A methodology to calibrate and to validate effective solid potentials of heterogeneous porous media from computed tomography scans and laboratory-measured nanoindentation data

Built on the framework of effective interaction potentials using lattice element method, a methodology to calibrate and to validate the elasticity of solid constituents in heterogeneous porous media from experimentally measured nanoindentation moduli and imported scans from advanced imaging techniques is presented. Applied to computed tomography (CT) scans of two organic-rich shales, spatial variations of effective interaction potentials prove instrumental in capturing the effective elastic behavior of highly heterogeneous materials via the first two cumulants of experimentally measured distributions of nanoindentation moduli. After calibration and validation steps while implicitly accounting for mesoscale texture effects via CT scans, Biot poroelastic coefficients are simulated. Analysis of stress percolation suggests contrasting pathways for load transmission, a reflection of microtextural differences in the studied cases. This methodology to calibrate elastic energy content of real materials from advanced imaging techniques and experimental measurements paves the way to study other phenomena such as wave propagation and fracture while providing a platform to fine-tune effective behavior of materials given advancements in additive manufacturing and machine learning algorithms.     

<Superscript>10</Superscript>Be surface exposure dating of the last deglaciation in the Aare Valley,Switzerland

The combined Rhone and Aare Glaciers presumably reached their last glacial maximum (LGM) extent on the Swiss Plateau prior to 24 ka. Two well-preserved, less extensive moraine stades, the Gurten and Bern Stade, document the last deglaciation of the Aare Valley, yet age constraints are very scarce. In order to establish a more robust chronology for the glacial/deglacial history of the Aare Valley, we applied ¹⁰Be surface exposure dating on eleven boulders from the Gurten and Bern Stade. Several exposure ages are of Holocene age and likely document post-depositional processes, including boulder toppling and quarrying. The remaining exposure ages, however yield oldest ages of 20.7 ± 2.2 ka for the Gurten Stade and 19.0 ± 2.0 ka for the Bern Stade. Our results are in good agreement with published chronologies from other sites in the Alps.     

Variation in the rate of land subsidence induced by groundwater extraction and its effect on the response pattern of soil microbial communities

Excessive extraction of groundwater leads to (irreversible) changes in the physical soil properties, causing land subsidence associated with soil compaction to occur. Using a combined image processing and field approach, we examined: (1) how variation in the land subsidence rate induces different soil compaction degrees; and (2) the response patterns of microbial communities to such variations. By using Sentinel Synthetic Aperture Radar image processing, we selected three locations that exhibited different land subsidence rates, including high (HSR), moderate (MSR), and low (LSR). Then, soil sampling was undertaken within these representative locations. Indicators of soil compaction, including total porosity, air-filled porosity, water-filled porosity, and bulk density, were measured. The soil microbial community was determined using qPCR and sequencing. The highest and lowest values for bulk density were observed in the HSR–MSR and LSR zones, respectively. The greatest values of total porosity and macropore volume were displayed in the LSR zone compared to other zones. Bacterial abundance in the LSR zone was significantly greater than that in the HSR and MSR zones. The relative abundances of bacterial taxa indirectly demonstrated that the anaerobic phyla were significantly increased (by 10–13%), and the aerobic phyla decreased (by 30–40%) in the HSR zone compared to the LSR zone. This result demonstrates that the aerobes declined as larger volumes of the soil became more anaerobic. Indeed, the increased abundance of anaerobes was not able to compensate for the larger decrease in the abundance of aerobes. Our work showed that at the increased rates of land subsidence, the abundance distribution of the microbial community critically declined. These findings highlight the critical impacts of increasing the land subsidence rate on the emergence of high soil compaction degrees, which can significantly affect the resilience thresholds of the microbial communities in dryland soils.     

Environmental impacts of household appliances in Europe and scenarios for their impact reduction

Assessing the environmental impact due to consumption of goods and services is a pivotal step towards achieving the sustainable development goal related to responsible production and consumption (i.e. SDG 12). Household appliances plays a crucial role and should be assessed in a systemic manner, namely considering all life cycle stages, technological efficiency, and affluence aspects. The present study assess the impact of such household appliances used in Europe, and tests scenarios of potential impact reduction at various scales. Life cycle assessment is applied to 14 different household appliances (ranging from dishwashers to television devices) selected to build a set of representative products, based on their economic value and diffusion in households in Europe. Related impacts are calculated with the Environmental Footprint method for calculating a Consumer Footprint “appliances” for the baseline year 2010. A number of scenarios encompassing eco-solutions on a technical level, changes in consumption pattern, behavioral changes, as well as the combination of all these aspects are run to estimate the Consumer Footprint related to household appliances for the year 2030, compared against this baseline scenario. The baseline Consumer Footprint is confirming the importance of the use phase in leading the impacts in almost all impact categories. Testing different scenarios concludes that there is a reduction of the impact for most of the categories (with up to 67% for the ozone depletion potential, and still around 35% for the global warming potential), while two of the here examined impact categories (i.e. land-use and mineral resource depletion) show an overall potential that is even negative – i.e. the results of all scenarios are higher than the ones of the 2010 baseline scenario. The increase in purchase and use of such appliances may offset energy efficiency benefits in some of the examined categories. Hence, the assessment of sustainability of appliances consumption should always include several scales, from the efficiency of the products (micro scale), to the improvement of the energy mix (meso scale), up to accounting for socio-economic drivers and patterns of consumption affecting the overall appliances stock (macro scale).     

