable degrees of corrosion, and sometimes partially amorphous rims (3 to 15 nm thick). Partially amorphous rims of similar thickness were also observed on some solitary kamacite grains. We speculate that the rims on the internal grains are most plausibly the result of atom bombardment caused by drift of grains with respect to the ambient gas, requiring relative outflow speeds ∼100 km/s (i.e., a few percent of the SN mass outflow speed).Energy dispersive X-ray spectrometry (EDXS) of TiCs revealed significant V in solid solution, with an average V/Ti ratio over all TiCs of ∼83% of the solar value of 0.122. Significant variations about the mean V/Ti ratio were also seen among TiCs in the same graphite, likely indicating chemical equilibration with the surrounding gas over a range of temperatures. In general, the diversity in internal TiC properties suggests that TiCs formed first and had substantially diverse histories before incorporation into the graphite, implying some degree of turbulent mixing in the SN outflows.In most graphites, there is a decrease in the number density of TiCs as a function of increasing radial dis- tance, caused by either preferential depletion of TiCs from the gas or an acceleration of graphite growth with decreasing ambient temperature. In several graphites, TiCs showed a trend of larger V/Ti ratios with increasing distance from the graphite center, an indication of progressive equilibration with the surrounding gas before they were sequestered in the graphites. In all but one graphite, no trend was seen in the TiC size vs. distance from the graphite center, implying that appreciable TiC growth had effectively stopped before the graphites formed, or else that graphite growth was rapid compared to TiC growth. Taken together, the chemical variations among internal grains as well as the presence of partially amorphous rims and epitaxial Fe phases on some TiCs clearly indicate that the phase condensation sequence was TiC, followed by the iron phases (only found in some graphites) and finally graphite. Since graphite typically condenses at a higher temperature than iron at low pressures (<10⁻³ bars) in a gas with C > O and otherwise solar composition, the observed condensation sequence implies a relative iron enrichment in the gas or greater supersaturation of graphite relative to iron.The TEM observations allow inferences to be made about the physical conditions in the gas from which the grains condensed. Given the TiC sizes and abundances, the gas was evidently quite dusty. From the observed TiC size range of ∼20 nm to ∼500 nm (assuming ∼1 yr growth time and T ∼ 1800°K), we infer minimum Ti number densities in the gas to be ∼7 × 10⁴ to ∼2 × 10⁶ atoms/cc, respectively. Although the gas composition is clearly not solar, for scale, these number densities would correspond to a pressure range of ∼0.2 μbar to ∼5.0 μbar in a gas of solar composition. They also correspond to minimum TiC grain number densities of ∼3 × 10⁻⁴ to ∼0.2 grains/cc, assuming complete condensation of Ti in TiC. We estimate the maximum ratio of mean TiC grain separation distance in the gas to grain diameter from the Ti number densities as ∼3 × 10⁵ to ∼1 × 10⁶.     

Formation of meteorite hydrocarbons from thermal decomposition of siderite (FeCO3)

Thermal decomposition of siderite has been proposed as a source of magnetite in martian meteorites. Laboratory experiments were conducted to evaluate the possibility that this process might also result in abiotic synthesis of organic compounds. Siderite decomposition in the presence of water vapor at 300°C generated a variety of organic products dominated by alkylated and hydroxylated aromatic compounds. The results suggest that formation of magnetite by thermal decomposition of siderite on the precursor rock of the martian meteorite ALH84001 would have been accompanied by formation of organic compounds and may represent a source of extraterrestrial organic matter in the meteorite and on Mars. The results also suggest that thermal decomposition of siderite during metamorphism could account for some of the reduced carbon observed in metasedimentary rocks from the early Earth.     

A late quaternary record of eolian silt deposition in a maar lake, St. Michael Island, western Alaska

Recent stratigraphic studies in central Alaska have yielded the unexpected finding that there is little evidence for full-glacial (late Wisconsin) loess deposition. Because the loess record of western Alaska is poorly exposed and not well known, we analyzed a core from Zagoskin Lake, a maar lake on St. Michael Island, to determine if a full-glacial eolian record could be found in that region. Particle size and geochemical data indicate that the mineral fraction of the lake sediments is not derived from the local basalt and is probably eolian. Silt deposition took place from at least the latter part of the mid-Wisconsin interstadial period through the Holocene, based on radiocarbon dating. Based on the locations of likely loess sources, eolian silt in western Alaska was probably deflated by northeasterly winds from glaciofluvial sediments. If last-glacial winds that deposited loess were indeed from the northeast, this reconstruction is in conflict with a model-derived reconstruction of paleowinds in Alaska. Mass accumulation rates in Zagoskin Lake were higher during the Pleistocene than during the Holocene. In addition, more eolian sediment is recorded in the lake sediments than as loess on the adjacent landscape. The thinner loess record on land may be due to the sparse, herb tundra vegetation that dominated the landscape in full-glacial time. Herb tundra would have been an inefficient loess trap compared to forest or even shrub tundra due to its low roughness height. The lack of abundant, full-glacial, eolian silt deposition in the loess stratigraphic record of central Alaska may be due, therefore, to a mimimal ability of the landscape to trap loess, rather than a lack of available eolian sediment.     

