Secondary Carbon Research Articles

Carbon-coated ZnS as a high-performance ORR/OER bifunctional cathode catalyst for zinc-air batteries

The commercial application of zinc-air batteries (ZABs) is hindered by the high cost and scarcity of precious metal catalysts. In this paper, we prepared high-performance ORR/OER bifunctional catalysts with a carbon-coated ZnS spherical structure (ZnS@C) through a hydrothermal method followed by a carbonization process. Characterized by their unique spherical coated pore structure, exhibit impressive electrocatalytic activity. Specifically, ZnS@C-2, produced by a secondary carbonization process demonstrates an ORR half-wave potential of 0.82 V (relative to RHE) and an OER overpotential of 377 mV at 10 mA cm−2. When employed in a ZAB, it achieves a maximum power density of 120.4 mW cm−2, a specific capacity of 836 mAh gZn−1, and maintains cycle stabilization for up to 165 h at 10 mA cm−2. The research results demonstrate that the unique carbon-coated internal porous structure not only significantly enhances the stability of the catalyst but also increases the number of active sites, thereby providing more abundant activation energy for the catalytic reaction and facilitating its efficient progress. This underscores the catalyst's excellent ORR and OER properties, suggesting promising practical application potential.

Laboratory experiments of carbon mineralization potential of the main terrestrial basalt reservoirs in China

Against the background of realizing the goal of “carbon peaking and carbon neutrality”, using basaltic rocks for carbon mineralization is one of the most promising approaches to reduce the rise in atmospheric CO2 concentrations. This study conducted a series of experiments to assess carbon mineralization in nine basalt samples from the main terrestrial basalt reservoirs in China within CO2-H2O/brine-rock systems at low temperatures (≤35 °C). The results indicate that the secondary carbonates formed in the CO2-H2O/brine-basalt system are predominantly calcite rather than Mg-carbonate minerals at low temperatures (≤35 °C). Hence, at low temperatures (≤35 °C), basalt rich in Ca-bearing minerals promotes the formation of stable carbonate minerals more effectively than basalt containing Mg-bearing minerals. Furthermore, under conditions of low temperatures (≤35 °C) and pressures of approximately 3 MPa, the results suggest that alkaline olivine basalt, with a higher content of Ca-minerals and typical alkaline minerals (nepheline and Na-sanidine), exhibits the highest pH value and the highest amount of calcite. Hence, the alkaline minerals, nepheline and Na-sanidine, serve as pH buffers to increase the pH and promote the precipitation of calcite within CO2-H2O– basalt systems at low temperatures (≤35 °C). Among the nine evaluated basalts, basalt from the Shandong Linqu-Changle volcanic basin exhibits the highest rate of carbon mineralization at low temperatures (≤35 °C). Hence, Cenozoic alkaline olivine basalt from Shandong Linqu-Changle volcanic basin is one of the most promising basalt reservoirs in China for future in- situ carbonation. As for ex- situ carbonation, compared with olivine, diopside or Ca-plagioclase may be more appropriate for increasing ocean negative emissions.

Preparation of aragonite from calcium carbonate via wet carbonation to improve properties of steel slag building materials

Smelting in steel mills emitted large amounts of CO2 and produced the waste product steel slag (SS). Therefore, the use of SS to fix CO2 and produce value-added products could treat waste with waste and promote the effective use of resources. In this study, aragonite-type calcium carbonate was prepared by wet carbonation of SS, and the aragonite-rich SS (ASS) was pressed and moulded in the raw material of SS for semi-dry carbonation to obtain SS products. Through a series of experiments, the optimal conditions for the modulation and the formation mechanism of aragonite whiskers were investigated, and the effects of aragonite as a crystal seed on the properties and the degree of carbonation of SS products were also explored. In this experiment, the carbonation products were characterised microscopically by XRD, TGA, FT-IR and SEM, and the strength was tested by press machine. The results showed that aragonite phase was produced by wet carbonation of SS suspension containing 0.1M/L MgCl2 at 120 °C for 2h. The compressive strength, flexural strength, and secondary carbonation degree of the prepared SS products were increased when 5% ASS was added.

