14C content of ten meteorites measured by tandem accelerator mass spectrometry

¹⁴C has been measured in three North American and seven Antarctic meteorites with the Chalk River MP tandem accelerator. In most cases cosmogenic¹⁴C, which is tightly bound, was separated from absorbed atmospheric radiocarbon by stepwise heating extractions. Terrestrial ages obtained by comparing cosmogenic¹⁴C in the meteorite to that in Bruderheim are (7.2 ± 0.6) × 10³ years for Yamato 7304, (11.6 ± 0.4) × 10³ years for Estacado, and range from (32.7 ± 0.5) × 10³ to (41.0 ± 0.8) × 10³ years for six meteorites recovered at Allan Hills and its vicinity. The present upper limit to age determination by the accelerator method varies from 50 × 10³ to 70 × 10³ years depending upon mass and carbon content of the sample. The natural limit caused by cosmic ray production of¹⁴C in silicate rocks at 2000 m elevation is estimated to be (55 ± 5) × 10³ years. “Weathering ages” were estimated for the Antarctic meteorites from the specific activity of loosely-bound CO₂ considered to be absorbed from the terrestrial atmosphere on weathering. The accelerator measurements are in accordance with previous low-level counting measurements but have higher precision and sensitivity.     

Application of stress mapping in cross‐section to understanding ore geometry,predicting ore zones and development of drilling strategies

Stress mapping is a numerical modelling technique used to determine the distribution and relative magnitude of stress during deformation in a mineralised terrane. It is based on the general principle that fluid flow in the Earth's crust is primarily related to pressure gradients. It is best applied to epigenetic hydrothermal mineral deposits, where fluid flow and fluid flux are enhanced in dilational sections of structures and in sites of enhanced rock permeability due to high fracture density. These are defined by sites of low minimum principal stress (σ₃). Most stress mapping is carried out in two dimensions in plan view using geological maps. This is suitable for terranes with steeply dipping lithostratigraphy and structures in which the distribution of mineral deposits is largely controlled by fault structures portrayed on the maps. However, for terranes with gently dipping sequences and structures, and for situations where deposits are sited in and near the hinges of complex fold structures, stress mapping in cross‐section is preferable. The effectiveness of stress mapping is maximised if mineralisation was late in the evolutionary history of the host terrane, and hence the structural geometry of the terrane and contained deposits were essentially that expressed today. The orientation of syn‐mineralisation far‐field stresses must also be inferred. Two examples of orogenic gold deposits, which meet the above criteria, are used to illustrate the potential of stress mapping in cross‐section. Sunrise Dam, located in the Archaean Yilgarn Craton, is a lode‐gold deposit sited in a thrust‐fold belt. Stress mapping illustrates the heterogeneity of stress distribution in the complex structural geometry of the deposit, and predicts the preferential siting of ore zones around the intersections of more steeply dipping, linking thrusts and banded iron‐formation units, and below the controlling more gently dipping basal thrust, the Sunrise Shear. The Howley Anticline in the Pine Creek block hosts several Palaeoproterozoic gold deposits, sited in complex anticlinal structures in greywacke sequences. Stress mapping indicates that gold ores should develop in the hinge zones of symmetrical anticlines, in the hinge zones and more steeply dipping to overturned limbs of asymmetric anticlines, and in and around thrusts in both anticlines and parasitic synclines. The strong correlation between the predictions of the stress mapping, based on the distribution of low σ₃, and the location of gold ores emphasises the potential of stress mapping in cross‐section, not only as an exploration tool for the discovery of additional resources or deposits, but also as a test of geological models. Knowledge of the potential siting of gold ores and their probable orientations also provides a guide to drilling strategies in both mine‐ and regional‐scale exploration.     

Phase equilibrium and calorimetric study of the transition of MnTiO3 from the ilmenite to the lithium niobate structure and implications for the stability field of perovskite

The phase boundary between MnTiO₃ I (ilmenite structure) and MnTiO₃ II (lithium niobate structure) has been determined by analysis of quench products from reversal experiments in a cubic anvil apparatus at 1073–1673 K and 43–75 kbar using mixtures of MnTiO₃ I and II as starting materials. Tight brackets of the boundary give P(kbar)=121.2−0.045 T(K). Thermodynamic analysis of this boundary gives ΔH^o=5300±1000 J·mol⁻¹, ΔS^o = 1.98 ±1J·K⁻¹· mol⁻¹. The enthalpy of transformation obtained directly by transposed-temperature-drop calorimetry is 8359 ±2575 J·mol⁻¹. Possible topologies of the phase relations among the ilmenite, lithium niobate, and perovskite polymorphs are constrained using the above data and the observed (reversible with hysteresis) transformation of II to III at 298 K and 20–30 kbar (Ross et al. 1989). The observed II–III transition is likely to lie on a metastable extension of the II–III boundary into the ilmenite field. However the reversed I–II boundary, with its negative dP/ dT does represent stable equilibrium between ilmenite and lithium niobate, as opposed to the lithium niobate being a quench product of perovskite. We suggest a topology in which the perovskite occurs stably at low T and high P with a triple point (I, II, III) at or below 1073 K near 70 kbar. The I–II boundary would have a negative P-T slope while the II–III and I–III boundaries would be positive, implying that entropy decreases in the order lithium niobate, ilmenite, perovskite. The inferred positive slope of the ilmenite-perovskite transition in MnTiO₃ is different from the negative slopes in silicates and germanates. These thermochemical parameters are discussed in terms of crystal structure and lattice vibrations.     

