An experimental and theoretical determination of oxygen isotope fractionation in the system magnetite-H2O from 300 to 800°C

Oxygen isotope fractionations have been determined between magnetite and water from 300 to 800°C and pressures between 10 and 215MPa. We selected three reaction pathways to investigate fractionation: (a) reaction of fine-grained magnetite with dilute aqueous NaCl solutions; (b) reduction of fine-grained hematite through reaction with dilute acetic acid; and (c) oxidation of fine iron power in either pure water or dilute NaCl solutions. Effective use of acetic acid was limited to temperatures up to about 400°C, whereas oxide-solution isotope exchange experiments were conducted at all temperatures. Equilibrium ¹⁸O/¹⁶O fractionation factors were calculated from the oxide-water experiments by means of the partial isotope exchange method, where generally four isotopically different waters were used at any given temperature. Each run product was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and on a limited basis, high-resolution transmission electron microscopy (HRTEM) and Mössbauer spectroscopy. Results from the microscopic examinations indicate the formation of well-crystallized octahedra and dodecahedra of magnetite where the extent of crystallization, grain size, and grain habit depend on the initial starting material, P, T, solution composition, and duration of the run.The greatest amount of oxygen isotope exchange (∼90% or greater) was observed in experiments where magnetite either recrystallized in the presence of 0.5 m NaCl from 500 to 800°C or formed from hematite reacted with 0.5 m acetic acid at 300, 350 and 400°C. Fractionation factors (10³ ln α_mt-H2O) determined from these partial exchange experiments exhibit a steep decrease (to more negative values) with decreasing temperature down to about 500°C, followed by shallower slope. A least-squares regression model of these partial exchange data, which accounts for analytical errors and errors generated by mass balance calculations, gives the following expression for fractionation that exhibits no minimum: 1000lnα_lmt-lw=−8.984(±0.3803)x+3.302(±0.377)x²—0.426(±0.092)x³ with an R² = 0.99 for 300 ≤ T≤ 800°C (x = 10⁶/T²). The Fe oxidation results also exhibit this type of temperature dependence but shifted to slightly more negative 10³ ln α values; there is the suggestion that a kinetic isotope effect may contribute to these fractionations. A theoretical assessment of oxygen isotope fractionation using β-factors derived from heat capacity and Mössbauer temperature (second-order Doppler) shift measurements combined with known β-factors for pure water yield fractionations that are somewhat more negative compared to those determined experimentally. This deviation may be due to the combined solute effects of dissolved magnetite plus NaCl (aq), as well as an underestimation of β_mt at low temperatures. The new magnetite-water experimental fractionations agree reasonably well with results reported from other experimental studies for temperatures ≥ 500°C, but differ significantly with estimates based on quasi-theoretical and empirical approaches. Calcite-magnetite and quartz-magnetite fractionation factors estimated from the combination of magnetite β’s calculated in this study with those for calcite and quartz reported by Clayton and Kieffer (1991) agree very closely with experimentally determined mineral-pair fractionations.     

Formation of chondritic refractory inclusions: The astrophysical setting

This study attempts to identify the astrophysical setting in which properties of the Ca,Al-rich inclusions (CAIs) found in chondritic meteorites are best understood. Importance is attached to the short time period in which most or all of the CAIs were formed (<∼0.5 Myr, corresponding to the observed dispersion of values of initial ²⁶Al/²⁷Al about the canonical value of ∼5 × 10⁻⁵), a constraint that has been overlooked. This period is dissimilar to the time scale of evolution of T Tauri stars, ∼10 Myr; it corresponds instead to the time scale of Class 0 and Class I young stellar objects, protostars as they exist during the massive infall of interstellar material that creates stars. The innermost portion of the sun’s rapidly accreting nebular disk, kept hot during that period by viscous dissipation, is the most plausible site for CAI formation. Once condensed, CAIs must be taken out of that hot zone rather promptly in order to preserve their specialized mineralogical compositions, and they must be transported to the radial distance of the asteroid belt to be available for accretion into the chondrites that contain them today. Though this paper is critical of some aspects of the x-wind model of CAI formation, something akin to the x-wind may be the best way of understanding this extraction and transport of CAIs.     