The Process of Soil Carbon Sequestration in Different Ecological Zones of Qingtu Lake in the Arid–Semi-Arid Region of Western China

As a vital component of the global carbon pool, soils in arid and semi-arid regions play a significant role in carbon sequestration. In the context of global warming, increasing temperatures and moisture levels promote the transformation of barren land into wetlands, enhancing carbon sinks. However, the overdevelopment of oases and excessive extraction of groundwater lead to the opposite effect, reducing carbon sequestration. This study examines two soil types—meadow soil (MS) and swamp soil (SS)—from Qingtu Lake, an arid lake in western China. It analyzes the sources of soil inorganic carbon, the composition and origin of dissolved organic matter (DOM), and the relationships between microbes, soil organic carbon (SOC), soil inorganic carbon (SIC), mineral composition, and soil texture. The results indicate that inorganic carbon in the study area consists of both primary carbonate minerals and secondary pedogenic carbonates. The DOM primarily consists of two components, both identified as terrestrial humic substances. In meadow soils, bacterial activity drives the weathering of plagioclase, which releases Ca2+ necessary for the formation of pedogenic carbonates. Plagioclase also provides colonization sites for microbes and, along with microbial activity, participates in the soil carbon cycle. Within the soil community, bacteria appear to play a more critical role than fungi. In contrast, microbial contributions to the carbon cycle in swamp soils are weaker, with minerals predominantly interacting with organic carbon to form mineral-associated organic matter, thus promoting the soil carbon cycle. These findings have important implications for understanding soil carbon sinks under different micro-ecological conditions in arid and semi-arid regions. Through targeted human intervention, it is possible to enhance carbon sequestration in these areas, contributing to the mitigation of global climate change.

Mechanisms of secondary carbonate precipitation on felsic, intermediate and mafic igneous rocks: a case study for NW Scotland

Silicate weathering is a natural regulator of atmospheric carbon dioxide (CO 2 ), where the majority of carbonate is stored in the oceans. In some instances, carbonates may form via bedrock weathering in terrestrial landscapes, but this is commonly noted in ultramafic rock owing to its desirable mineralogy. In NW Scotland, carbonate minerals surround felsic, intermediate and mafic igneous bedrock. Their abundance suggests that these rocks could potentially be targeted for carbonation, given the absence of other known cation sources nearby. We present geochemical and mineralogical data for bedrock samples and mineralogy and stable carbon and oxygen isotope data for the carbonate samples. Whole-rock geochemistry demonstrates that major abundances of CaO and MgO are present in the bedrock samples and would be sourced from plagioclase and pyroxene, which are target minerals for CO 2 mineralization. The stable carbon and oxygen isotope data demonstrate that there are probably mixed carbon sources (atmospheric and organic), and other environmental factors including temperature, CO 2 degassing or evaporation and nearby waters influence the isotopic composition. Results suggest that rocks traditionally overlooked in CO 2 mineralization studies have the potential to serve as a feedstock for carbonation, given the abundance of secondary carbonates found in NW Scotland.

Stark seasonal contrast of fine aerosol levels, composition, formation mechanism, and characteristics in a polluted megacity.