Arsenite sequestration at the surface of nano-Fe(OH)2, ferrous-carbonate hydroxide, and green-rust after bioreduction of arsenic-sorbed lepidocrocite by Shewanella putrefaciens

X-ray Absorption Fine Structure (XAFS) spectroscopy was used in combination with high resolution transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS), X-ray energy dispersive spectroscopy (XEDS), X-ray powder diffraction, and Mössbauer spectroscopy to obtain detailed information on arsenic and iron speciation in the products of anaerobic reduction of pure and As(V)- or As(III)-adsorbed lepidocrocite (γ-FeOOH) by Shewanella putrefaciens ATCC 12099. We found that this strain of S. putrefaciens is capable of using Fe(III) in lepidocrocite and As(V) in solution or adsorbed on lepidocrocite surfaces as electron acceptors. Bioreduction of lepidocrocite in the absence of arsenic resulted in the formation of hydroxycarbonate green rust 1 [Fe^II₄Fe^III₂(OH)₁₂CO₃: GR1(CO₃)], which completely converted into ferrous-carbonate hydroxide (Fe^II₂(OH)₂CO₃: FCH) over nine months. This study thus provides the first evidence of bacterial reduction of stoichiometric GR1(CO₃) into FCH. Bioreduction of As(III)-adsorbed lepidocrocite also led to the formation of GR1(CO₃) prior to formation of FCH, but the presence of As(III) slows down this transformation, leading to the co-occurrence of both phases after 22-month of aging. At the end of this experiment, As(III) was found to be adsorbed on the surfaces of GR1(CO₃) and FCH. After five months, bioreduction of As(V)-bearing lepidocrocite led directly to the formation of FCH in association with nanometer-sized particles of a minor As-rich Fe(OH)₂ phase, with no evidence for green rust formation. In this five-month experiment, As(V) was fully converted to As(III), which was dominantly sorbed at the surface of the Fe(OH)₂ nanoparticles as oligomers binding to the edges of Fe(OH)₆ octahedra at the edges of the octahedral layers of Fe(OH)₂. These multinuclear As(III) surface complexes are characterized by As-As pairs at a distance of 3.32 ± 0.02 Å and by As-Fe pairs at a distance of 3.50 ± 0.02 Å and represent a new type of As(III) surface complex. Chemical analyses show that the majority of As(III) produced in the experiments with As present is associated with iron-bearing hydroxycarbonate or hydroxide solids, reinforcing the idea that, at least under some circumstances, bacterial reduction can promote As(III) sequestration instead of mobilizing it into solution.     

A comparison of the thick-target model with stereo data on the height structure of solar hard x-ray bursts

The height structure of a thick-target solar hard X-ray source is predicted for a beam injected vertically downward with a power-law spectrum and dominated by Coulomb collisional energy losses. This structure is characterised by the ratio of hard X-ray flux from an upper part of the source to that from the entire source, and is essentially a function only of the atmospheric column density ΔN (cm^?2) in the upper region. These predictions are compared with the flux ratios at 150 keV and 350 keV observed by two spacecraft for five events in which the solar limb occults part of the source for one spacecraft. In three events the occulting levels h ranged from 0 to 2500 km. For these the theoretical and observed ratios are found to be comparable for values of ΔN in reasonable accord with those found at these altitudes by optical and UV spectroscopic modelling of flare chromospheres. In one event the occultation ratio was observed to rise after the burst peak and it is found that this rise is consistent with an increase in ΔN due to conductively driven chromospheric evaporation. However the energy dependence of the occultation ratio is not consistent with that predicted by the model and it is concluded that non-collisional losses must be significant in beam dynamics. In the other two events, the occultation level h was ? 25 000 km. For these the energy dependence of the occultation ratio is comparable with the model predictions. However the values of ΔN required demand extremely high coronal densities and/or acceleration altitudes. Furthermore, the one observed evolution of the occultation ratio is entirely inconsistent with the model. It is concluded that in these, bremsstrahlung emissions other than that from a beam must be important.     

