Nucleosynthetic zirconium isotope anomalies in acid leachates of carbonaceous chondrites

Stepwise dissolutions of the carbonaceous chondrites Orgueil (CI), Murchison (CM) and Allende (CV) reveal large nucleosynthetic anomalies for Zr isotopes that contrast with the uniform compositions found in bulk meteorites. Two complementary nucleosynthetic components are observed: one enriched and one depleted in s-process nuclides. The latter component, characterized by excess ⁹⁶Zr, is most distinctive in the acetic acid leachate (up to ε⁹⁶Zr ≈ 50). The excess decreases with increasing acid strength and the final leaching steps of the experiment are depleted in ⁹⁶Zr and thus enriched in s-process nuclides. Presolar silicon carbide grains are likely host phases for part of the anomalous Zr released during these later stages. However, by mass balance they cannot account for the ⁹⁶Zr excesses observed in the early leaching steps and this therefore hints at the presence of at least one additional carrier phase with significant amounts of anomalous Zr. The data provide evidence that average solar system material consists of a homogenized mixture of different nucleosynthetic components, which can be partly resolved by leaching experiments of carbonaceous chondrites.     

Gold partitioning in melt-vapor-brine systems

We used laser-ablation inductively coupled plasma mass spectrometry to measure the solubility of gold in synthetic sulfur-free vapor and brine fluid inclusions in a vapor + brine + haplogranite + magnetite + gold metal assemblage. Experiments were conducted at 800°C, oxygen fugacity buffered at Ni-NiO (NNO), and pressures ranging from 110 to 145 MPa. The wt% NaCl eq. of vapor increases from 2.3 to 19 and that of brine decreases from 57 to 35 with increasing pressure. The composition of the vapors and brines are dominated by NaCl + KCl + FeCl₂ + H₂O. Gold concentrations in vapor and brine decrease from 36 to 5 and 50 to 28 μg/g, respectively, and the calculated vapor:brine partition coefficients for gold decrease from 0.72 to 0.17 as pressure decreases from 145 to 110 MPa. These data are consistent with the thermodynamic boundary condition that the concentration of gold in the vapor and brine must approach a common value as the critical pressure is approached along the 800°C isotherm in the NaCl-KCl-FeCl₂-HCl-H₂O system.We use the equilibrium constant for gold dissolution as AuOH⁰, extrapolated from lower temperature and overlapping pressure range, to calculate expected concentrations of AuOH⁰ in our experimental vapors. These calculations suggest that a significant quantity of gold in our experimental vapors is present as a non-hydroxide species. Possible chloridogold(I) species are hypothesized based on the positively correlated gold and chloride concentrations in our experimental vapors. The absolute concentration of gold in our synthetic vapor, brine, and melt and calculated mass partition coefficients for gold between these physicochemically distinct magmatic phases suggests that gold solubility in aqueous fluids is a function of aqueous phase salinity, specifically total chloride concentration, at magmatic conditions. However, though we highlight here the effect of salinity, the combination of our data with data sets from lower temperatures evinces a significant decrease in gold solubility as temperature drops from 800°C to 600°C. This decrease in solubility has implications for gold deposition from ascending magmatic fluids.     

The emergence of a Galápagos shield volcano, Roca Redonda

Roca Redonda volcano is a mostly submarine shield volcano that rises nearly 3 km from the adjacent seafloor. Over twenty lava flows and palagonite tuff are exposed in a 60 meter high oblong outcrop above sea level, and several other flows are exposed in the shallow water surrounding the islet. Thick, slightly alkaline picritic flows form the base of the section. Thinner picrites interbedded with sparsely porphyritic alkali-olivine basaltic pahoehoe toes characterize the upper section. The subaerial section probably records the filling of a palagonite tuff cone with younger lavas. Numerous fumaroles that may have a magmatic component are present in the shallow (<30 m) submarine zone and indicate that the volcano is probably still active. Three lava types are exposed: the basal picrites with 19% > MgO > 14%, high-Mg basalts with MgO of about 9%, and low-Mg basalts with MgO of about 6%. The Sr and Nd isotopic ratios of the three lava types are within analytical uncertainty. Olivine compositions indicate that the picrites are basaltic liquids that have accumulated olivine whose composition is in equilibrium with the host basaltic liquid. Apparently, basaltic magmas percolated through dunite and troctolite that had crystallized from slightly older Roca Redonda basaltic magma. Lavas from Roca Redonda have enriched trace element contents and isotopic ratios relative to nearby Wolf volcano, but they are quite similar to lavas from Cerro Azul and Ecuador volcanoes. The common characteristic of these volcanoes is that they lie on the periphery of the archipelago and are in a stage of subaerial growth. This suggests that Galápagos volcanoes may go through a juvenile alkaline stage before a mature tholeiitic stage, analogous to the Loihi stage of Hawaiian volcanism. A low ³He/⁴He ratio in olivine from one of the picrites indicates a small contribution by the Galápagos mantle plume. Received: 15 December 1997 / Accepted: 6 May 1998     