In this study, we investigated the temporal variation of organic and inorganic aerosol with its optical properties in Mumbai (India), an urban coastal region. Mean PM2.5concentrations during the sampling period were 175μg/m3 (winter) and 90μg/m3 (summer). During winter, the average concentrations of organic (OC), elemental (EC), and water-soluble organic carbon (WSOC) were three times higher than in summer. Secondary organic carbon (SOC) contribution in OC was higher in summer (78%) than in winter (53%), and strong solar radiation in summer likely caused this outcome. Aerosols were slightly acidic in both seasons, with an average pH of 5.7 (winter) and 6.0 (summer). A correlation was observed between SOC and the acidity of particles in summer (R2 = 0.6), indicating some amount of acid-catalysed SOC formation. In both seasons, the sulphate oxidation ratio (SOR) was higher than the nitrate oxidation ratio (NOR), which may reflect a preference for SO2 oxidation over NO2 or the difference in partitioning ammonium nitrate into ammonium sulphate under high RH. The dominant mechanism of SOC formation (gas vs aqueous phase oxidation) also showed seasonal variation. In winter, a relatively steep reduced major axis (RMA) slope of O3/CO suggests gas phase oxidation was the dominant mechanism of SOC production. Winter has more BrC fraction than summer, indicating higher absorbing aerosols, though the efficiency of absorbing the light was higher in summer. To assess the radiative forcing of PM2.5 on a local scale, an effective carbon ratio (ECR) was computed. The findings pointed to a local radiative heating impact caused by PM2.5. The spectral slope ratio and MAE at 250 to 300nm ratio (E2/E3) revealed a higher abundance of high molecular weight species in WSOC during summer than in winter.

Ratios of organic mass to organic carbon in fine particulate matter at urban sites in China and Korea during winter and summer.

This study evaluates the composition and seasonal characteristics of fine particulate matter (PM2.5) during winter and summer through simultaneous measurements conducted at the Gwangju Institute of Science and Technology in South Korea and the Changping campus of Peking University in China. PM2.5 samples were concurrently collected at both sites, and chemical analyses were conducted to quantify various components, including carbonaceous materials, ionic species, and metals. Although the average PM2.5 concentrations were comparable between the two sites, there were distinct differences in the concentrations of major components. Organic indicator compounds were analyzed to discern the contributions of primary and secondary pollution sources. Changping displayed a mix of primary and secondary pollution, characterized by higher concentrations of primary organic carbon (POC) such as polycyclic aromatic hydrocarbons and hopanes, compared to Gwangju. In contrast, Gwangju demonstrated a higher prevalence of secondary organic carbon (SOC), particularly water-soluble organic carbon not related to biomass burning (WSOCnbb) and various polar organic compounds. The organic mass to organic carbon (OM/OC) ratios estimated using the mass balance method revealed significant differences, with Gwangju showing a higher ratio of 2.3 compared to 1.9 at Changping, indicating a greater influence of secondary pollutants at Gwangju. Additionally, both Changping and Gwangju exhibited higher OM/OC ratios in summer (Changping: 2.0, Gwangju: 2.5) compared to winter (Changping: 1.8, Gwangju: 2.2), indicating seasonal differences in organic mass contributions to PM2.5. These findings underscore the importance of accounting for spatial and seasonal variations in air pollution studies and suggest that updating commonly used OM/OC ratios could enhance the reliability of research outcomes.

Exogenous glutathione (GSH/GSSG) promoted the synthesis of patchoulol and pogostone, main active components of Pogostemon cablin (Patchouli)

Glutathione redox pair (GSH/GSSG) is the main characterizing substance that regulates the redox balance in cells and affects several physiological processes, such as plant metabolism, antioxidants, and detoxification. Pogostemon cablin was treated with different concentrations of reduced glutathione (GSH) and oxidized glutathione (GSSG), and it was found that 2 mM GSH and 4 mM GSSG treatments promoted the synthesis of patchoulol and pogostone. A total of 6620 significant differentially expressed gene were identified by transcriptome analysis. KEGG analysis showed that DEGs were mainly enriched in metabolic pathways, secondary metabolite biosynthesis, carbon metabolism, and phytohormone signaling pathways; 388 DEGs in the 2 mM GSH (11d) group, and 254 DEGs in the 4 mM GSSG (11d) group, were related to the biosynthesis of secondary metabolites. Further analysis by Gene Set Enrichment Analysis (GSEA) revealed that there were 139 and 83 DEGs associated with terpene synthesis between the two treatment groups, respectively, and the expression of key genes in the synthesis pathway (11 HMGR, 4 DXR, 2 GPPS, and 8 PTS) was up-regulated, which may be the result of transcription factors regulating their expression. The present study preliminarily showed that glutathione redox pair induced the expression of genes related to the terpene biosynthesis pathway, thereby promoting the biosynthesis of patchoulol and pogostone, which provides a reference basis for the technique of regulating and controlling the content of medicinal constituents of patchouli.

