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.     

The mutual climatic range method of palaeoclimate reconstruction based on insect fossils: New applications and interhemispheric comparisons

The Mutual Climatic Range (MCR) method of palaeoclimate reconstruction has been employed in Europe for the last decade. A quantitative, calibrated method, MCR has many advantages over qualitative methods. More recent applications deal with eastern and central North America, and the method is also being developed for desert and arctic faunas. The climate envelopes for North American beetles have been compiled using a 25-km gridded North American climate database that pairs climate parameters with modern collection sites. Modern tests of the reliability of the MCR method for North American species yielded similar results to prior European tests. Linear regressions of predicted on observed values yielded equations used to calibrate the MCR estimates. Work is under way to develop MCR estimates of mean annual precipitation for fossil assemblages from the desert southwest, where moisture conditions may play a more important role in determining beetle species' ranges.An examination of British and North American mean July temperature reconstructions during the Late Wisconsinan glacial interval compares and contrasts three sets of records. The North American records show no indication of the Younger Dryas cooling that is clearly marked in records from northwest Europe. The MCR method adds vigour to our reconstructions, and allows us to compare between regions and with other palaeoenvironmental methods.     

Fluvial process and the establishment of bottomland trees

The effects of river regulation on bottomland tree communities in western North America have generated substantial concern because of the important habitat and aesthetic values of these communities. Consideration of such effects in water management decisions has been hampered by the apparent variability of responses of bottomland tree communities to flow alteration. When the relation between streamflow and tree establishment is placed in a geomorphic context, however, much of that variability is explained, and prediction of changes in the tree community is improved.The relation between streamflow and establishment of bottomland trees is conditioned by the dominant fluvial process or processes acting along a stream. For successful establishment, cottonwoods, poplars, and willows require bare, moist surfaces protected from disturbance. Channel narrowing, channel meandering, and flood deposition promote different spatial and temporal patterns of establishment. During channel narrowing, the site requirements are met on portions of the bed abandoned by the stream, and establishment is associated with a period of low flow lasting one to several years. During channel meandering, the requirements are met on point bars following moderate or higher peak flows. Following flood deposition, the requirements are met on flood deposits ;high above the channel bed. Flood deposition can occur along most streams, but where a channel is constrained by a narrow valley, this process may be the only mechanism that can produce a bare, moist surface high enough to be safe from future disturbance. Because of differences in local bedrock, tributary influence, or geologic history, two nearby reaches of the same stream may be dominated by different fluvial processes and have different spatial and temporal patterns of trees. We illustrate this phenomenon with examples from forests of plains cottonwood (Populus deltoides ssp. monilifera) along meandering and constrained reaches of the Missouri River in Montana.     

Blast Induced Damage and Dynamic Behaviour of Hangingwalls in Bench Stoping

This paper presents the results of a comprehensive monitoring program designed to investigate the extent of blast induced damage experienced by rock masses extracted by bench stoping methods. An array of triaxial geophones and extensometers were used to monitor blast vibration attenuation and measure hangingwall deformations during stope extraction. In addition, pre and post surveys of the hangingwall rock mass were conducted using a TV borehole camera and cavity survey instrumentation. These surveys were later used to calibrate damage profiles into the stope hangingwalls.

Peak particle velocity, hangingwall deformation measurements and stope surveys were used to develop a site specific damage model that allowed engineers to asses drilling and blasting configurations to minimise the extent of pre-conditioning and damage. In addition the study included the analysis of the frequency response, displacements and accelerations experienced by the excavation as extraction and mine filling progressed. This work aimed at improving our understanding of the influence of blasting on the dynamic behaviour of stope hangingwalls.

The study demonstrated that estimates of the maximum extent of rock mass pre-conditioning and/or damage made through the application of the Holmberg-Persson approach compared well with measured results. In addition, the study found that dynamic loading imparted on an exposed hangingwall from subsequent stope blasting was also expected to contribute to rock mass weakening and that mine filling was crucial to arrest further deterioration. Hangingwall accelerations were used to demonstrate that larger openings may be more susceptible to dynamic loading.     

The Elusive AD 1826 Tsunami, South Westland, New Zealand

In AD 1826 sealers reported earthquake and tsunami activity in Fiordland, although, contemporary or near‐contemporary accounts of tsunami inundation at the time are elusive. A detailed analysis of recent sediments from Okarito Lagoon builds on contextual evidence provided by earlier research concerning past tsunami inundation. Sedimentological, geochemical, micropalaeontological and geochronological data are used to determine palaeoenvironments before, during and after what was most probably tsunami inundation in AD 1826. The most compelling chronological control is provided fry a young cohort of trees growing on a raised shoreline bench stranded fry a drop in the lagoon water level following tsunami inundation.     

