How network-sensitive mesopore sorption descriptors relate to bis(trifluoromethanesulfonyl)imide anion [TFSI−] displacement and cell-level charging remains poorly understood for hierarchical porous carbons. Herein, we compare predominantly mesoporous, hard-templated CMK-3 with combined hard-and-salt-templated ST-CMK-3, which additionally contains a substantial micropore fraction, using network-aware sorption, quantitative transmission electron microscopy (TEM), 19F pulsed-field-gradient nuclear magnetic resonance (PFG NMR), and electrochemistry. The CMK-3 sorption response is adequately described by the chain-limit model, whereas ST-CMK-3 is better represented by a model permitting higher effective coordination, indicating departure from a simple chain-like mesopore response. Analysis of selected TEM micrographs reveals comparable local fringe spacing and retained mesoscale periodic contrast, but lower region-of-interest (ROI)-scale fast Fourier transform (FFT) annular anisotropy and shorter image texture correlation scales for ST-CMK-3, indicating weaker directional concentration within the selected spatial-frequency band despite comparable local coherency. Two-component analysis of the 19F PFG NMR attenuation yields a larger constraint-dependent point estimate of the effective transverse TFSI− diffusion coefficient for ST-CMK-3 in physically constrained fits at matched bulk-like ex-pore signal fractions. Although fitted parameters reach bounds and the nominal conditional transverse 95% confidence intervals overlap, this ordering persists across the tested ex-pore fractions. It also matches the ordering of effective transverse coefficients previously derived from 19F two-dimensional exchange spectroscopy (2D EXSY) NMR exchange rates within an exchange model, although the methods probe different observables. In 1 M aqueous lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), ST-CMK-3 delivers higher low-rate capacitance and energy density at comparable average power, but lower high-current capacitance retention and slower capacitive relaxation. These pair-specific observations are consistent with complementary contributions from mesopore-associated electrolyte access and redistribution and micropore-associated charge storage and equilibration, without isolating connectivity as the causal variable.
Calcium is widely used to improve apple postharvest performance and reduce bitter pit development, but the mechanisms linking calcium accumulation with cold storage tolerance remain unclear. This study investigated calcium-mediated responses in peel and flesh tissues of two apple cultivars, ‘King Roat’ and ‘Golden Chief’, during harvest and cold storage. Repeated preharvest calcium applications increased calcium accumulation in both tissues, maintained fruit firmness, and markedly reduced bitter pit symptoms after cold storage. Integrated cell wall, metabolomic, and transcriptomic analysis showed that calcium protection extended beyond its classical structural role. Calcium reshaped pectin-, xyloglucan-, and arabinogalactan protein-associated cell wall domains in a cultivar- and tissue-dependent manner, supporting improved wall cohesion and reduced tissue destabilization. Metabolomic profiling revealed coordinated changes in carbohydrate, organic acid, lipid, phenolic, and glutathione-related pathways, consistent with metabolic adjustment during storage. Transcriptomic analysis in ‘King Roat’ further indicated that calcium repressed genes associated with cell wall loosening, flavonoid biosynthesis, and programmed cell death, while activating redox-related components. Among the validated genes, MdGRXC11L was consistently induced by calcium across cultivars, tissues, and storage stages, indicating a potential role for glutaredoxin-mediated redox recovery in calcium-associated protection. Overall, these findings support a model in which calcium reduces bitter pit expression by reinforcing cell wall cohesion, maintaining metabolic homeostasis, and promoting glutathione-linked redox regulation during cold storage, providing potential molecular targets for predicting and managing postharvest physiological disorders in apple.