Regeneration of secondary forest following anthropogenic disturbance from 1985 to 2021 for Amazonas, Brazil.

Following old-growth forest loss and subsequent land abandonment, secondary forest grows throughout the Amazon biome. For Amazonas, agricultural colonization was unsuccessful in many regions, leading to the regeneration of secondary forest and carbon storage under favorable climate conditions. Herein, the extent of regeneration in Amazonas and its timescale are investigated, including a granular analysis of its 62 municipalities, based on the MapBiomas dataset from 1985 to 2021. By 2021, 10,495 km2 of secondary forest had grown, corresponding to 28% of the lost old-growth forest. After normalization for algorithmic differences, this estimate was 17%-38% lower than prior studies for Amazonas that used earlier versions of the MapBiomas dataset, indicating increased accuracy in landcover assignments for more current versions of the dataset. For the northeastern microregion, representing the 15 municipalities of economic and population dominance in Amazonas, the growth of secondary forest varied from 3.0% to 9.8% of the total land area. For the southern microregion, constituting seven municipalities adjacent to large-scale deforestation of Mato Grosso and Rondônia, regeneration of secondary forest constituted 0.4%-1.2% of the land area. For the remaining interior municipalities, the regeneration was 0.0%-1.9%. Among the municipalities, the median regeneration interval, corresponding to the duration between the loss of old-growth forest and the appearance of secondary forest, ranged from 2 to 7 years. The median regeneration intervals of the interior, northeastern, and southern microregions were 3, 4, and 5 years, respectively. Even as the secular trend of deforestation continues in the Amazon biome and encroaches into the southern border of Amazonas state, the results herein indicate a possible resiliency toward secondary forest for undisturbed land on a timescale of several years, at least for mixed pasture-forest landscapes of kilometer-scale heterogeneity and assuming that a favorable climate persists for regeneration even as global change occurs.

Secondary carbon skeletons constructed in porous carbon for electric double layer capacitors

In this work, a secondary skeleton was constructed by filling the larger spaces of porous carbon derived from passion fruit peels with glucose to created more carbon surface in same volume. The combined use of KOH activation and simultaneous etching of micropores on the carbon skeleton and secondary skeleton resulted in the preparation of porous carbon (PGC1-0.5) containing a large number of micropores. PGC1-0.5 have less total pore volume (0.987 cm3 g-1), but more micropore volume (0.821 cm3 g-1), different with 1.171 cm3 g-1, 0.668 cm3 g-1 of PGC1-0, which without glucose. Symmetric supercapacitor bases on PPGC1-0.5 have an obvious improvement in specific capacity (275.6 F g-1 (175 F cm-3), 0.1 A g-1) in 6M KOH electrolyte compared to PGC1-0 (215.2 F g-1 (121.5 F cm-3), 0.1 A g-1). Additionally, the device exhibits excellent cycling performance and retained 103% of its specific capacity after 10,000 cycles and notable reduction in transfer internal resistance in comparison to the sample without glucose. This study shows that filling space with glucose to reduce macropores is an effective method for adjusting the pore size distribution of porous carbon.

