Solubility of Pt and Pd sulfides and Au metal in aqueous bisulfide solutions

An experimental study of the solubility of Pt and Pd sulfides and Au metal in aqueous bisulfide solutions was conducted at temperatures from 200° to 350 °C and at saturated vapor pressure. A 500-mL Bridgemantype pressure vessel constructed of titanium, and equipped with a motor-driven magnetic stirrer was employed. The pH and the oxidation state were buffered by the coexistence of H₂S/HS^–/SO _inf4 ^sup2– . The pH at temperature was calculated to be in the range 5.91–9.43, and S was 0.3–2.2 m. Under the experimental conditions, the measured solubility of gold is about two to three orders of magnitude greater than that of either platinum and palladium, and the measured solubility of platinum is, in general, approximately equal to that of palladium, in molal units. The solubilities are found to be in the range: platinum 4–800 ppb, palladium 1–400 ppb, and gold 2–300 ppm. The solubility data can be modeled adequately using the following reactions: Au+H₂S+HH^–=Au(HS) ₂ ^– +1/2H₂ (K₁₄); PtS+HS^–+H⁺=Pt (HS) ₂ ⁰ (K₁₅); PdS+HS^–+H⁺=Pd (HS) ₂ ⁰ (K₁₆); PtS₂+H₂=Pt (HS) ₂ ⁰ (K₂₁).With equilibrium constants determined as follows (errors represent two standard deviations): Preliminary measurements of the solubilities of metallic Pt, Pd and Au as hydroxide complexes were also conducted using a second titanium pressure vessel, at temperatures of 200° to 350 °C and vapor saturation pressure, with pH and the oxidation state controlled or buffered by adding known amounts of NaOH and H₂ gas. The concentration of NaOH was in the range 0.01–1.3 m, and the partial pressure of H₂ at 200 °C was 62–275 bars, initially. Under the temperature and pressure conditions of these experiments, the solubility of platinum in 1 m NaOH solution is less than 100 ppb, that of palladium is less than 10 ppb and that of gold is less than 0.2 ppm; and in 0.01 m NaOH solutions, both Pt and Pd solubilities are less than 1 ppb. These data indicate that the contributions of hydroxide complexes to the total solubilities in the bisulfide runs, where the pH was in the range of 5.9–9.4, are negligible. The concentrations of both Pt and Pd as bisulfide complexes in the Salton Sea geothermal system predicted using the stability constants determined in this work agree very well with those values measured by McKibben et al. (1990). This calculation strongly suggests that the PGE are transported in moderately reducing, near neutral hydrothermal fluids as bisulfide complexes, as is gold. However, the much lower maximum solubility of the PGE relative to gold severely constrains models of re genesis, and may explain the relative rarity of hydrothermal PGE deposits compared to the relative abundance of hydrothermal Au deposits.     

Is C/O enhanced in NGC 253?

We have mapped the nuclear region of the starburst galaxy NGC 253 in the³ P ₁ ³ P ₀ line of neutral carbon using the JCMT. Carbon is widespread across the nuclear region with a similiar distribution to CO as expected. Previous studies of Galactic star-forming regions showed that carbon emission is enhanced in photon-dominated regions (where UV photons impinge upon molecular clouds). Previous observations of other PDR tracers such as ionized carbon and FIR continuum constrain the physical conditions in the PDR gas of NGC 253. The carbon we have observed is far brighter than predicted by theoretical models of PDRs with solar elemental values. This indicates that carbon emission is not a reliable diagnostic of the physical conditions in the nuclear region of a galaxy undergoing a burst of star formation.     

Baroclinic instabilities in Jupiter's zonal flow

The baroclinic stability of Jupiter's zonal flow is investigated using a model consisting of two continuously stratified fluid layers. The upper layer, containing a zonal shear flow and representing the Jovian cloudy regions above p ～ 5 bars, is the same as Eady's (1949) model for the Earth. The lower layer has a relatively large but finite depth with a quiescent basic state, representing the deep Jovian fluid bulk below p ～ 5 bars. Due to the presence of the lower layer, the linearized non-dimensional growth rates are drastically reduced from the O(1) growth rates of the original Early model. Only very long wavelengths relative to the upper fluid's radius of deformation L₁ are unstable. Eddy transports of heat are also reduced relative to estimates based on scaling arguments alone. Since the hydrostatic approximation for the lower-layer perturbation breaks down at great depths, a second model is presented in which energy propagates downward in an infinitely deep lower fluid obeying the full linearized fluid equations. In this model, the growth rates are again very small, but now all wavelengths are unstable with maximum growth rates occurring for wavelengths O(1) relative to L₁. These results illustrate the importance for the upper-layer meteorology of the interface boundary condition with the lower fluid, which is radically different from the rigid lower boundary of the Earth's troposphere.     