Dynamic simulation of littoral zone habitats in low Chesapeake Bay. II. Seagrass habitat primary production and water quality relationships

Seagrasses are indicators of ecosystem state because they are sensitive to variations in water composition and clarity resulting from watershed-level impacts. A simulation model designed to studyZostera marina (eelgrass) habitat dynamics in a variable littoral zone environment was used to address the potential ecological responses to eutrophication in lower Chesapeake Bay. The adjacent channel boundary environment is a source of dissolved and particulate materials to the littoral zone. In the simulations, concentrations of key water quality variables in the adjacent estuarine channel boundary were either halved or doubled relative to the base case to investigate light versus nitrogen effects. The role of the seagrass meadow in littoral zone carbon and nitrogen dynamics was evaluated when meadow size was changed in the model. Particulate and dissolved organic carbon accounted for 83% of the submarine light attenuation in the seagrass meadow. In all model runs, the water column concentrations of chlorophylla and dissolved inorganic nitrogen (DIN) were below the habitat criteria proposed as critical to seagrass survival. Eelgrass community production was carefully regulated by the interactive effects of light, nitrogen, and grazing on epiphyte growth. Increased eelgrass coverage in the littoral zone led to a simulated doubling of ecosystem primary production but reduced the fraction of production by planktonic and sediment microalgae. The simulation model presented here demonstrated the importance of material input from the channel in littoral zone biogeochemical dynamics. Submarine ligh regulated primary production more strongly than inorganic nitrogen concentrations in the model. External DIN concentrations influenced seagrass survival indirectly: enrichment stimulated growth of epiphytes and phytoplankton and promoted shading of the seagras leaf. The model was based upon a unimpacted ecosystem and deteriorated water quality negatively influenced primary production greater than the increases triggered by improved condition. Increased material loading to the littoral zone reduced submarine light availability, increased phytoplankton production, lowered ecosystem production, and reduced subtidal vegetated habitat. This simulation model of the estuarine littoral zone model combines hydrodynamics, biogeochemical sources and sinks, and living resources in order to better understand structure, function, and change in aquatic ecosystems.     

Submarine hydrothermal activity and gold-rich mineralization at Brothers Volcano, Kermadec Arc, New Zealand