Se-functionalized metal-free catalysts rich in sp3-hybridized carbon enable efficient oxygen electroreduction

Carbon-based metal-free materials are emerging as leading candidates to replace noble-metal catalysts in the oxygen reduction reaction (ORR). Herein, we introduce a facile secondary carbonation technique for fabricating Se and N co-doped metal-free catalysts using a zeolite imidazole framework (ZIF-8) as the precursor. The optimal electrocatalyst, designated SeNC-900, exhibited good ORR performance under both alkaline and acidic conditions, with half-wave potentials of 0.864 V and 0.731 V (vs. RHE), respectively. Density functional theory (DFT) calculations reveal that the enhanced activity of SeNC-900 originates from Se doping, which triggers an increase in the intrinsic defects of sp3-hybridized C. Concurrently, the sp3-hybridized C, in concert with Se dopant, modulates the electronic structure of the active C atoms. This work not only underscores the significance of tuning the electronic structure to boost catalytic performance by enriching intrinsic defects but also presents a fresh insight into the effect of heteroatom doping on carbon-based materials for electrocatalysis.

Gold Mineralisation and their Lithological Controls at Nagavi Area, Gadag Schist Belt, in Karnataka, India

Dharwar craton is located in southern India is part of the Dharwar-Singhbhum proto-continent and is known for its complex tectonic and structural controls. It’s made up of two distinct parts, Western Dharwar Craton (WDC) and the Eastern Dharwar Craton (EDC) house several schist belts. Many of these schist belts, such as the Kolar schist belt, Hutti schist belt, Chitradurga schist belt and the Gadag schist belt, are auriferous. In such schist belts, gold occurs in association with sulphides such as pyrite, pyrrhotite, arsenopyrite and chalcopyrite. Gold mineralization in these belts is found to occur in different lithologies. The Gadag schist belt is composed dominantly of metabasalt in its western half and meta sediments in the eastern half. Quartz-carbonate veins are observed to cut across these lithologies as well as the Banded Iron Formations (BIFs). This paper aimed to study the gold mineralization in different lithologies of the Gadag schist belt and found that metabasalts and BIFs are the dominant rocks hosting gold. It is also observed that mineralization is strata-bound. Most of the places’ auriferous sheared zones were observed in the study area. In Nagavi area, BIF hosted gold mineralization is observed, and major gold concentration varies from <21 to <26 ppb (parts per billion). Pyrite occurs as characteristic cubic crystals and as clusters of small grains. In carbonated sheared anorthosite, the rock is fine to medium-grained and in-equigranular. It consists of simple to polysynthetically twinned subhedral (100-200 by 400-600 μm) laths (~40-45%) set in a groundmass of irregular anhedral grains of secondary carbonate (~35-40%), chlorite (~8-10%), opaque (~5-7%) and accessory epidote and quartz.

Research on the Biogas Production Mechanism of Mudstone in the Qaidam Basin under Different CO2 Pressures.

Mudstone, a class of sedimentary rocks rich in organic matter, possesses considerable potential for biogas production. Mudstones possess a rich biological origin, which is conducive to refining the mechanisms and enrichment patterns of biogenic gas reservoirs. This has significant theoretical and practical implications for guiding the exploration and development of Quaternary mudstone gas reservoirs. Furthermore, the Qaidam Basin is an excellent place for the geological storage of CO2 due to its rich petroleum reservoir conditions. Experimental research on biogas production under diverse CO2 pressure-mudstone-microorganism-water interactions is conducted to determine the biogas production mechanism of mudstone under different CO2 pressures during sequestration circumstances. According to the results: (1) under supercritical carbon dioxide conditions, there is a slight initial increase in biogas production, followed by a gradual decrease. The periods and peaks of gas production vary among the different reaction groups. As carbon dioxide pressure increases, the gas production cycle lengthens significantly, while the gas yield declines. (2) Siderite and secondary carbonate minerals have increased in the mudstone's mineral fraction both before and after biogas production, while clay mineral groups have decreased. Specifically, there was a notable drop in chlorite and kaolinite. (3) Microorganism species in the system were analyzed, and the results showed that there was a gap in each microorganism's ability to adapt to its surroundings, and the diversity and quantity of bacteria declined with increasing pressure. After carbon dioxide was fluxed, there was a considerable shift in the pattern of biogas generation, which consequently had a major impact on the alterations in mineral fractions.

