Fractionation of platinum, palladium, nickel, and copper in sulfide–arsenide systems at magmatic temperature

Experimentally derived phase relations of arsenide in sulfide melt are presented to quantify the fractionation paths of As-bearing sulfide melts. When a natural sulfide melt reaches arsenide saturation, a separate Ni–PGE-rich arsenide melt exsolves. The arsenic saturation concentration in an Fe–Ni–Cu sulfide melt is between 0.5 and 1.5 wt%. The affinities of the chalcophile metals for an immiscible arsenide melt follow the order Pt > Pd > Ni ? Fe ≈ Cu. In natural systems, arsenide exsolution will be triggered by the activity of the nickel arsenide components dissolved in sulfide melt, Ni being the most common base metal with strong affinity to the As^n? anionic species. Arsenic may have a major effect on the fractionation paths of sulfide melts even if no separate arsenide phase forms. Arsenic, and probably many other chalcogens and metalloids in magmatic melts, may undergo associations with Pt and Pd well before discrete PGE minerals become stable phases.     

Vapour source and spatiotemporal variation of precipitation isotopes in Southwest Spain

The δ²H and δ¹⁸O composition of 77 precipitation samples collected between January 2014 and April 2019 from two sites across the Guadalquivir Basin, SW Spain, were analysed. The first site is located in an urban area of Seville at 100 km distance to the Atlantic coast and the second site is located in a dune area of the Doñana National Park a few kilometres from the coast. Sampling was performed within intervals of at least 14 days if rain occurred but frequently intervals were longer according to the rainfall incidence. Samples from both sites are available for the period February 2016 to June 2018 with six samples containing identical rain events at both locations. Precipitation weighted averages and local meteoric water lines produced by weighting and non-weighting regression methods are presented for its use in hydrological applications. Results show a remarkably high variability in δ²H and δ¹⁸O values and precipitation weighted average d-excess values of 11.8‰ and 13‰ at the sites Plaza de España and Doñana, respectively. Temperature and amount effects were found to be weak. A significant influence of secondary evaporation for single rainfall events during summer was identified by enriched isotopic signatures with reduced d-excess values plotting close or below the global meteoric water line. Backward trajectory analysis of 115 days with daily rainfall above 3 mm yield a predominant Atlantic Ocean vapour source with negligible Mediterranean influence and therefore, d-excess variability is attributed to the different ocean surface conditions of relative humidity and sea surface temperature. Parallel sampling indicate very similar isotopic signatures at both sites and point to the existence of thermal effects of the Plaza de España site in Seville city during the summer season.     

Timing of high-pressure metamorphic events in the Bulgarian Rhodopes from Lu–Hf garnet geochronology

Within the Mediterranean realm, the Rhodopes represent a nappe stack of oceanic and continental fragments assembled along the Eurasian continental margin during the Alpine orogeny. The timing of the high-pressure (HP) metamorphism has long been ambiguous, lacking detailed geochronological and geochemical control on subduction-exhumation and nappe stacking processes. Here we apply the Lu–Hf and Sm–Nd chronometers to a suite of representative eclogite samples covering two different key units of the Rhodopean nappe stack: (1) the Kimi Complex (Upper Allochthon) and (2) the Middle Allochthon. In addition to geochronology, we also determined whole rock Hf and Nd isotope compositions as well as major and trace element concentrations in order to constrain the nature of the eclogite protoliths. Two HP metamorphic events were revealed by Lu–Hf geochronology: (1) a Lower Cretaceous event in the Upper Allochthon (126.0 ± 1.7 Ma) and (2) an Eocene event in the Middle Allochthon (44.6 ± 0.7 Ma; 43.5 ± 0.4 Ma; 42.8 ± 0.5 Ma), at conditions of ca. 700°C/20–25 kbar. Our new data provide direct evidence for multiple subduction events in the Rhodopes. Exhumation and subsequent thrusting of the Middle Allochthon on the Lower Allochthon can be narrowed down to the time span between 42 and 34 Ma. In a broader tectonic context, the Eocene ages for the HP metamorphism support the view that the Rhodopes represent a large-scale tectonic window, exposing the deepest nappe units of the Hellenides.     

On the shearing behaviour of an artificially cemented soil

Ground improvement by cementation is a technique widely used because of the easiness of application and relatively low cost. To date, however, there is no global understanding of the behaviour of artificially cemented soil with respect to its dosage, so that in practice methodologies still rely on previous used scenarios rather than scientific facts. This paper presents results of low-to-high-pressure triaxial tests performed on pure and cemented specimens of decomposed granite where the dosage was controlled, chosen as a function of the ratio of porosity to volumetric cement content or adjusted porosity/cement index. The behaviour of the cemented soil was analysed in terms of peak strength and failure envelopes, stress dilatancy and state boundary surfaces, on which the influence of the porosity/cement index was examined.     

Solubility of palladium in picritic melts: 1. The effect of iron

In order to improve our understanding of HSE geochemistry, we evaluate the effect of Fe on the solubility of Pd in silicate melts. To date, experimentally determined Pd solubilities in silicate melt are only available for Fe-free anorthite-diopside eutectic compositions. Here we report experiments to study the solubility of Pd in a natural picritic melt as a function of pO₂ at 1300 °C in a one atm furnace. Palladium concentrations in the run products were determined by laser-ablation-ICP-MS. Palladium increases from 1.07 ± 0.26 ppm at FMQ-2, to 306 ± 19 ppm at FMQ+6.6. At a relative pO₂ of FMQ the slope in log Pd concentration vs. log pO₂ space increases considerably, and Pd concentrations are elevated over those established for AnDi melt compositions. In the same pO₂ range, ferric iron significantly increases relative to ferrous iron. Furthermore, at constant pO₂ (FMQ+0.5) Pd concentrations significantly increase with increasing X_FeO-total in the melt. Therefore, we consider ferric Fe to promote the formation of Pd²⁺ enhancing the solubility of Pd in the picrite melt significantly.The presence of FeO in the silicate melt has proven to be an important melt compositional parameter, and should be included and systematically investigated in future experimental studies, since most natural compositions have substantial FeO contents.     

Interaction of acid mine drainage with waters and sediments at the Corona stream, Lousal mine (Iberian Pyrite Belt, Southern Portugal)

This study investigates the geochemical characteristics of the acid mine drainage discharged from the abandoned mine adits and tailing piles in the vicinity of the Lousal mine and evaluates the extent of pollution on water and on the stream sediments of the Corona stream. Atmospheric precipitation interacting with sulphide minerals in exposed tailings produces runoff water with pH values as low as 1.9–2.9 and high concentrations of (9,249–20,700 mg l⁻¹), Fe (959–4,830 mg l⁻¹) and Al (136–624 mg l⁻¹). The acidic effluents and mixed stream water carry elevated Cu, Pb, Zn, Cd and As concentrations that exceed the water quality standards. However, the severity of contamination generally decreases 4 km downstream of the source due to mixing with fresh waters, which causes the dilution of dissolved toxic metals and neutralization of acidity. Some natural attenuation of the contaminants also occurs due to the general reduced solubility of most trace metals, which may be removed from solution, by either co-precipitation or adsorption to the iron and aluminium precipitates.