Brothers volcano, of the Kermadec intraoceanic arc, is host to a hydrothermal system unique among seafloor hydrothermal systems known anywhere in the world. It has two distinct vent fields, known as the NW Caldera and Cone sites, whose geology, permeability, vent fluid compositions, mineralogy, and ore-forming conditions are in stark contrast to each other. The NW Caldera site strikes for ??600?m in a SW?CNE direction with chimneys occurring over a ??145-m depth interval, between ??1,690 and 1,545?m. At least 100 dead and active sulfide chimney spires occur in this field and are typically 2?C3?m in height, with some reaching 6?C7?m. Their ages (at time of sampling) fall broadly into three groups: <4, 23, and 35?years old. The chimneys typically occur near the base of individual fault-controlled benches on the caldera wall, striking in lines orthogonal to the slopes. Rarer are massive sulfide crusts 2?C3?m thick. Two main types of chimney predominate: Cu-rich (up to 28.5?wt.% Cu) and, more commonly, Zn-rich (up to 43.8?wt.% Zn). Geochemical results show that Mo, Bi, Co, Se, Sn, and Au (up to 91?ppm) are correlated with the Cu mineralization, whereas Cd, Hg, Sb, Ag, and As are associated with the dominant Zn-rich mineralization. The Cone site comprises the Upper Cone site atop the summit of the recent (main) dacite cone and the Lower Cone site that straddles the summit of an older, smaller, more degraded dacite cone on the NE flank of the main cone. Huge volumes of diffuse venting are seen at the Lower Cone site, in contrast to venting at both the Upper Cone and NW Caldera sites. Individual vents are marked by low-relief (??0.5?m) mounds comprising predominately native sulfur with bacterial mats. Vent fluids of the NW Caldera field are focused, hot (??300°C), acidic (pH????2.8), metal-rich, and gas-poor. Calculated end-member fluids from NW Caldera vents indicate that phase separation has occurred, with Cl values ranging from 93% to 137% of seawater values. By contrast, vent fluids at the Cone site are diffuse, noticeably cooler (??122°C), more acidic (pH?1.9), metal-poor, and gas-rich. Higher-than-seawater values of SO₄ and Mg in the Cone vent fluids show that these ions are being added to the hydrothermal fluid and are not being depleted via normal water/rock interactions. Iron oxide crusts 3?years in age cover the main cone summit and appear to have formed from Fe-rich brines. Evidence for magmatic contributions to the hydrothermal system at Brothers includes: high concentrations of dissolved CO₂ (e.g., 206?mM/kg at the Cone site); high CO₂/³He; negative ??D and ??¹⁸O_H2O for vent fluids; negative ??³⁴S for sulfides (to ?4.6??), sulfur (to ?10.2??), and ??¹⁵N₂ (to ?3.5??); vent fluid pH values to 1.9; and mineral assemblages common to high-sulfidation systems. Changing physicochemical conditions at the Brothers hydrothermal system, and especially the Cone site, occur over periods of months to hundreds of years, as shown by interlayered Cu?+?Au- and Zn-rich zones in chimneys, variable fluid and isotopic compositions, similar shifts in ³He/⁴He values for both Cone and NW Caldera sites, and overprinting of ??magmatic?? mineral assemblages by water/rock-dominated assemblages. Metals, especially Cu and possibly Au, may be entering the hydrothermal system via the dissolution of metal-rich glasses. They are then transported rapidly up into the system via magmatic volatiles utilizing vertical (??2.5?km long), narrow (??300-m diameter) ??pipes,?? consistent with evidence of vent fluids forming at relatively shallow depths. The NW Caldera and Cone sites are considered to represent stages along a continuum between water/rock- and magmatic/hydrothermal-dominated end-members.     

A Numerical Simulation of Residual Circulation in Tampa Bay. Part II: Lagrangian Residence Time

Lagrangian retention and flushing are examined by advecting neutrally buoyant point particles within a circulation field generated by a numerical ocean model of Tampa Bay. Large temporal variations in Lagrangian residence time are found under realistic changes in boundary conditions. Two 90-day time periods are examined. The first (P1) is characterized by low freshwater inflow and weak baroclinic circulation. The second (P2) has high freshwater inflow and strong baroclinic circulation. At the beginning of both time periods, 686,400 particles are released uniformly throughout the bay. Issues relating to particle distribution and flushing are examined at three different spatial scales: (1) at the scale of the entire bay, (2) the four major regions within the bay, and (3) at the scale of individual model grid cells. Two simple theoretical models for the particle number over time, N(t), are fit to the particle counts from the ocean model. The theoretical models are shown to represent N(t) reasonably well when considering the entire bay, allowing for straightforward calculation of baywide residence times: 156 days for P1 and 36 days for P2. However, the accuracy of these simple models decreases with decreasing spatial scale. This is likely due to the fact that particles may exit, reenter, or redistribute from one region to another in any sequence. The smaller the domain under consideration, the more this exchange process dominates. Therefore, definitions of residence time need to be modified for “non-local” situations. After choosing a reasonable definition, and removal of the tidal and synoptic signals, the residence times at each grid cell in P1 is found to vary spatially from a few days to 90 days, the limit of the calculation, with an average residence time of 53 days. For P2, the overall spatial pattern is more homogeneous, and the residence times have an average value of 26 days.     