High-Pressure Rate Rules for Ether Alkylperoxy Radical Isomerization.

The first isomerization reaction of an alkylperoxy (RO2) radical holds significant importance in low-temperature oxidation, as it governs the branching ratios of the hydroperoxyalkyl (QOOH) radicals, which influence the competition between the chain-propagation and chain-branching reactions. In this study, we systematically calculated high-pressure rate rules for the RO2 isomerization reaction of monoethers, exploring 5-, 6-, 7-, and 8-membered ring transition states. Primary, secondary, and tertiary carbon sites, where both the abstracting peroxy group and the abstracted hydrogen are located, were considered, with particular emphasis on distinguishing between secondary carbons adjacent (alpha) and nonadjacent to the ether functional group. Using the G4//B3LYP/6-311++G(2df,2pd) level of theory and the transition state theory, we estimated the rate constants and the Arrhenius coefficient for over 120 possible isomerization reactions. We examined the effect of ring size and ring atoms, revealing that 6- and 7-membered ring isomerizations were generally the fastest. The impact of the ether functional group on transition states was investigated by comparing reactions with identical ring size, peroxy, and radical positions, but with the ether functional group positioned either outside (i.e., out) or inside (i.e., in) the transition state ring, leading to differences in the rate constants. When comparing to analogous alkane rate constants, differences of up to an order of magnitude were observed, underscoring the need for caution when assigning rate rules by analogy. We applied our rate constants in the di-iso-butyl ether kinetic model and evaluated their influence on low-temperature chemistry finding that they altered the branching ratios by up to a factor of 9, highlighting the significance of site-specific rate constants for more accurate low-temperature modeling.

Denudation and Weathering Rates of Carbonate Landscapes From Meteoric 10Be/9Be Ratios

AbstractKnowledge of the rates of carbonate rock denudation, the relative apportionment of chemical weathering versus physical erosion, and their sensitivity to climate, vegetation, and tectonics is essential for disclosing feedbacks within the carbon cycle and the functioning of karst landscapes that supply important services to humans. Currently, however, for carbonate lithologies, no method exists that allows to simultaneously partition denudation into erosion and weathering fluxes at spatial scales ranging from soil to watersheds. To determine total denudation rates in carbonate landscapes from an individual soil or river sample, we adapted a published framework that combines cosmogenic meteoric 10Be as an atmospheric flux tracer with stable 9Be that is released from rocks by weathering, to the limestone‐dominated French Jura Mountains. By analyzing water, soil, sediment, travertine, and bedrock for 10Be/9Be, major and trace elements, carbon stable isotopes and radiogenic strontium, we quantified contributions of Be from primary versus secondary carbonate phases and its release during weathering from carbonate bedrock versus silicate impurities. We calculated partitioning of Be between solids and solutes, and rates of catchment‐wide (from sediment) and point source (from soil) denudation, weathering and erosion. Our results indicate that average denudation rates are 300–500 t/km2/yr. Denudation is dominated by weathering intensity (W/D) ratios of >0.92, and a non‐negligible contribution from deeper (below soil) weathering. Our rates agree to within less than a factor of two with decadal‐scale denudation rates from combined suspended and dissolved fluxes, highlighting the substantial potential of this method for future Earth surface studies.

