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.     

The Composition of Garnets from Pelitic Schists in relation to the Grade of Regional Metamorphism

Analyses of garnets are presented from a wide variety of metamorphicterrains, in relation to which there appears to be a regularpattern of substitution of (FeO+MgO) for (CaO+MnO), the valuesof these components reflecting the metamorphic grade of thepelitic schists. This provides a method for indicating variationsin grade in metamorphic terrains and for comparing the variationsin different areas. In areas of repeated metamorphism this wouldappear to have a particular value in establishing the gradeof the various episodes of metamorphism. It is also demonstratedthat by the determination of selected physical propertics (unitcell edge a and refractive index) of garnets in the peliticschists, and evaluating the significance of their variations,it is possible to work out the local changes of metamorphicgrade within a particular area.     

Observed daily large-scale rainfall patterns during BOBMEX-1999

A daily rainfall dataset and the corresponding rainfall maps have been produced by objective analysis of rainfall data. The satellite estimate of rainfall and the raingauge values are merged to form the final analysis. Associated with epochs of monsoon these rainfall maps are able to show the rainfall activities over India and the Bay of Bengal region during the BOBMEX period. The intra-seasonal variations of rainfall during BOBMEX are also seen using these data. This dataset over the oceanic region compares well with other available popular datasets like GPCP and CMAP. Over land this dataset brings out the features of monsoon in more detail due to the availability of more local raingauge stations.     

Cosmic‐ray exposure history of two Frontier Mountain H‐chondrite showers from spallation and neutron‐capture products

Abstract— We measured the concentrations of ¹⁰Be, ²⁶Al, ³⁶Cl, ⁴¹Ca and ¹⁴C in the metal and/or stone fractions of 27 Antarctic chondrites from Frontier Mountain (FRO), including two large H‐chondrite showers. To estimate the pre‐atmospheric size of the two showers, we determined the contribution of neutron‐capture produced ³⁶Cl (half‐life = 3.01 times 10⁵ years) and ⁴¹Ca (1.04 times 10⁵ years) in the stone fraction. The measured activities of neutron‐capture ³⁶Cl and ⁴¹Ca, as well as spallation produced ¹⁰Be and ²⁶Al, were compared with Monte Carlo‐based model calculations. The largest shower, FRO 90174, includes eight fragments with an average terrestrial age of (100 ± 30) × 10³ years; the neutron‐capture saturation activities extend to 27 dpm/kg stone for ³⁶Cl and 19 dpm/kg stone for ⁴¹Ca. The concentrations of spallation produced ¹⁰Be, ²⁶Al and ³⁶Cl constrain the radius (R) to 80–100 cm, while the neutron‐capture ⁴¹Ca activities indicate that the samples originated from the outer 25 cm. With a pre‐atmospheric radius of 80–100 cm, FRO 90174 is among the largest of the Antarctic stony meteorites. The large pre‐atmospheric size supports our hypothesis that at least 50 of the ～150 classified H5/H6‐chondrites from the Frontier Mountain stranding area belong to this single fall; this hypothesis does not entirely account for the high H/L ratio at Frontier Mountain. The smaller shower, FRO 90001, includes four fragments with an average terrestrial age of (40 ± 10) × 10³ years; they contain small contributions of neutron‐capture ³⁶Cl, but no excess of ⁴¹Ca. FRO 90001 experienced a complex exposure history with high shielding conditions in the first stage (150 < R < 300 cm) and much lower shielding in the second stage (R < 30 cm), the latter starting ～1.0 million years (Ma) ago. Based on the measured ¹⁰Be/²¹Ne and ²⁶Al/²¹Ne ratios, the cosmic‐ray exposure ages of the two showers are 7.2 ± 0.5 Ma for FRO 90174 and 8 ± 1 Ma for FRO 90001. These ages coincide with the well‐established H‐chondrite peak and corroborate the observation that the exposure age distribution of FRO H‐chondrites is similar to that of non‐Antarctic falls. In addition, we found that corrections for neutron‐capture ³⁶Ar (from decay of ³⁶Cl) result in concordant ²¹Ne and ³⁸Ar exposure ages.     

Organochlorine compounds in bottom sediments of a delta Branch of the Northern Dvina

Organochlorine compounds in bottom sediments of a delta branch of the Northern Dvina have been studied. Data on the concentration and distribution of organically bound chlorine are given. The specific features of the formation of the levels and profiles of chlorinated phenolic compounds in bottom sediments under the effect of specific primary and secondary sources in the territory of Arkhangelsk Industrial Center are demonstrated.     

EISCAT/CRRES observations: nightside ionospheric ion outflow and oxygen-rich substorm injections

We present combined observations made near midnight by the EISCAT radar, all-sky cameras and the combined released and radiation efects satellite (CRRES) shortly before and during a substorm. In particular, we study a discrete, equatorward-drifting auroral arc, seen several degrees poleward of the onset region. The arc passes through the field-aligned beam of the EISCAT radar and is seen to be associated with a considerable upflow of ionospheric plasma. During the substorm, the CRRES satellite observed two major injections, 17 min apart, the second of which was dominated by O⁺ ions. We show that the observed are was in a suitable location in both latitude and MLT to have fed O⁺ ions into the second injection and that the upward flux of ions associated with it was sufficient to explain the observed injection. We interpret these data as showing that arcs in the nightside plasma-sheet boundary layer could be the source of O⁺ ions energised by a dipolarisation of the mid- and near-Earth tail, as opposed to ions ejected from the dayside ionosphere in the cleft ion fountain.     

Possible creep-related tilt precursors obtained in the Central Apennines (Italy) and in the Southern Caucasus (Georgia)

Daily averaged tilt component data from two sites of the Central Apennines (Italy) and of the Southern Caucasus (Georgia), respectively, revealed intermediate-term tilts as possible precursors to earthquakes (M=3.0÷4.7) which occurred in the above-mentioned seismic areas within a distance of 50 km from the sites. A good temporal correlation as well as a fair spatial correspondence between these residual tilts (with amplitude and duration of some microradians and months, respectively) and main shocks were pointed out, by removing both secular trends and seasonal thermoelastic effects from the raw tilts. An attempt was made to justify the above-mentioned results, based on the assumption that the observed intermediate-term preseismic tilts are the manifestation of aseismic creep episodes of comparable duration in the fault materials of thrust faults close to the tilt sites. The mechanism refers to a strain field slowly propagating from the preparation focal area to the tilt site, through crustal blocks separated by weak transition zones. This propagation is thought to be the cause of the local aseismic fault slip recorded by the tiltmeters. Previously, both discrete structures and strain propagation effects were revealed in the Central Apennines and are thought also to exist in the Southern Caucasus. As in the past, the rheological properties of fault materials are revealed as viscoelastic ones. In fact, creep equations obtained by applying several viscoelastic models on our data, proved to fit quite well some of the observed tilt precursors, producing viscosity and rigidity values very similar to those reported in literature.Professor Petr Viktorovich Manjgaladze died during the writing of this paper