Determination of predevelopment denudation rates of an agricultural watershed (Cayaguás River, Puerto Rico) using in-situ-produced Be in river-borne quartz

Accurate estimates of watershed denudation absent anthropogenic effects are required to develop strategies for mitigating accelerated physical erosion resulting from human activities, to model global geochemical cycles, and to examine interactions among climate, weathering, and uplift. We present a simple approach to estimate predevelopment denudation rates using in-situ-produced cosmogenic ¹⁰Be in fluvial sediments. Denudation processes in an agricultural watershed (Cayaguás River Basin, Puerto Rico) and a matched undisturbed watershed (Icacos River Basin) were compared using ¹⁰Be concentrations in quartz for various size fractions of bed material. The coarse fractions in both watersheds bear the imprint of long subsurface residence times. Fine material from old shallow soils contributes little, however, to the present-day sediment output of the Cayaguás. This confirms the recent and presumably anthropogenic origin of the modern high denudation rate in the Cayaguás Basin and suggests that pre-agricultural erosional conditions were comparable to those of the present-day Icacos.     

Nanoscale study of As biomineralization in an acid mine drainage system

Spatial and seasonal variations of the oxidation of Fe(II) and As(III) have been previously documented in the Carnoulès (Gard, France) Acid Mine Drainage (AMD) by bulk analyses. These variations may be correlated with the variations in the activity of indigenous As(III)- and Fe(II)-oxidizing bacteria living in the As-rich Carnoulès water. The activity of these bacteria indeed plays an important role in the nature and composition of the solid phases that sequester arsenic at this site. In order to better understand the interactions of microbes with Fe and As in the Carnoulès AMD, we combined Transmission Electron Microscopy (TEM) and Scanning Transmission X-ray Microscopy (STXM) to collect near-edge X-ray absorption fine structure (NEXAFS) spectra at high spatial and energy resolution and to perform high spatial resolution imaging at the 30-50 nm scale. Spectromicroscopy was performed at the C K-edge, Fe L_2,3-edge, and As L_2,3-edge, which allowed us to locate living and/or mineralized bacterial cells and to characterize Fe and As oxidation states in the vicinity of those cells. TEM was used to image the same areas, providing higher resolution images and complementary crystallographic and compositional information through electron diffraction and EDXS analysis. This approach provides unique information on heterogeneous geochemical processes that occur in a complex microbial community in an AMD environment at the micrometer and submicrometer-scale. Bacterial cells in the Carnoulès AMD were frequently associated with mineral precipitates, and a variety of biomineralization patterns were observed. While many mineral precipitates were not associated with bacterial cells, they were associated with pervasive organic carbon. Finally, abundant biomineralized organic vesicles were observed in the Carnoulès AMD. Such vesicles may have been overlooked in highly mineralized extreme environments in the past and may represent an important component in a common biomineralization process in such environments.     

New constraints on UHT metamorphism in the Eastern Ghats Province through the application of phase equilibria modelling and in situ geochronology

High Mg–Al granulites from the Sunki locality in the central portion of the Eastern Ghats Province record evidence for the high-temperature peak and retrograde evolution. Peak metamorphic phase assemblages from two samples are garnet + orthopyroxene + quartz + ilmenite + melt and orthopyroxene + spinel + sillimanite + melt, respectively. Isochemical phase diagrams (pseudosections) based on bulk rock compositions calculated in the chemical system Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ (NCKFMASHTO) and Al contents in orthopyroxene indicate peak UHT metamorphic conditions in excess of 960 °C and 9.7 kbar. Microstructures and the presence of cordierite interpreted to record the post-peak evolution show that the rocks underwent decompression and minor cooling from conditions of peak UHT metamorphism to conditions of ~ 900 °C at ~ 7.5 kbar. In situ U–Pb isotope analyses of monazite associated with garnet and cordierite using the Sensitive High Resolution Ion Microprobe (SHRIMP) yield a weighted mean ²⁰⁷Pb/²³⁵U age of ca. 980 Ma, which is interpreted to broadly constrain the timing of high-temperature monazite growth during decompression and melt crystallization at ~ 900–890 °C and 7.5 kbar. However, the range of ²⁰⁷Pb/²³⁵U monazite ages (from ca. 1014 Ma to 959 Ma for one sample and ca. 1043 Ma to 922 Ma for the second sample) suggest protracted monazite growth during the high-temperature retrograde evolution, and possibly diffusive lead loss during slow cooling after decompression. The results of the integrated petrologic and geochronologic approach presented here are inconsistent with a long time gap between peak conditions and the formation of cordierite-bearing assemblages at lower pressure, as proposed in previous studies, but are consistent with a simple evolution of a UHT peak followed by decompression and cooling.     

Investigation of effect of near-fault motions on substandard bridge structures

The objective of this study was to investigate the effects of near-fault ground motions on substandard bridge columns and piers. To accomplish these goals, several large scale reinforced concrete models were constructed and tested on a shake table using near- and far-field ground motion records. Because the input earthquakes for the test models had different characteristics, three different measures were used to evaluate the effect of the input earthquake. These measures are peak shake table acceleration, spectral acceleration at the fundamental period of the test specimens, and the specimen drift ratios. For each measure, force-displacement relationships, strains, curvatures, drift ratios, and visual damage were evaluated. Results showed that regardless of the measure of input or response, the near-fault record generally led to larger strains, curvatures, and drift ratios. Furthermore, residual displacements were small compared to those for columns meeting current seismic code requirements.