Stable isotope compositions, source apportionment and transformation processes of carbonaceous aerosols in PM10 in the urban city of Hyderabad, India

This study apportions sources of carbonaceous aerosols using isotopic characteristics of total carbon (TC) and elemental carbon (EC) in PM10 aerosols using filter-based CTO-375 method for pre-monsoon (summer), post-monsoon, and winter (2019–2021) over Hyderabad, India. Highest secondary organic carbon, SOC (primary organic carbon, POC) of 13.78 ± 10.25 (7.87 ± 2.48) μg/m3 was during post-monsoon 2020 (2019), while lowest was 8.90 ± 5.55 (4.18 ± 0.92) μg/m3 during pre-monsoon 2021 (post-monsoon 2020), respectively. Average effective carbon ratio (ECR) > 1 indicates dominance of light scattering aerosols during pre-monsoon and post-monsoon. δ13CTC and δ13CEC varied from – 28.1 to – 24.7 ‰ (avg. – 26.5 ± 0.7) and - 32.5 to – 24.6 ‰ (avg. – 27.4 ± 1.1), indicating contribution from C3 plant burning and liquid fuel combustion. Positive value of δ13COC – δ13CEC and heavier δ13CTC, along with gradual enrichment in δ13CTC and δ13CEC from December 2020 to March 2021, suggested photochemical aging of carbonaceous aerosols. Lighter δ13CTC and OC/EC > 4 for all seasons indicates dominance of biomass burning (wood and crop residue burning), photochemical oxidation and secondary organic aerosol (SOA) formation. The tropical study experiences dominance of lighter δ13CEC compared to subtropical, high latitude regions.

Estimates of carbon sequestration potential in an expanding Arctic fjord (Hornsund, Svalbard) affected by dark plumes of glacial meltwater

Abstract. In polar regions, glaciers are retreating onto land, gradually widening ice-free coastal waters, which are known to act as new sinks of atmospheric carbon. However, the increasing delivery of inorganic suspended particulate matter (iSPM) with meltwater might significantly impact their capacity to contribute to carbon sequestration. Here, we present an analysis of satellite, meteorological, and SPM data as well as results of a coupled physical–biogeochemical model (1D GOTM-ECOSMO-E2E-Polar) with a newly implemented iSPM group to show the impact of iSPM on the ecosystem dynamics in a warming polar fjord (Hornsund, European Arctic) with numerous shallow-grounded marine-terminating glaciers. Our results indicate that with a longer melt season (9 d per decade, 1979–2022), the loss of sea ice cover (44 d per decade, 1982–2021) and the formation of new marine habitats after the retreat of marine-terminating glaciers (around 100 km2 in 1976–2022, a 38 % increase in the total area), glacial meltwater has transported increasing loads of iSPM from land (3.7 g m−3 per decade, reconstructed for 1979–2022). The simulated light limitation induced by the iSPM input delayed and decreased the peaks in phytoplankton, zooplankton, and macrobenthos. The newly ice-free areas still markedly contributed to plankton primary and secondary production and carbon burial in sediments (5.1, 2.0, and 0.9 Gg C yr−1, respectively, on average for 2005–2009 in the iSPM scenario). However, these values would have been 5.0, 2.1, and 0.1 Gg C yr−1 higher, respectively, without the iSPM input. Since carbon burial was the least affected by iSPM (a decrease of around 16 %, in comparison to 50 % for plankton primary and secondary production), the impact of marine ice loss and enhanced land–ocean connectivity should be investigated further in the context of carbon fluxes in expanding polar fjords.

Development of fluid pathways and associated diagenetic variations in a natural CO2 leaking fault zone.

