The great sulfur depletion of Earth’s mantle is not a signature of mantle–core equilibration

The extreme depletion of the Earth’s mantle in sulfur is commonly seen as a signature of metal segregation from Earth’s mantle to Earth’s core. However, in addition to S, the mantle contains other elements as volatile as S that are hardly depleted relative to the lithophile volatility trend although they are potentially as siderophile as sulfur. We report experiments in metal-sulfide–silicate systems to show that the CI normalized abundances of S, Pb, and Sn in Earth’s mantle cannot be reproduced by element partitioning in Fe ± S–silicate systems, neither at low nor at high pressure. Much of the volatile inventory of the Earth’s mantle must have been added late in the accretion history, when metal melt segregation to the core had become largely inactive. The great depletion in S is attributed to the selective segregation of a late sulfide matte from an oxidized and largely crystalline mantle. Apparently, the volatile abundances of Earth’s mantle are not in redox equilibrium with Earth’s core.     

Along-strike shear-sense reversal in the Vals-Scaradra Shear Zone at the front of the Adula Nappe (Central Alps,Switzerland)

The Adula Nappe in the Central Alps comprises pre-Mesozoic basement and minor Mesozoic sediments, overprinted by Paleogene eclogite-facies metamorphism. Peak pressures increase southward from ca. 1.2 GPa to values over 3 GPa, which is interpreted to reflect exhumation from a south-dipping subduction zone. The over- and underlying nappes experienced much lower Alpine pressures. To the north, the Adula Nappe ends in a lobe surrounded by Mesozoic metasediments. The external shape of the lobe is simple but the internal structure highly complicated. The frontal boundary of the nappe represents a discontinuity in metamorphic peak temperatures, between higher T in the Adula Nappe and lower T outside. A shear zone with steeply dipping foliation and shallowly-plunging, WSW-ENE oriented, i.e. orogen-parallel stretching lineation overprinted the northernmost part of the Adula Nappe and the adjacent Mesozoic metasediments (Vals-Scaradra Shear Zone). It formed during the local Leis deformation phase. The shear sense in the Vals-Scaradra Shear Zone changes along strike; from sinistral in the W to dextral in the E. Quartz textures also vary along strike. In the W, they indicate sinistral shearing with a component of coaxial (flattening) strain. A texture from the middle part of the shear zone is symmetric and indicates coaxial flattening. Textures from the eastern part show strong, single c-axis maxima indicating dextral shearing. These relations reflect complex flow within the Adula Nappe during a late stage of its exhumation. The structures and reconstructed flow field indicate that the Adula basement protruded upward and northward into the surrounding metasediments, spread laterally, and expelled the metasediments in front towards west and east.     

Influence of Decarbonisation and Phosphate Dosage on Copper Corrosion in Drinking Water Systems

The effect of softening/decarbonisation and dosage of orthophosphate on copper corrosion was studied in pipe rigs according to the German standard DIN 50931, part 1. A literature study with regard to the effects of phosphate dosing on copper corrosion has shown that on the one hand and in most of the cases a dosage of phosphate led to lower copper concentrations. On the other hand phosphate aggravated the copper corrosion in some cases. The mechanisms are not yet clear and the influence of phosphate on the corrosion of copper remains a question to be answered. Using standardised on‐site corrosion tests (DIN 50931‐1) with virgin copper pipes softening/decarbonisation has decreased the copper concentration. Two effects of phosphate on copper corrosion were noticed: Phosphate dosing decreased the copper oxidation and resulted in lower copper concentration in water. Likewise phosphate hindered the precipitation of cupric ions, which prolonged the existence of copper in water and resulted in a higher copper concentration. As a consequence, dosing phosphate can decrease or increase the copper corrosion, this depends on which effect is dominating.     