Laboratory and case studies of thermal cycling and stored strain on the stability of selected marbles

Studies of marble panels from the exterior of two buildings document the processes leading to bowing of the material. Bowing of panels is most extensive in those areas that are exposed to direct or reflected thermal energy. The thermal anisotropic behavior of calcite results in grain-boundary separation, grain sliding and microfracturing. The resulting loss of strength is one factor leading to bowing. The development of bows further reduces the panel strength as the outer portions elongate by inelastic deformation mechanisms. Laboratory experiments cycling marble samples for over 200 cycles at three temperatures up to 107°C above room conditions show similar strength losses as the natural situation. The second factor contributing to the bowing process is the release of residual elastic strain. The strain is in part stored in the marble from its geologic history, but may also be accumulated during thermal cycling due to the properties of calcite. Marble panels have been found to bow when stored outside, but not attached to any framework, indicating that the release of residual strain is a critical factor in producing the bows.     

Morphology and distribution of fossil soils in the Permo-Pennsylvanian Wichita and Bowie Groups, north-central Texas, USA: implications for western equatorial Pangean palaeoclimate during icehouse–greenhouse transition

Analysis of stacked Permo‐Pennsylvanian palaeosols from north‐central Texas documents the influence of palaeolandscape position on pedogenesis in aggradational depositional settings. Palaeosols of the Eastern shelf of the Midland basin exhibit stratigraphic trends in the distribution of soil horizons, structure, rooting density, clay mineralogy and colour that record long‐term changes in soil‐forming conditions driven by both local processes and regional climate. Palaeosols similar to modern histosols, ultisols, vertisols, inceptisols and entisols, all bearing morphological, mineralogical and chemical characteristics consistent with a tropical, humid climate, represent the Late Pennsylvanian suite of palaeosol orders. Palaeosols similar to modern alfisols, vertisols, inceptisols, aridisols and entisols preserve characteristics indicative of a drier and seasonal tropical climate throughout the Lower Permian strata. The changes in palaeosol morphology are interpreted as being a result of an overall climatic trend from relatively humid and tropical, moist conditions characterized by high rainfall in the Late Pennsylvanian to progressively drier, semi‐arid to arid tropical climate characterized by seasonal rainfall in Early Permian time. Based on known Late Palaeozoic palaeogeography and current hypotheses for atmospheric circulation over western equatorial Pangea, the Pennsylvanian palaeosols in this study may be recording a climate that is the result of an orographic control over regional‐scale atmospheric circulation. The trend towards a drier climate interpreted from the Permian palaeosols may be recording the breakdown of this pre‐existing orographic effect and the onset of a monsoonal atmospheric circulation system over this region.     

Middle Campanian–lowermost Maastrichtian nannofossil and foraminiferal biostratigraphy of the northwestern Australian margin