Abstract Permeability within fault zones can vary through time due to repeated deformation events and rock–fluid interactions. Understanding the history of fault zone alteration is critical when building hydrogeologic models and evaluating the risk of mechanical rock failure during subsurface storage. Newly acquired drill core recovered within the fault damage zone and fault core of the Little Grand Wash fault (LGWF) is combined with observations from outcrop, optical petrography, computerized tomography image analysis, and ultrasonic velocity measurements to characterize the rock types and preserved structural deformation features within this fault zone. These data are used to understand the history of mechanical rock failure and mineralization associated with this fluid-charged fault system. We identify multiple structural features and use their cross-cutting relationships to understand the history of deformation and their association with changes in fault zone permeability and rock mechanical properties. At the LGWF zone, structural deformation features vary temporally and are used to recognize a decoupling between fault slip and fluid flow. The formation of most open-mode veins occurred after shear failure within the LGWF zone. Early-developed shear bands are cut by carbonate veins, that are in turn cut by shear fractures, followed by a second phase of vein formation and ultimately by folding in the fault core. This sequence of formation reflects changes in mechanical rock properties due to subsurface rock–fluid interactions and indicates that the alteration of rock matrix by secondary carbonate cement results in increased unconfined compressive strength, decreased permeability, and increased ultrasonic velocity. In this fault zone, and possibly other fault zones, the changes in rock properties associated with deformation can be detected through their geophysical response.

Upcycling waste polymer membranes through eco-friendly solvent-catalysed valorisation for energy and environmental solutions

A facile pathway of upcycling waste/discarded polysulfone (WPSF) membranes has been proposed using deep eutectic solvent (DES) system composed of choline chloride and ethylene glycol (CC:EG) in 1:1 ratio as a green template. This approach offers a viable solution for addressing polymer membrane waste management challenges while simultaneously promoting feasible method, resource efficiency and economic viability. The WPSF was doped with Mn ions prior to the solvothermal conversion at 200 °C and pyrolysis at 900 °C. The obtained functional porous carbon showed superior adsorption capacity towards Malachite green (MG) (423.72 mg/g), Eriochrome black-T (EBT) (326.79 mg/g), Diclofenac (DCF) (195.31 mg/g), and Ofloxacin (OFX) (121.8 mg/g). The adsorption followed pseudo second order kinetics and well agreed with Langmuir isotherm. Further, the optimised carbon material i.e., Mn-WPSF-01 was used as an adsorptive-based membrane water filtration system, in which a remarkable water flux about 965 L.m−2.h−1 for different feed streams with outstanding rejection of >90% even after ten cycles of regeneration was obtained. Therefore, Mn-doped carbon materials integrate the advantages of easy preparation, robustness, and effective adsorption performances, as well as good recyclability. Furthermore, the utilized or secondary carbon materials were used as electrode system in supercapacitors after the pyrolysis, where they displayed a specific capacitance of 110.88 F/g at 0.1 A/g of current density with capacity retention 90.85% for about 20,000 cycles with a current density increased to 5 A/g. Therefore, this approach promises to recycle the WPSF via potential applications in water treatment and energy applications through greener way.

Site-selective α-C(sp3)-H arylation of dialkylamines via hydrogen atom transfer catalysis-enabled radical aryl migration.

Site-selective C(sp3)-H arylation is an appealing strategy to synthesize complex arene structures but remains a challenge facing synthetic chemists. Here we report the use of photoredox-mediated hydrogen atom transfer (HAT) catalysis to accomplish the site-selective α-C(sp3)-H arylation of dialkylamine-derived ureas through 1,4-radical aryl migration, by which a wide array of benzylamine motifs can be incorporated to the medicinally relevant systems in the late-stage installation steps. In contrast to previous efforts, this C-H arylation protocol exhibits specific site-selectivity, proforming predominantly on sterically more-hindered secondary and tertiary α-amino carbon centers, while the C-H functionalization of sterically less-hindered N-methyl group can be effectively circumvented in most cases. Moreover, a diverse range of multi-substituted piperidine derivatives can be obtained with excellent diastereoselectivity. Mechanistic and computational studies demonstrate that the rate-determining step for methylene C-H arylation is the initial H atom abstraction, whereas the radical ipso cyclization step bears the highest energy barrier for N-methyl functionalization. The relatively lower activation free energies for secondary and tertiary α-amino C-H arylation compared with the functionalization of methylic C-H bond lead to the exceptional site-selectivity.