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.     

Assessing the contribution of off‐fault deformation to slip‐rate estimates within the Taupo Rift,New Zealand,using 3‐D ground‐penetrating radar surveying and trenching

We demonstrate that conventional palaeoseismic trenching and mapping techniques that do not account for the effects of off‐fault deformation can significantly underestimate a fault’s slip rate. Using combined interpretations of 3‐D ground‐penetrating radar (GPR) and palaeoseismic trench data, we show that drag folding and hangingwall and footwall horizontal‐axis rotations have accommodated up to 41% of total extension across a normal fault within the Taupo Rift, New Zealand, over the past 24.6 ± 1.0 cal. ka BP. Our results may explain why geologically determined fault‐slip rates for the central and southern Taupo Rift are anomalously low when compared with geodetic estimates. We suggest that a combination of GPR surveying and palaeoseismic trenching may help resolve differences between geodetically and geologically determined strain rates observed across active extensional regimes worldwide.     

Response of the uppermost mantle to Indo-Eurasian collisional tectonics

The rheological law for the power law creep field of peridotite suggested by Chopra and Paterson (1981, 1984) is combined with theoretically modelled thermal and stress perturbations for continent-continent collisions (Bird et al., 1975; Bird, 1978a) to determine the effect of such collisions on the uppermost mantle below the zone of convergence. The model predicts a change from continental to oceanic geotherms during the oceanic subduction phase, followed by a rapid rise in differential stress during the collisional phase.These perturbations, when combined, cause a cyclical change in the steady state flow of the uppermost mantle ending with a re-equilibration of thermal and stress regimes. The thermal re-equilibration proceeds at a much slower rate, with a suggested total re-equilibration period of about 100 m.y. after collision has ceased. The combination of the flow law with the model predicts that the perturbations in the mantle are limited in depth with no changes in mantle behavior below about 100 km.     

A middle–late Ediacaran volcano‐sedimentary record from the eastern Arabian‐Nubian shield

The Ediacaran Jibalah Group comprises volcano‐sedimentary successions that filled small fault‐bound basins along the NW–SE‐trending Najd fault system in the eastern Arabian‐Nubian Shield. Like several other Jibalah basins, the Antaq basin contains exquisitely preserved sedimentary structures and felsic tuffs, and hence is an excellent candidate for calibrating late Ediacaran Earth history. Shallow‐marine strata from the upper Jibalah Group (Muraykhah Formation) contain a diversity of load structures and intimately related textured organic (microbial) surfaces, along with a fragment of a structure closely resembling an Ediacaran frond fossil and a possible specimen of Aspidella. Interspersed carbonate beds through the Muraykhah Formation record a positive δ¹³C shift from ?6 to 0‰. U‐Pb zircon geochronology indicates a maximum depositional age of ~570 Ma for the upper Jibalah Group, consistent with previous age estimates. Although this age overlaps with that of the upper Huqf Supergroup in nearby Oman, these sequences were deposited in contrasting tectonic settings on opposite sides of the final suture of the East African Orogen.     

Impact of irrigated agriculture on groundwater-recharge salinity: a major sustainability concern in semi-arid regions

Intensive irrigated agriculture substantially modifies the hydrological cycle and often has major environmental impacts. The article focuses upon a specific concern—the tendency for progressive long-term increases in the salinity of groundwater recharge derived from irrigated permeable soils and replenishment of unconfined aquifers in more arid regions. This process has received only scant attention in the water-resource literature and has not been considered by agricultural science. This work makes an original contribution by analysing, from scientific principles, how the salinisation of groundwater recharge arises and identifies the factors affecting its severity. If not proactively managed, the process eventually will impact irrigation waterwell salinity, the productivity of agriculture itself, and can even lead to land abandonment. The types of management measure required for mitigation are discussed through three detailed case histories of areas with high-value groundwater-irrigated agriculture (in Spain, Argentina and Pakistan), which provide a long-term perspective on the evolution of the problem over various decades.     

Three varieties of alpine-type ultramafic rocks in the Norwegian Caledonides and basal gnesis complex

Three varieties of alpine-type ultramafic rocks are distinguish in the Norwegian Caledonides associated Basal Gneiss Complex. Type one rocks have primary (magmatic) olivine, clinopyroxene, orthopyroxene and chromite, and are partly or completely serpentinised. They are found exclusively in rocks of Cambro-Silurian age. Type two are polymetamorphic metaperidotites or sagvandites consisting of olivine, enstatite and carbonate minerals, with talc and amphibole commonly being present. They are found in medium- to high-grade metamorphic rocks. Type three also show a metamorphic mineral association of olivine, orthopyroxene and minor chromite, while clinopyroxene, amphibole and chrome-bearing chlorite may also be present in some samples. Garnet may or may not occur and, where present, is often surrounded by reaction rims of spinel and amphibole. The type three ultramafic bodies are serpentinised to varying degrees and occur in high-grade metamorphic gneisses which may also contain eclogites and anorthosites. Distinction of these three varieties of ultramafic body may be useful for correlation purposes and for more detailed studies on the nature of their metamorphism.     