Book Review: Experiments: Planning,Analysis, and Parameter Design Optimization. By C. F. Jeff Wu and Michael Hamada. John Wiley & Sons,Inc., New York, 2000, 630 p., U.S.$89.95 (hb), ISBN 0-471-25511-4

Mathematical Geosciences -     

A comparison of three image-object methods for the multiscale analysis of landscape structure

Within the conceptual framework of Complex Systems, we discuss the importance and challenges in extracting and linking multiscale objects from high-resolution remote sensing imagery to improve the monitoring, modeling and management of complex landscapes. In particular, we emphasize that remote sensing data are a particular case of the modifiable areal unit problem (MAUP) and describe how image-objects provide a way to reduce this problem. We then hypothesize that multiscale analysis should be guided by the intrinsic scale of the dominant landscape objects composing a scene and describe three different multiscale image-processing techniques with the potential to achieve this. Each of these techniques, i.e., Fractal Net Evolution Approach (FNEA), Linear Scale-Space and Blob-Feature Detection (SS), and Multiscale Object-Specific Analysis (MOSA), facilitates the multiscale pattern analysis, exploration and hierarchical linking of image-objects based on methods that derive spatially explicit multiscale contextual information from a single resolution of remote sensing imagery. We then outline the weaknesses and strengths of each technique and provide strategies for their improvement.     

Understanding Climatic Impacts, Vulnerabilities, and Adaptation in the United States: Building a Capacity for Assessment

Based on the experience of the U.S. National Assessment, we propose a program of research and analysis to advance capability for assessment of climate impacts, vulnerabilities, and adaptation options. We identify specific priorities for scientific research on the responses of ecological and socioeconomic systems to climate and other stresses; for improvement in the climatic inputs to impact assessments; and for further development of assessment methods to improve their practical utility to decision-makers. Finally, we propose a new institutional model for assessment, based principally on regional efforts that integrate observations, research, data, applications, and assessment on climate and linked environmental-change issues. The proposed program will require effective collaboration between scientists, resource managers, and other stakeholders, all of whose expertise is needed to define and prioritize key regional issues, characterize relevant uncertainties, and assess potential responses. While both scientifically and organizationally challenging, such an integrated program holds the best promise of advancing our capacity to manage resources and the economy adaptively under a changing climate.     

Column Amounts of ClONO2, HCl, HNO3, and HF from Ground-Based FTIR Measurements Made Near Kiruna, Sweden, in Late Winter 1994

During SESAME phase I ground-based FTIR measurements were performed atEsrange near Kiruna, Sweden, from 28 January to 26 March 1994. Zenith columnamounts of ClONO₂, HCl, HF, HNO₃,O₃, N₂O, CH₄, and CFC-12 werederived from solar absorption spectra. Time series of ClONO₂and HCl indicate a chlorine activation at the end of January and around 1March. On 1 March a very low amount of HCl of 2.09times; 10¹⁵molec. cm^-2 was detected, probably caused by a second chlorineactivation phase starting from an already decreased amount of HCl. The ratioof column amounts of HCl to ClONO₂ decreased inside the vortexfrom about 1 in January to 0.4 in late March compared to values of about 2outside the vortex. Although the Arctic stratosphere was rather warm in winter1993/94 and PSCs occurred seldom, chlorine partitioning into its reservoirspecies HCl and ClONO₂ changed during that winter andClONO₂ is the major chlorine reservoir at the end of thewinter as in cold winters like 1991/92 and 1994/95.     

Calculations of horizontal mixing rates using222Rn and the controls on hypoxia in western Long Island Sound, 1991

Late summer hypoxia (<3 ppm oxygen) in western Long Island Sound (WLIS) is a persistent environmental and management issue whose controlling processes are poorly understood. Measured rates of sediment and water-column oxygen consumption in the bottom water suggest that a condition of no oxygen should be attained on the time scale of 13–30 d. Observations, however, indicate the onset of hypoxia is of the order 150 d. Therefore, horizontal and/or vertical transport of oxygen into the area of hypoxia must play an important role. Hypoxia decreases benthic activity and the sediment flux of²²²Rn. The resulting horizontal gradient in bottom water²²²Rn was measured and used to estimate the effective horizontal transport rate (>5–50 m² s^?1), which is considerably slower than previous estimates. Scale analysis of the hypoxia process indicates that horizontal transport rates alone can explain the slow progression of hypoxia in XLIS but that vertical processes may also be capable of delaying the onset of hypoxia especially under conditions of weak stratification or weak intermediate layer oxygen consumption. This scale analysis indicates a delicately balanced process that is sensitive to both climatologically-driven variability in the rates of horizontal and vertical transport as well as the biologically-driven rates of oxygen consumption. An improved ability to predict and/or control hypoxia must be based on a better understanding of temporal and spacial variations in circulation, mixing, and stratification as well as the biological processes in the water column and the sediments.