The middle–late Campanian was marked by an increase in the bioprovinciality of calcareous microfossil assemblages into distinct Tethyan, Transitional, and Austral Provinces that persisted to the end of the Maastrichtian. The northwestern Australian margin belonged to the Transitional Province and the absence of key Tethyan marker species such as Radotruncana calcarata and Gansserina gansseri has led petroleum companies operating in the area to use the locally developed KCCM integrated calcareous microfossil zonation scheme. The KCCM zonation is a composite scheme comprising calcareous nannofossil (KCN), planktonic foraminiferal (KPF) and benthonic foraminiferal (KBF) zones. This paper presents the definitions and revisions of Zones KCCM8–19, from the highest occurrence (HO) of Aspidolithus parcus constrictus to the lowest occurrence (LO) of Ceratolithoides aculeus, and builds on our previous early–late Maastrichtian study. The presence of a middle–upper Campanian disconformity is confirmed by microfossil evidence from the Vulcan Sub-basin, Exmouth and Wombat plateaus, and the Southern Carnarvon Platform. In the Vulcan Sub-basin and on the Exmouth Plateau (ODP Hole 762C) the hiatus extends from slightly above the LO of common Rugoglobigerina rugosa to above the LO of Quadrum gothicum. On the Wombat Plateau (ODP Hole 761B) it spans from above the LO of Heterohelix semicostata to above the LO of Quadrum gothicum; and in the Southern Carnarvon Platform the disconformity has its longest duration from above the HO of Heterohelix semicostata to above the LO of Quadrum sissinghii. A significant revision of the events which define Zones KCCM18 and 19 was necessary owing to the observation that the LO of Ceratolithoides aculeus occurs below the HOs of Archaeoglobigerina cretacea and Stensioeina granulata incondita and the LO of common Rugoglobigerina rugosa. In the original zonation these events were considered to be coincident.     

Barite deposition resulting from phototrophic sulfide-oxidizing bacterial activity

Barite (BaSO₄) deposits generally arise from mixing of soluble barium-containing fluids with sulfate-rich fluids. While the role of biological processes in modulating barium solubility has been shown, no studies have shown that the biological oxidation of sulfide to sulfate leads to barite deposition. Here we present an example of microbially mediated barite deposition in a continental setting. A spring in the Anadarko Basin of southwestern Oklahoma produces water containing abundant barium and sulfide. As emergent water travels down a stream to a nearby creek, sulfate concentration increases from 0.06 mM to 2.2 mM while Ba²⁺ concentration drops from 0.4 mM to less than 7 μM. Stable isotope analysis, microbial activity studies, and in situ experiments provide evidence that as sulfide-rich water flows down the stream, anaerobic, anoxygenic, phototrophic bacteria play a dominant role in oxidizing sulfide to sulfate. Sulfate then precipitates with Ba²⁺ producing barite as travertine, cements, crusts, and accumulations on microbial mats. Our studies suggest that phototrophic sulfide oxidation and concomitant sulfur cycling could prove to be important processes regulating the cycling of barium in continental sulfur-containing systems.     

Weights of Evidence Modeling of Mineral Potential: A Case Study Using Small Number of Prospects,Abra, Philippines

Weights of evidence (WofE) modeling usually is applied to map mineral potential in areas with large number of deposits/prospects. In this paper, WofE modeling is applied to a case study area measuring about 920 km² with 12 known porphyry copper prospects. A pixel size of 100 m × 100 m was used in the spatial data analyses to represent in a raster-based GIS lateral extents of prospects and of geological features considered as spatial evidence. Predictor maps were created based on (a) estimates of studentized values of positive spatial association between prospects and spatial evidence; (b) proportion of number of prospects in zones where spatial evidence is present; and (c) geological interpretations of positive spatial association between prospects and spatial evidence. Uncertainty because of missing geochemical evidence is shown to have an influence on tests of assumption of conditional independence (CI) among predictor maps with respect to prospects. For the final predictive model, assumption of CI is rejected based on omnibus test but is accepted based on a new omnibus test. The final predictive model, which delineates 30% of study area as zones with potential for porphyry copper, has 83% success rate and 73% prediction rate. The results demonstrate plausibility of WofE modeling of mineral potential in large areas with small number of mineral prospects.     

Black Holes and Loose Connections in a Global Urban Network

This paper introduces the concept of black holes and loose connections in a global urban hierarchy. Black holes are defined as large cities, with a population of over 3 million, that are not classified as world cities. The paper draws upon a classification that uses advanced producer services as an indicator of world city status. Large, nonworld cities are identified, and provisional ideas about explaining their position are outlined. Connectivity and population data are used in a simple regression analysis to identify loose connections: cities whose connectivity is less than that predicted by their population.