Garnet–biotite–sillimanite gneisses from the hanging wall and footwall of Pb–Zn mineralization in the Proterozoic Rampura–Agucha SEDEX belt (NW India) were investigated to constrain their pressure–temperature (P–T) evolution. Quartz-in-garnet (QuiG) elastic barometry and near-peak Ti-in-biotite thermometry were applied alongside conventional chemical thermobarometry (garnet–biotite thermometry and GASP (garnet–Al2SiO5–plagioclase–quartz) barometry). Unlike conventional chemical thermometers, elastic barometry is significantly less susceptible to retrograde Fe–Mg re-equilibration and post-peak modification. Quartz entrapment pressures (Pentr) of 6.2–8.2 kbar, calculated using Ti-in-biotite temperatures of 621–722 °C, are broadly consistent with GASP pressures of 6.7–8.8 kbar calculated at the same temperatures, with GASP pressures only modestly higher (∼0.5–1.0 kbar) and the two methods overlapping within propagated uncertainty. In contrast, garnet–biotite temperatures of 506–576 °C are systematically 68–146 °C lower than Ti-in-biotite temperatures, indicating substantial retrograde Fe–Mg re-equilibration during cooling and exhumation. Peak conditions inferred from elastic barometry fall within the sillimanite stability field, within ∼ 1 kbar of the kyanite–sillimanite transition. The absence of kyanite is attributed to kinetically inhibited Al2SiO5 polymorph transformation at relatively low temperature, consistent with the exclusive occurrence of metastable fibrolite in three distinct textural settings. A subset of quartz inclusions records negative residual pressures, interpreted as evidence for deformation-induced elastic stress relaxation during exhumation. These results demonstrate that quartz-in-garnet elastic barometry preserves near-peak pressures only partially overprinted by later deformation and exhumation. The close agreement between elastic barometry, GASP barometry, and previously published peak metamorphic estimates indicates peak metamorphism at approximately 6–9 kbar and 620–720 °C in the Rampura–Agucha deposit.
Periodic technical inspections (PTI) are used globally to ensure in-use vehicle fleet roadworthiness. Since 2022, five European countries have added a particle number test (PN-PTI) to PTI for diesel vehicles with particulate filters to identify high ultrafine particle emitters and mandate repairs. This study examines PN-PTI results from nearly two million Euro 5 and Euro 6 diesel vehicles inspected between 2022 and 2024 in the Flemish region of Belgium and the Netherlands and evaluates different PN limits. The analysis reveals lower failure rates in newer vehicles meeting more recent Euro standards and significant differences between brands. High mileage increases failure rates in older vehicles but has little effect on newer ones. Using three machine learning models, the study identifies first registration year as generally the most important feature associated with PN-PTI failure, followed by brand and mileage. Overall, PN-PTI emerges as an effective policy tool for mitigating gross particle emitters.
The Aegean Sea is a transboundary marine system facing increasing ecological pressure from overfishing, habitat degradation, pollution, and climate change, while fisheries management remains fragmented between neighbouring jurisdictions. Marine Protected Areas (MPAs) have therefore emerged as a key policy tool for supporting ecosystem recovery and sustainable fisheries. Recent initiatives by Greece and Türkiye provide a timely opportunity to evaluate how alternative spatial protection strategies may influence ecological and fisheries outcomes in a shared marine basin. Using an established Ecopath with Ecosim (EwE) model and its spatial module (Ecospace), we assessed five hypothetical MPA scenarios reflecting individual (country based) and combined protection configurations associated with recent proposals and designations, relative to a baseline scenario representing current management. To allow direct comparison among alternative spatial designs, the additional MPAs were implemented as hypothetical no-fishing zones, with fishing excluded for all modelled fleets from 2025 to 2035, followed by a return to baseline management conditions until 2040. By 2040, five years after the additional MPA restrictions ended, changes in total ecosystem biomass were small across scenarios, while spatially localized and functional group-specific responses persisted. The magnitude and direction of responses varied among spatial configurations and functional groups, with both positive and negative legacy effects on biomass and catches. The combined transboundary spatial configuration produced stronger and more extensive persistent spatial responses than the individual configurations tested. These findings underscore the importance of spatial design and cross-border considerations when evaluating MPA strategies for reconciling conservation and fisheries objectives in the Aegean Sea.