Spatially enabled bushfire recovery

Over the last decade growth in spatial information use for disaster management has been considerable. Maps and spatial data are now recognized as critical elements in each of the four phases of disaster management: mitigation, preparedness, response, and recovery. The use of spatial information to support the phases of mitigation, preparedness and response to bushfires is widely understood. Less attention, however, has been given to the role of spatial information in the recovery. Moreover, the application of the spatially enabled society concept to bushfire recovery has not been explored. This paper explores the role that spatial information plays and could play in the recovery phase of a bushfire disaster. The bushfires in Victoria, Australia that took place during February 2009 are used as the primary case study. It is found that: Spatial information for recovery requires a pre-existing infrastructure; Spatial capacity must be developed across agencies dealing with recovery; Spatially enabled address and parcel information are the key dataset required to support all recovery tasks; Spatial integration of bushfire datasets (spread and intensity) require linking with planning regimes, and Spatial information that is volunteered could be incorporated into recovery activities.     

A Cambrian mixed carbonate–siliciclastic platform in SW Gondwana: evidence from the Western Sierras Pampeanas (Argentina) and implications for the early Paleozoic paleogeography of the proto-Andean margin

International Journal of Earth Sciences - The Western Sierras Pampeanas (WSP) of Argentina record a protracted geological history from the Mesoproterozoic assembly of the Rodinia supercontinent to...     

Seal integrity and feasibility of CO<Subscript>2</Subscript> sequestration in the Teapot Dome EOR pilot: geomechanical site characterization

This paper reports a preliminary investigation of CO₂ sequestration and seal integrity at Teapot Dome oil field, Wyoming, USA, with the objective of predicting the potential risk of CO₂ leakage along reservoir-bounding faults. CO₂ injection into reservoirs creates anomalously high pore pressure at the top of the reservoir that could potentially hydraulically fracture the caprock or trigger slip on reservoir-bounding faults. The Tensleep Formation, a Pennsylvanian age eolian sandstone is evaluated as the target horizon for a pilot CO₂ EOR-carbon storage experiment, in a three-way closure trap against a bounding fault, termed the S1 fault. A preliminary geomechanical model of the Tensleep Formation has been developed to evaluate the potential for CO₂ injection inducing slip on the S1 fault and thus threatening seal integrity. Uncertainties in the stress tensor and fault geometry have been incorporated into the analysis using Monte Carlo simulation. The authors find that even the most pessimistic risk scenario would require ∼10 MPa of excess pressure to cause the S1 fault to reactivate and provide a potential leakage pathway. This would correspond to a CO₂ column height of ∼1,500 m, whereas the structural closure of the Tensleep Formation in the pilot injection area does not exceed 100 m. It is therefore apparent that CO₂ injection is not likely to compromise the S1 fault stability. Better constraint of the least principal stress is needed to establish a more reliable estimate of the maximum reservoir pressure required to hydrofracture the caprock.     

Radiation-induced defects in quartz. III. Single-crystal EPR,ENDOR and ESEEM study of a peroxy radical

The X- and W-band single-crystal electron paramagnetic resonance spectra of an electron-irradiated natural quartz permit quantitative analysis of a ²⁹Si hyperfine structure (A ~12.6 MHz) and an ²⁷Al hyperfine structure (A ≤ 0.8 MHz) for a previously reported hole-like center. The ²⁹Si hyperfine structure arises from interaction with two equivalent Si atoms and is characterized by the direction of the unique A axis close to a Si–O bond direction. The ²⁷Al hyperfine structure, confirmed by pulsed electron nuclear double resonance and electron spin echo envelope modulation spectra, is characterized by the unique A axis approximately along a twofold symmetry axis. These ²⁹Si and ²⁷Al hyperfine data, together with published theoretical results on peroxy radicals in SiO₂ as well as our own density functional theory (DFT) calculations on model peroxy centers, suggest this hole-like center to have the unpaired spin on a pair of oxygen atoms linked to two symmetrically equivalent Si atoms and a substitutional Al³⁺ ion across the c-axis channel, a first peroxy radical in quartz. The nuclear quadrupole matrix P also suggests that the Al³⁺ ion corresponds closely to the diamagnetic precursor to the [AlO₄]⁰ center. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.