Molecular signature and sources of biochemical recalcitrance of organic C in Amazonian Dark Earths

Amazonian Dark Earths (ADE) are a unique type of soils developed through intense anthropogenic activities that transformed the original soils into Anthrosols throughout the Brazilian Amazon Basin. We conducted a comparative molecular-level investigation of soil organic C (SOC) speciation in ADE (ages between 600 and 8700 years B.P.) and adjacent soils using ultraviolet photo-oxidation coupled with ¹³C cross polarization-magic angle spinning nuclear magnetic resonance (CP-MAS NMR), synchrotron-based Fourier transform infrared-attenuated total reflectance (Sr-FTIR-ATR) and C (1s) near edge X-ray absorption fine structure (NEXAFS) spectroscopy to obtain deeper insights into the structural chemistry and sources of refractory organic C compounds in ADE. Our results show that the functional group chemistry of SOC in ADE was considerably different from adjacent soils. The SOC in ADE was enriched with: (i) aromatic-C structures mostly from H- and C-substituted aryl-C, (ii) O-rich organic C forms from carboxylic-C, aldehyde-C, ketonic-C and quinine-C, and (iii) diverse group of refractory aliphatic-C moieties. The SOC in adjacent soils was predominantly composed of O-alkyl-C and methoxyl-C/N-alkyl-C structures and elements of labile aliphatic-C functionalities. Our study suggests that the inherent molecular structures of organic C due to selective accumulation of highly refractory aryl-C structures seems to be the key factor for the biochemical recalcitrance and stability of SOC in ADE. Anthropogenic enrichment with charred carbonaceous residues from biomass-derived black C (BC) is presumed to be the precursor of these recalcitrant polyaromatic structures. Our results also highlight the complementary role that might be played by organic C compounds composed of O-containing organic C moieties and aliphatic-C structures that persisted for millennia in these anthropic soils as additional or secondary sources of chemical recalcitrance of SOC in ADE. These organic C compounds could be the products of: (i) primary recalcitrant biomolecules from non-BC sources or (ii) secondary processes involving microbial mediated oxidative or extracellular neoformation reactions of SOC from BC and non-BC sources; and stabilized through physical inaccessibility to decomposers due to sorption onto the surface or into porous structures of BC particles, selective preservation or through intermolecular interactions involving clay and BC particles.     

Late Cretaceous eclogite in the Eastern Rhodopes (Bulgaria): evidence for subduction under the Sredna Gora magmatic arc

International Journal of Earth Sciences - The Rhodopes in Bulgaria and Greece represent a nappe stack of high-grade units with polymetamorphic history. Constraining the time of metamorphism in...     

Sensitivity-guided reduction of parametric dimensionality for multi-objective calibration of watershed models

Problem complexity for watershed model calibration is heavily dependent on the number of parameters that can be identified during model calibration. This study investigates the use of global sensitivity analysis as a screening tool to reduce the parametric dimensionality of multi-objective hydrological model calibration problems while maximizing the information extracted from hydrological response data. This study shows that by expanding calibration problem formulations beyond traditional, statistical error metrics to also include metrics that capture indices or signatures of hydrological function, it is possible to reduce the complexity of calibration while maintaining high quality model predictions. The sensitivity-guided calibration is demonstrated using the Sacramento Soil Moisture Accounting (SAC-SMA) conceptual rainfall–runoff model of moderate complexity (i.e., up to 14 freely varying parameters). Using both statistical and hydrological metrics, optimization results demonstrate that parameters controlling at least 20% of the model output variance (through individual effects and interactions) should be included in the calibration process. This threshold generally yields 30–40% reductions in the number of SAC-SMA parameters requiring calibration – setting the others to a priori values – while maintaining high quality predictions. Two parameters are recommended to be calibrated in all cases (percent impervious area and lower zone tension water storage), three parameters are needed in drier watersheds (additional impervious area, riparian zone vegetation, and percent of percolation going to tension storage), and the lower zone parameters are crucial unless the watershed is very dry. Overall, this study demonstrates that a coupled, multi-objective sensitivity and calibration analysis better captures differences between watersheds during model calibration and serves to maximize the value of available watershed response time series. These contributions are particularly important given the ongoing development of more complex integrated models, which will require new tools to address the growing discrepancy between the information content of hydrological data and the number of model parameters that have to be estimated.