Vertical extent of zonal winds on Venus

Possible interrelationships of different observations have been studied to clear up some obvious inconsistencies and develop a coherent picture of the kinematics of the Venus atmosphere. There is a wind shear in the vicinity of 60 km with vertical dimensions on the order of a scale height. The kinematical model has negligible surface winds, speeds increasing with altitude to approximately 45 km, a layer of high-speed retrograde zonal winds extending from approximately 45 to 60 km, a wind shear between 60 and 65 km, and slow atmospheric motions above this. Spacecraft data show that the region of high-speed winds is thicker on the day side of the planet than on the night side.     

Boulder 1, Station 2, Apollo 17: Petrology and petrogenesis

Boulder 1, Station 2, Apollo 17 is a stratified boulder containing dark clasts and dark-rimmed light clasts set in a light-gray friable matrix. The gray to black clasts (GCBx and BCBx) are multigenerational, competent, high-grade metamorphic, and partially melted breccias. They contain a diverse suite of lithic clasts which are mainly ANT varieties, but include granites, basaltic-textured olivine basalts, troctolitic and spinel troctolitic basalts, and unusual lithologies such as KREEP norite, ilmenite (KREEP) microgabbro, and the Civet Cat norite, which is believed to be a plutonic differentiate. The GCBxs and BCBxs are variable in composition, averaging a moderately KREEPy olivine norite. The matrix consists of mineral fragments derived from the observed lithologies plus variable amounts of a component, unobserved as a clast-type, that approximates a KREEP basalt in composition, as well as mineral fragments of unknown derivation. The high-temperature GCBxs cooled substantially before their incorporation into the friable matrix of Boulder 1. The light friable matrix (LFBx) is texturally distinct from the competent breccia clasts and, apart from the abundant ANT clasts, contains clasts of a KREEPy basalt that is not observed in the competent breccias. The LFBx lacks such lithologies as the granites and the Civet Cat norite observed in the competent breccias and in detail is a distinct chemical as well as textural entity. We interpret the LFBx matrix as Serenitatis ejecta deposited in the South Massif, and the GCBx clasts as remnants of an ejecta blanket produced by an earlier impact. The source terrain for the Serenitatis impact consisted of the competent breccias, crustal ANT lithologies, and the KREEPy basalts, attesting to substantial lunar activity prior to the impact. The age of the older breccias suggests that the Serenitatis event is younger than 4.01±0.03 b.y.     

First record of a Cretaceous cheilostome bryozoan from Hokkaido, Japan

A small collection of recrystallised, encrusting colonies of a single species from the Mikasa Formation (lower Middle Cenomanian), represents the first record of cheilostome (malacostegan or anascan) bryozoans from Hokkaido, Japan.     

An investigation of upper mantle heterogeneity beneath the Archaean and Proterozoic crust of western Canada from Lithoprobe controlled-source seismic experiments

