Compositional effects on element partitioning between Mg-silicate perovskite and silicate melts

High-pressure melting experiments were performed at ~26 GPa and ~2,200–2,400°C on synthetic peridotite compositions with varying FeO and Al₂O₃ contents and on a synthetic CI chondrite analogue composition. Peridotite liquids show a crystallisation sequence of ferropericlase (Fp) followed down temperature by Mg-silicate perovskite (MgPv) + Fp, which contrasts a sequence of MgPv followed by MgPv + Fp observed in the chondritic composition. The difference in crystallisation sequence is a consequence of the different bulk Mg/Si ratios. MgPv/melt partition coefficients for major, minor and trace elements were determined by electron microprobe and secondary ion mass spectrometry. Partition coefficients of tri- and tetravalent elements increase with increasing Al concentration in MgPv. A lattice strain model indicates that Al³⁺ substitutes predominantly onto the Si-site in MgPv, whereas most elements substitute onto the Mg-site, which is consistent with a charge-compensating coupled substitution mechanism. MgPv/melt partition coefficients for Mg (D_Mg) and Si (D_Si) are related to the melt Mg/Si ratio such that D_Si becomes lower than D_Mg at low Mg/Si melt ratios. We use a crystal fractionation model, based on upper mantle refractory lithophile element ratios, to constrain the amount of MgPv and Ca-silicate perovskite (CaPv) that could have fractionated during a Hadean magma ocean event and could still be present as a chemically distinct heterogeneity in the lower mantle today. We show that a fractionated crystal pile composed of 96% MgPv and 4% CaPv could comprise up to 13 wt% of the entire mantle.     

Iridium enrichment and poor fractionation from gold, platinum and palladium in clausthalite (PbSe), Tilkerode, eastern Harz, Germany

Enrichments in platinum-group elements were found in clausthalite, PbSe, which occurs in carbonate–hematite veins hosted in black shale of Upper Wenlockian age in the eastern Harz, Germany. Spot measurements by laser ablation–quadrupole inductively coupled plasma mass spectrometry (LA–QICPMS) show that the clausthalite has Pt contents that average 0.459?ppm and range from 0.003 to 2.83?ppm. Other noble metals quantified in the present work include Au (0.226?ppm, 0.109–0.451?ppm), Ru (0.061?ppm, 0.006–0.264?ppm), Ir (0.071?ppm, 0.010–0.185?ppm), Pd (0.046?ppm, 0.017–0.107?ppm) and Os (0.010?ppm, <0.003–0.024?ppm). Elemental ratios of Au/Ir, Pd/Ir and Pt/Ir, the average values of which are respectively 4.6, 0.8, and 4.9, suggest that Au, Pd and Pt are poorly fractionated from Ir. The resulting Ir enrichment is unusual and should reflect a particularly soluble (and stable) aqueous complex of Ir in a highly oxidizing, low-temperature, Se-rich solution.     

δ53Cr values of catchment runoff exhibit seasonality regardless of bedrock Cr concentrations: Role of periodically changing chromium export fluxes

One pre-requisite for the construction of a global chromium isotope mass balance is detailed understanding of Cr isotope systematics in the critical zone where redox-processes can modify the isotope signature of geogenic Cr input into the hydrosphere. A Cr isotope inventory of bedrock, soil, and runoff was performed in a Central European headwater catchment underlain by amphibolite, situated in the vicinity of two previously studied catchments underlain by different bedrock types (serpentinite and leucogranite). Fresh bedrock in the amphibolite catchment NAZ contained ~300 mg/kg Cr, serpentinite at PLB contained ~800 mg/kg Cr, and leucogranite at LYS contained ~2 mg/kg Cr. Monthly hydrochemical monitoring at all three sites revealed higher Cr(VI) export fluxes in winter than in summer. NAZ was characterized by a distinct seasonality in the δ⁵³Cr values, with minima during winter/spring snowmelts (−0.35‰) and maxima during dry summers (0.40‰). Similar seasonality in δ⁵³Cr values had been reported from PLB and LYS. Bedrock at all three sites had similar Cr isotope composition close to −0.10‰, a value indistinguishable from the δ⁵³Cr value of bulk silicate Earth (BSE). Positive mean δ⁵³Cr value of NAZ runoff indicated Cr-isotope fractionations during weathering of geogenic Cr(III), combined with adsorption of the resulting Cr(VI) on soil particles during pedogenesis. However, the mass-weighted mean δ⁵³Cr of NAZ runoff was lower (−0.08‰), indistinguishable from the Cr isotope signature of bedrock. The same pattern of lower mass-weighted mean δ⁵³Cr values of runoff, compared to arithmetic mean δ⁵³Cr values of runoff, were observed also at PLB and LYS. We suggest that elevated Cr runoff fluxes in winter remove some of the residual isotopically light Cr that accumulated in the soil during summer. Seasonality in runoff δ⁵³Cr values appears to be a relatively widespread phenomenon, de-coupled from Cr availability for chemical weathering.     