Experimental partitioning of halogens and other trace elements between olivine, pyroxenes, amphibole and aqueous fluid at 2 GPa and 900–1,300 °C

We present new partition coefficients for various trace elements including Cl between olivine, pyroxenes, amphibole and coexisting chlorine-bearing aqueous fluid in a series of high-pressure experiments at 2 GPa between 900 and 1,300 °C in natural and synthetic systems. Diamond aggregates were added to the experimental capsule set-up in order to separate the fluid from the solid residue and enable in situ analysis of the quenched solute by LA–ICP–MS. The chlorine and fluorine contents in mantle minerals were measured by electron microprobe, and the nature of OH defects was investigated by infrared spectroscopy. Furthermore, a fluorine-rich olivine from one selected sample was investigated by TEM. Results reveal average Cl concentrations in olivine and pyroxenes around 20 ppm and up to 900 ppm F in olivine, making olivine an important repository of halogens in the mantle. Chlorine is always incompatible with Cl partition coefficients D _Cl ^{olivine/fluid} varying between 10^?5 and 10^?3, whereas D _Cl ^{orthopyroxene/fluid} and D _Cl ^{clinopyroxene/fluid} are ~10^?4 and D _Cl ^{amphibole/fluid} is ~5 × 10^?3. Furthermore, partitioning results for incompatible trace element show that compatibilities of trace elements are generally ordered as D ^amph/fluid ≈ D ^cpx/fluid > D ^opx/fluid > D ^ol/fluid but that D ^{mineral/fluid} for Li and P is very similar for all observed silicate phases. Infrared spectra of olivine synthesized in a F-free Ti-bearing system show absorption bands at 3,525 and ~3,570 cm^?1. In F ± TiO₂-bearing systems, additional absorption bands appear at ~3,535, ~3,595, 3,640 and 3,670 cm^?1. Absorption bands at ~3,530 and ~3,570 cm^?1, previously assigned to humite-like point defects, profit from low synthesis temperatures and the presence of F. The presence of planar defects could not be proved by TEM investigations, but dislocations in the olivine lattice were observed and are suggested to be an important site for halogen incorporation in olivine.     

Multistage growth of Fe–Mg–carpholite and Fe–Mg–chloritoid,from field evidence to thermodynamic modelling

We provide new insights into the prograde evolution of HP/LT metasedimentary rocks on the basis of detailed petrologic examination, element-partitioning analysis, and thermodynamic modelling of well-preserved Fe–Mg–carpholite- and Fe–Mg–chloritoid-bearing rocks from the Afyon Zone (Anatolia). We document continuous and discontinuous compositional (ferromagnesian substitution) zoning of carpholite (overall X _Mg = 0.27–0.73) and chloritoid (overall X _Mg = 0.07–0.30), as well as clear equilibrium and disequilibrium (i.e., reaction-related) textures involving carpholite and chloritoid, which consistently account for the consistent enrichment in Mg of both minerals through time, and the progressive replacement of carpholite by chloritoid. Mg/Fe distribution coefficients calculated between carpholite and chloritoid vary widely within samples (2.2–20.0). Among this range, only values of 7–11 correlate with equilibrium textures, in agreement with data from the literature. Equilibrium phase diagrams for metapelitic compositions are calculated using a newly modified thermodynamic dataset, including most recent data for carpholite, chloritoid, chlorite, and white mica, as well as further refinements for Fe–carpholite, and both chloritoid end-members, as required to reproduce accurately petrologic observations (phase relations, experimental constraints, Mg/Fe partitioning). Modelling reveals that Mg/Fe partitioning between carpholite and chloritoid is greatly sensitive to temperature and calls for a future evaluation of possible use as a thermometer. In addition, calculations show significant effective bulk composition changes during prograde metamorphism due to the fractionation of chloritoid formed at the expense of carpholite. We retrieve P–T conditions for several carpholite and chloritoid growth stages (1) during prograde stages using unfractionated, bulk-rock XRF analyses, and (2) at peak conditions using compositions fractionated for chloritoid. The P–T paths reconstructed for the Kütahya and Afyon areas shed light on contrasting temperature conditions for these areas during prograde and peak stages.     