Observations of upper mantle reflectivity at numerous locations around the world have been linked to the presence of a heterogeneous distribution of rock types within a broad layer of the upper mantle. This phenomenon is observed in wide-angle reflection data from Lithoprobe's Alberta Basement Transect [the SAREX and Deep Probe experiments of 1995] and Trans-Hudson Orogen Transect [the THoRE experiment of 1993]. SAREX and Deep Probe image the Archaean lithosphere of the Hearne and Wyoming Provinces, whereas THoRE images the Archaean and Proterozoic lithosphere of the Trans-Hudson Orogen and neighbouring areas.Finite-difference synthetic seismograms are used to constrain the position and physical properties of the reflective layer. SAREX/Deep Probe modelling uses a 2-D visco-elastic finite-difference routine; THoRE modelling uses a pseudospectral algorithm. In both cases, the upper mantle is parameterized in terms of two media. One medium is the background matrix; the other is statistically distributed within the first as a series of elliptical bodies. Such a scheme is suitable for modelling: (1) variations in lithology (e.g., a peridotite matrix with eclogite lenses) or (2) variations in rheology (e.g., lenses of increased strain within a less strained background).The synthetic seismograms show that the properties of heterogeneities in the upper mantle do not change significantly between the two Lithoprobe transects. Beneath the Trans-Hudson Orogen in Saskatchewan, the layer is best modelled to lie at depths between 80 and 150 km. Based on observations from perpendicular profiles, anisotropy of the heterogeneities is inferred. Beneath the Precambrian domains of Alberta, 400 km to the west, upper mantle heterogeneities are modelled to occur between depths of 90 and 140 km. In both cases the heterogeneous bodies within the model have cross-sectional lengths of tens of kilometers, vertical thicknesses less than 1 km, and velocity contrasts from the background of − 0.3 to − 0.4 km/s. Based on consistency with complementary data and other results, the heterogeneous layer is inferred to be part of the continental lithosphere and may have formed through lateral flow or deformation within the upper mantle.     

Monte Carlo simulation of mixing in Ca3Fe2Ge3O12–Ca4Ge4O12 garnets and implications for the thermodynamic stability of pyrope–majorite solid solution

Static lattice energy calculations, based on empirical pair potentials, were performed for a large set of structures differing in the arrangement of octahedral cations within the garnet 2 × 2 × 2 supercell. The compositions of these structures varied between Ca₃Fe₂Ge₃O₁₂ and Ca₄Ge₄O₁₂. The energies were cluster expanded using pair and quaternary terms. The derived ordering constants were used to constrain Monte Carlo simulations of temperature-dependent mixing properties in the ranges of 1,073–3,673 K and 0–10 GPa. The free energies of mixing were calculated using the method of thermodynamic integration. The calculations predict a wide miscibility gap between Fe-rich (cubic) and Fe-pure (tetragonal) garnets consistent with recent experimental observations of Iezzi et al. (Phys Chem Miner 32:197–207, 2005). It is shown that the miscibility gap arises due to a very strong cation ordering at the Fe-pure composition, driven by the charge difference between Ca²⁺ and Ge⁴⁺ cations. The structural and thermodynamic analogies between Ca–Ge and Mg–Si systems suggest that a similar miscibility gap should exist between pyrope and Mg–Si-majorite.     

Ultra-rapid landscape response and sediment yield following glacier retreat, Icy Bay, southern Alaska

The páramo is a neotropical alpine ecosystem that covers more than 75,000 km² of the northern Andes of Colombia, Ecuador, Venezuela, and Peru. It provides important environmental services: more than 10 million people in the Andean highlands benefit from the water supply and regulation function, which is attributed to the volcanic soils that underlie the ecosystem. The soils are also major carbon sinks of global significance. Severe land use changes and soil degradation threaten both the hydrology and carbon sink function. Nevertheless, soil genesis and properties in the páramo is rather poorly understood, nor are their ecological functions well documented. The impact of the geomorphology of the páramo on soil genesis was studied in the rio Paute basin, south Ecuador. Two toposequences were described and analysed. In each toposequence, four pedons were selected representing summit, backslope, undrained plain situation, and valley bottom positions in the landscape. The soils are classified as Hydric Andosols in the World Reference Base for Soil Resources and Epiaquands or Hydrudands in Soil Taxonomy. They are very acidic and have a high organic matter content, high P deficiency, and Al toxicity. Their water content ranges from 2.64 g g^− 1 at saturation, down to 1.24 g g^− 1 at wilting point, resulting in a large water storage capacity. Two major soil forming processes are identified: (1) volcanic ash deposition and (2) accumulation of organic carbon. Volcanic ash deposits may vary in depth as a result of regional geomorphological factors such as parent material, orientation, slope, and altitude. Organic carbon accumulation is an interaction of both waterlogging, which depends on the position in the landscape, and the formation of organometallic complexes with Al and Fe released during volcanic ash breakdown. Despite the high variability in parent material and topography, the soil is characterised by a notable homogeneity in physico-chemical properties. Statistical analysis reveals that only topographic location has a slight but significant influence on soil pH as well as the organic matter content, saturated conductivity and water retention at high pressure. Finally, the exceptional properties of these soils provide useful insights to improve classification of the Andosols reference group of the FAO World reference Base for Soil Resources.