Fatty acid transfer in the food web of a coastal Mediterranean lagoon: Evidence for high arachidonic acid retention in fish

The transfer of fatty acids (FAs) in the food web of a Mediterranean lagoon was studied using FA compositional patterns across several trophic levels. The structure of the food web was inferred from C and N stable isotopes values and an isotope mixing model was used in order to estimate the relative contribution of the different potential food sources to the biomass of consumers. Bidimensional plots of FA composition of food web components against their δ¹⁵N values indicated a general trend of increasing proportions of highly unsaturated fatty acids (HUFAs) with increasing trophic levels while the proportions of saturated fatty acids (SAFAs) and 18-carbon polyunsaturated fatty acids (PUFAs) decreased. Using the relative contributions of food sources to consumers and their FA compositions, a model was built in order to estimate the PUFA composition of consumer mixed diets which was compared to consumer PUFA profiles. The latter allowed the identification of the PUFAs which were mostly enriched/retained in consumer lipids. There was a surprisingly high retention of arachidonic acid (ARA), a trend which challenges the idea of low ARA needs in marine fish and suggests the important physiological role of this essential FA for fish in estuarine environments.     

Least-cost adaptation options for global climate change impacts on the Brazilian electric power system

Global climate change induced by the emission of greenhouse gases may pose challenges to energy security. The vulnerability of energy sources, in particular of renewable sources, to climate change raises the need to identify adaptation measures. This paper applies an integrated resource planning approach to calculate least-cost adaptation measures to a set of projected climate impacts on the Brazilian power sector. The methodology used has the advantage of finding optimal solutions that take into consideration the whole energy chain and the interactions between energy supply and demand. Results point in the direction of an increased installed capacity based, mostly, on natural gas, but also sugarcane bagasse, wind power and coal/nuclear plants, to compensate for a lower reliability of hydroelectric production, amongst other impacts. The indirect effect of these results is the displacement of natural gas from other consuming sectors, such as industry, in favor of its use for power generation. Results obtained are, however, based on the techno-economic premises used in the simulation, which may vary in the long term.     

Ultimate grout-to-soil bond strength of micropiles in glacial deposits

Acta Geotechnica - This paper analyzed the ultimate grout-to-soil bond strength based on a database of 40 full-scale static load tests conducted on micropiles in glacial deposits in the province of...     

Sediment density flow distribution on wave-influenced deltas

Deltas are at the transition between fluvial and marine sedimentary environments where sediment density flows are often triggered during high river discharge events, forming submarine channels and sediment waves. On wave-influenced deltas, longshore currents are particularly efficient at transporting sediment alongshore, reducing the likelihood of sediment density flows from occurring at river mouths. This study describes four deltaic sedimentary systems at different stages of their evolution on a formerly glaciated continental inner shelf of eastern Canada in order to better understand the distribution of sediment density flows on wave-influenced deltas. Three types of settings are recognized as being prone to sediment density flows: (i) in the early stages of wave-influence and on large deltas, converging longshore currents can lead to offshelf sediment transport; (ii) on wave-influenced to wave-dominated deltas, a sandy spit can re-route the river mouth and sediment density flows form where the spit intersects the delta lip; (iii) in advanced stages of wave-dominated deltas and during their demise, rocky headlands are exposed and can intersect the slope, where off-shelf sediment transport occurs. These types of sediment density flows were all characterized by debris flows or surge-type turbidity currents which have limited offshore run-out. More rarely, hyperpycnal flows form at the river mouths, especially where the river incises glaciomarine clays prone to landsliding in the river, which increases fine-grained fluvial suspended sediment concentration. Overall, these results highlight the predominance of fluvial-dominated deltas during a phase of relative sea-level fall combined with high sediment supply. However, as soon as sediment supply diminishes, wave action remobilizes sediment alongshore modifying the distribution and types of sediment density flows occurring on wave-influenced deltas.     

Land use and land cover dynamics in Leiria City: relation between peri-urbanization processes and hydro-geomorphologic disasters

Natural Hazards - The objective of the present study is to evaluate the relation between the spatial and temporal dynamics of Land Use and Land Cover (LULC) and the hydro-geomorphological processes...     

Mercury's capture into the 3/2 spin-orbit resonance including the effect of core-mantle friction

The rotation of Mercury is presently captured in a 3/2 spin-orbit resonance with the orbital mean motion. The capture mechanism is well understood as the result of tidal interactions with the Sun combined with planetary perturbations [Goldreich, P., Peale, S., 1966. Astron. J. 71, 425-438; Correia, A.C.M., Laskar, J., 2004. Nature 429, 848-850]. However, it is now almost certain that Mercury has a liquid core [Margot, J.L., Peale, S.J., Jurgens, R.F., Slade, M.A., Holin, I.V., 2007. Science 316, 710-714] which should induce a contribution of viscous friction at the core-mantle boundary to the spin evolution. According to Peale and Boss [Peale, S.J., Boss, A.P., 1977. J. Geophys. Res. 82, 743-749] this last effect greatly increases the chances of capture in all spin-orbit resonances, being 100% for the 2/1 resonance, and thus preventing the planet from evolving to the presently observed configuration. Here we show that for a given resonance, as the chaotic evolution of Mercury's orbit can drive its eccentricity to very low values during the planet's history, any previous capture can be destabilized whenever the eccentricity becomes lower than a critical value. In our numerical integrations of 1000 orbits of Mercury over 4 Gyr, the spin ends 99.8% of the time captured in a spin-orbit resonance, in particular in one of the following three configurations: 5/2 (22%), 2/1 (32%) and 3/2 (26%). Although the present 3/2 spin-orbit resonance is not the most probable outcome, we also show that the capture probability in this resonance can be increased up to 55% or 73%, if the eccentricity of Mercury in the past has descended below the critical values 0.025 or 0.005, respectively.