The International Laser Ranging Service and its support for IGGOS

The International Laser Ranging Service (ILRS) was established in September 1998 as a service within the IAG to support programs in geodetic, geophysical, and lunar research activities and to provide data products to the International Earth Rotation Service (IERS) in support of its prime objectives. Now in operation for 5 years, the ILRS develops: (1) the standards and specifications necessary for product consistency and (2) the priorities and tracking strategies required to maximize network efficiency. The service collects, merges, analyzes, archives and distributes satellite and lunar laser ranging data to satisfy a variety of scientific, engineering, and operational needs and encourages the application of new technologies to enhance the quality, quantity, and cost effectiveness of its data products. The ILRS works with: (1) the global network to improve station performance; (2) new satellite missions in the design and building of retroreflector targets to maximize data quality and quantity and (3) science programs to optimize scientific data yield. The ILRS Central Bureau maintains a comprehensive web site as the primary vehicle for the distribution of information within the ILRS community. The site, which can be accessed at: http://ilrs.gsfc.nasa.gov is also available at mirrored sites at the Communications Research Laboratory (CRL) in Tokyo and the European Data Center (EDC) in Munich.During the last 2 years, the ILRS has addressed very important challenges: (1) data from the field stations are now submitted hourly and made available immediately through the data centers for access by the user community; (2) tracking on low satellites has been significantly improved through the sub-daily issue of predictions, drag functions, and the real-time exchange of time biases; (3) analysis products are now submitted in SINEX format for compatibility with the other space geodesy techniques; (4) the Analysis Working Group is heavily engaged in Pilot Projects as it works toward an ILRS “standard” global solution and (5) SLR has significantly increased its participation in the International Terrestrial Reference Frame (ITRF) activity, which is important to the success of IGGOS.     

Effects of pressure on aqueous chemical equilibria at subzero temperatures with applications to Europa

Pressure plays a critical role in controlling aqueous geochemical processes in deep oceans and deep ice. The putative ocean of Europa could have pressures of 1200 bars or higher on the seafloor, a pressure not dissimilar to the deepest ocean basin on Earth (the Mariana Trench at 1100 bars of pressure). At such high pressures, chemical thermodynamic relations need to explicitly consider pressure. A number of papers have addressed the role of pressure on equilibrium constants, activity coefficients, and the activity of water. None of these models deal, however, with processes at subzero temperatures, which may be important in cold environments on Earth and other planetary bodies. The objectives of this work were to (1) incorporate a pressure dependence into an existing geochemical model parameterized for subzero temperatures (FREZCHEM), (2) validate the model, and (3) simulate pressure-dependent processes on Europa. As part of objective 1, we examined two models for quantifying the volumetric properties of liquid water at subzero temperatures: one model is based on the measured properties of supercooled water, and the other model is based on the properties of liquid water in equilibrium with ice.The relative effect of pressure on solution properties falls in the order: equilibrium constants(K) > activity coefficients (γ) > activity of water (a_w). The errors (%) in our model associated with these properties, however, fall in the order: γ > K > a_w. The transposition between K and γ is due to a more accurate model for estimating K than for estimating γ. Only activity coefficients are likely to be significantly in error. However, even in this case, the errors are likely to be only in the range of 2 to 5% up to 1000 bars of pressure. Evidence based on the pressure/temperature melting of ice and salt solution densities argue in favor of the equilibrium water model, which depends on extrapolations, for characterizing the properties of liquid water in electrolyte solutions at subzero temperatures, rather than the supercooled water model. Model-derived estimates of mixed salt solution densities and chemical equilibria as a function of pressure are in reasonably good agreement with experimental measurements.To demonstrate the usefulness of this low-temperature, high-pressure model, we examined two hypothetical cases for Europa. Case 1 dealt with the ice cover of Europa, where we asked the question: How far above the putative ocean in the ice layer could we expect to find thermodynamically stable brine pockets that could serve as habitats for life? For a hypothetical nonconvecting 20 km icy shell, this potential life zone only extends 2.8 km into the icy shell before the eutectic is reached. For the case of a nonconvecting icy shell, the cold surface of Europa precludes stable aqueous phases (habitats for life) anywhere near the surface. Case 2 compared chemical equilibria at 1 bar (based on previous work) with a more realistic 1460 bars of pressure at the base of a 100 km Europan ocean. A pressure of 1460 bars, compared to 1 bar, caused a 12 K decrease in the temperature at which ice first formed and a 11 K increase in the temperature at which MgSO₄·12H₂O first formed. Remarkably, there was only a 1.2 K decrease in the eutectic temperatures between 1 and 1460 bars of pressure. Chemical systems and their response to pressure depend, ultimately, on the volumetric properties of individual constituents, which makes every system response highly individualistic.     

Proterozoic copper deposits in NW Queensland,Australia: Sulfur isotopic data

Sulfur isotopic disequilibrium is commonly observed between associated pyrite and copper sulfides in NW Queensland. A sulfur isotopic study of copper mineralization in dolomites at Paradise Valley and arenites at Mammoth has allowed the significance of such disequilibrium to be evaluated. Copper mineralization at Paradise Valley is characterized by a greater enrichment in ³⁴S, with δ³⁴S values often greater than +30‰, for both copper sulfides and associated syngenetic/diagneetic pyrite. At Mammoth, copper sulfides have isotopic compositions (δ³⁴S=?15.9 to ?0.3‰) transitional between disseminated syngenetic/diagenetic pyrite (δ³⁴S=?5.7 to ?1.7‰) and epigenetic vein pyrite (δ³⁴S=?17.9 to ?7.1‰) suggesting progressive reaction and replacement of syngenetic/diagenetic pyrite by a copper-bearing mineralizing fluid under oxidizing conditions. The isotopic data, within the constraints imposed by geological and geochemical factors, support a model of reaction between copper-bearing mineralizing fluids and pre-existing syngenetic/diagenetic pyrite for both the carbonate- and arenite-hosted deposits.