Processes affecting geochemistry and contaminant movement in the middle Claiborne aquifer of the Mississippi embayment aquifer system

Groundwater chemistry and tracer-based age data were used to assess contaminant movement and geochemical processes in the middle Claiborne aquifer (MCA) of the Mississippi embayment aquifer system. Water samples were collected from 30 drinking-water wells (mostly domestic and public supply) and analyzed for nutrients, major ions, pesticides, volatile organic compounds (VOCs), and transient age tracers (chlorofluorocarbons, tritium and helium-3, and sulfur hexafluoride). Redox conditions are highly variable throughout the MCA. However, mostly oxic groundwater with low dissolved solids is more vulnerable to nitrate contamination in the outcrop areas east of the Mississippi River in Mississippi and west Tennessee than in mostly anoxic groundwater in downgradient areas in western parts of the study area. Groundwater in the outcrop area was relatively young (apparent age of less than 40 years) with significantly (p < 0.05) higher dissolved oxygen and nitrate–N concentrations and higher detections of pesticides and VOCs compared to water samples from wells in downgradient areas. Oxygen reduction and denitrification rates were low compared to other aquifers in the United States (zero order rate constants for oxygen reduction and denitrification were 4.7 and 5–10 μmol/L/year, respectively). Elevated concentrations of nitrate–N, and detections of pesticides and VOCs in some deep public supply wells (>50 m depth) indicated contaminant movement from shallow parts of the aquifer into deeper oxic zones. Given the persistence of nitrate in young oxic groundwater that was recharged several decades ago, and the lack of a confining unit, the downward movement of young contaminated water may result in higher nitrate concentrations over time in deeper parts of the aquifer containing older oxic water.     

Absence of oxygen isotope fractionation/exchange of (hemi-) cellulose derived sugars during litter decomposition

Aiming at developing a novel tool for palaeoclimate research, we recently proposed a new method for determining the oxygen isotope composition of monosaccharides (Zech, M., Glaser, B., 2009. Compound-specific δ¹⁸O analyses of neutral sugars in soils using GC-Py-IRMS: problems, possible solutions and a first application. Rapid Communications in Mass Spectrometry 23, 3522-3532). In order to answer the question whether isotope fractionation and oxygen exchange reactions during litter decomposition affect the climatically controlled δ¹⁸O values of plant derived sugars, such as for instance xylose and arabinose from hemicelluloses, we studied the compound specific δ¹⁸O values of five different litter species having been decomposed in a field litterbag experiment for 27 months.While δ¹⁸O values of bulk organic matter yielded a systematic ¹⁸O depletion of 3.3‰ (pine) to 4.6‰ (spruce) accompanying total cellulose decomposition of 51% (beech) to 86% (ash), δ¹⁸O values of individual sugars show no significant trend with time. In addition to the observed absence of isotope fractionation during decomposition, we also rule out ¹⁸O exchange reactions affecting the δ¹⁸O signature of sugar molecules during diagenetic processes as well as during analytical procedure based on experimental findings and on theoretical biochemical mechanistic considerations. We conclude that our new method may become an analytical tool that elegantly overcomes extraction, purity and hygroscopicity problems of previous ¹⁸O cellulose methods. It furthermore has the potential to be applied to a wide range of climate archives such as tree rings, lacustrine sediments and loess palaeosol sequences.     

A late Pleistocene glacial chronology from the Kitschi-Kurumdu Valley,Tien Shan (Kyrgyzstan), based on 10Be surface exposure dating

Surface exposure dating has become a helpful tool for establishing numeric glacial chronologies, particularly in arid high-mountain regions where radiocarbon dating is challenging due to limited availability of organic material. This study presents 13 new ¹⁰Be surface exposure ages from the Kitschi-Kurumdu Valley in the At Bashi Range, Tien Shan. Three moraines were dated to ~ 15, 21 and > 56 ka, respectively, and corroborate previous findings that glacial extents in the Tien Shan during Marine Oxygen Isotope Stage (MIS) 2 were limited compared to MIS 4. This likely documents increasingly arid conditions in Central Asia during the last glacial cycle. Morphological evidence in the Kitschi-Kurumdu Valley and a detailed review of existing numeric glacial chronologies from the Tien Shan indicate that remnants of the penultimate glaciation (MIS 6) are preserved, whereas evidence for MIS 5 glacier advances remains equivocal. Reviewed and recalculated exposure ages from the Pamir mountains, on the other hand, reveal extensive MIS 5 glacial extents that may indicate increased monsoonal precipitation. The preservation of MIS 3 moraines in the Tien Shan and the southern Pamir does not require any monsoonal influence and can be explained alternatively with increased precipitation via the westerlies.