The Otago schist megaculmination: Its possible origins and tectonic significance in the Rangitata orogen of New Zealand

In South Island, New Zealand, the Otago schist, 30,000 square km in extent, consists mainly of greenschist facies quartzo-feldspathic metagreywacke and meta-argillite with minor metavolcanics and metacherts. Before metamorphism the sediments were probably Carboniferous to Jurassic; the flanking, steeply dipping greywackes are Triassic in the northeast and southeast, and Permian in the west and southwest.Regional metamorphism culminating in the Late Jurassic was accompanied by pervasive deformation generating a variety of interrelated folds on all scales. The scarcity of distinctive reference units makes recognition of macroscopic structures difficult, and much progress has depended on observations of vergence of mesoscopic folds interpreted as defining macroscopic folds having axial plane separation of between 2 km and 6 km.At least two phases of synmetamorphic deformation are distinguishable locally, but regionally have an overlapping multiphase relationship. The regional schistosity structure is an irregular flat-crested antiform trending S and SE. The internal megascopic structure defined by the mesoscopic folds, appears to consist of a stack of nappe-folds facing east and northeast, which pass into reclining isoclinal folds in the west, southwest and north-east, and is interpreted to be a megaculmination. Mineral and textural metamorphic zones were developed during deformation, and a relatively simple regional pattern established at a late stage by continuing recrystallisation.The Otago schist originated in a complex sequence of Paleozoic—Mesozoic plate interactions near the southwest Pacific margin of Gondwanaland. It included part of a volcaniclastic frontal arc-basin assemblage (Murihiku and Caples Terranes) lying north or northeast of an older crystalline foreland, and a quartzo-feldspathic assemblage of plutonic-metamorphic provenance lying further to the northeast (Torlesse Terrane). Parts of these terranes underwent mainly greenschist facies metamorphism during Late Jurassic subduction-collision to form the Haast Schist Terrane of which the Otago schist is a major part.The earliest Torlesse sediments are thought to have prograded as a vast fan complex onto oceanic crust from the southwesterly crystalline foreland in the Carboniferous, then in the Permian were separated from their source by a spreading zone which thereafter isolated them from the sedimentary province of the newly developing arc system. Tectonic recycling of these sediments at a Permian to Jurassic oceanic subduction zone is considered to have developed the westward progradation features and the products of limited vulcanism found in the present Torlesse Terrane. The New Zealand Geosyncline appears to have consisted of a spreading zone between two inwardly facing convergent zones, one flanked by a foreland to the southwest, the other wholly oceanic.The metamorphic climax of the Rangitata Orogeny was the result of the medial spreading zone passing into the westerly subduction zone, so permitting the convergent zones to collide, with the Torlesse sediments caught between them.The mantle system driving the spreading zone appears to have continued to function, and soon after the collisional climax caused Late Jurassic—Cretaceous rifting of the sialic edge of Gondwanaland, igneous activity, differential shear of the New Zealand region, and initiation of the Alpine Fault. It subsequently commenced sea-floor spreading in the Tasman Sea, and later in the southwest Pacific Ocean.     

High-precision osmium isotopes in enstatite and Rumuruti chondrites

Isotopic heterogeneity within the solar nebula has been a long-standing issue. Studies on primitive chondrites and chondrite components for Ba, Sm, Nd, Mo, Ru, Hf, Ti, and Os yielded conflicting results, with some studies suggesting large-scale heterogeneity. Low-grade enstatite and Rumuruti chondrites represent the most extreme ends of the chondrite meteorites in terms of oxidation state, and might thus also present extremes if there is significant isotopic heterogeneity across the region of chondrite formation. Osmium is an ideal tracer because of its multiple isotopes generated by a combination of p-, r-, and s-process and, as a refractory element; it records the earliest stages of condensation.Some grade 3-4 enstatite and Rumuruti chondrites show similar deficits of s-process components as revealed by high-precision Os isotope studies in some low-grade carbonaceous and ordinary chondrites. Enstatite chondrites of grades 5-6 have Os isotopic composition identical within error to terrestrial and solar composition. This supports the view of digestion-resistant presolar grains, most likely SiC, as the major carrier of these anomalies. Destruction of presolar grains during parent body processing, which all high-grade enstatite chondrites, but also some low-grade chondrites seemingly underwent, makes the isotopically anomalous Os accessible for analysis. The magnitude of the anomalies is consistent with the presence of a few ppm of presolar SiC with a highly unusual isotopic composition, produced in a different stellar environment like asymptotic giant branch stars (AGB) and injected into the solar nebula. The presence of similar Os isotopic anomalies throughout all major chondrite groups implies that carriers of Os isotopic anomalies were homogeneously distributed in the solar nebula, at least across the formation region of chondrites.