Search Results (177)

Within a waste biorefinery framework, integrating agro-industrial by-products into the circular economy requires a detailed understanding of the thermochemical conversion behaviour of low-grade carbonaceous materials. This study evaluates the co-pyrolysis characteristics of Soma lignite (SL) and pectin-rich sugar beet pulp (SBP) as a sustainable route for upgrading these resources into clean energy carriers. Interactions between the two feedstocks were analysed by thermogravimetric measurements, triple-region kinetic modelling, and quantitative synergy indices at six mixing ratios, including the pure samples (100:0, 80:20, 60:40, 40:60, 20:80, and 0:100 wt% SL:SBP). The Reactivity Index ($R_{\mathrm{m}}$) increased from 0.97 × 10⁻⁴ s⁻¹K⁻¹ for pure SL to 8.65 × 10⁻⁴ s⁻¹K⁻¹ for the 20:80 blend, showing that SBP acts as a highly reactive biomass component that accelerates devolatilisation in the main pyrolysis region. Synergy analysis indicated a shift from inhibitory behaviour in coal-rich blends to slightly positive synergy in SBP-rich mixtures, with the onset of positive $\Delta TC$ around 60 wt% SBP under the present single-heating-rate, non-replicated TGA conditions. This tentative threshold-like behaviour suggests that a critical level of literature-supported, hypothesised hydrogen-donating biomass radicals may be required to overcome the structural resistance of the coal matrix. Within these experimental limitations, the apparent macro-kinetic deviations and first-order Arrhenius parameters suggest that SL/SBP co-pyrolysis follows a complex, non-additive pathway that should be further validated by multi-heating-rate and product characterisation studies in future work. The primary contribution of this work lies in proposing this distinct threshold-like biomass fraction at the macro-kinetic level that governs the transition from heat-transfer-limited antagonism to radical-influenced synergy in low-rank coal and pectin-rich biomass blends. Overall, the combined $\Delta TC$, $\Delta E$ and $R_{\mathrm{m}}$ descriptors provide useful macro-kinetic benchmarks for guiding the optimisation of thermochemical processes for low-grade carbonaceous resources. Full article

In situ hydrogen generation can extend in situ combustion (ISC) by converting part of the heavy oil in place into H₂-containing gas while allowing part of the carbonaceous products to remain in the reservoir. To clarify how operating conditions affect hydrogen behavior, this study recalibrated key Arrhenius parameters in a pseudo-component kinetic network through least-squares-guided manual history matching against high-temperature/high-pressure (HTHP) reactor data obtained under three gas atmospheres (air, N₂, and CO₂). Model performance was evaluated through a direct comparison between raw simulator predictions and measured gas compositions using parity plots with a 1:1 reference line and residual-based statistics calculated from the simulated values rather than from regression-fitted values. The calibrated model was then used to compare hydrogen responses over 150–425 °C, 4–8 MPa, and 0.25–10 days. Within the tested range, three temperature regimes were identified: initiation (150–250 °C), pyrolysis-controlled (250–325 °C), and high-yield (325–425 °C). Oxygen and CO₂ generally reduced net hydrogen accumulation through competing pathways, whereas an inert N₂ background produced the highest H₂ fraction, reaching 28.6 vol% at 425 °C and 6 MPa after 10 days. These results provide a reactor-scale basis for selecting favorable operating windows and for subsequent reservoir-scale evaluation of in situ hydrogen generation under ISC conditions. Full article

This study investigates the feasibility of producing an Fe-Cr-Mn complex alloy through the recycling of technogenic wastes from metallurgical operations. The feed materials comprised chromium-bearing dust collected from the gas-cleaning system of high-carbon ferrochrome production, iron–manganese ore fines (<10 mm) from the Tur deposit (Kazakhstan), and coal sludge used as a carbonaceous reducing agent. Thermodynamic modeling of the carbothermic reduction of Cr and Mn oxides and the predicted distribution of components among the metal, slag, and gas phases were performed using the HSC Chemistry 10 software package over a high-temperature range. At 1800 °C, the calculated chemical composition of the target alloy was as follows (wt.%): Cr-35.84, Mn-24.47, Si-16.25, Fe-22.63, and C-0.82. To validate the modeling results, experimental smelting trials were carried out in a 100 kVA electric arc furnace, producing both metallic and slag phases. The average composition of the metal phase was (wt.%): Cr-37.17, Mn-14.46, Si-11.48, Fe-33.23, C-3.48, P-0.15, and S-0.021. The experimental results indicate the formation of a Cr-Mn alloy with elevated Cr and Fe contents and a noticeable C level, confirming the carbothermic nature of the reduction reactions. The composition and microstructural features of the smelting products were examined by scanning electron microscopy coupled with energy-dispersive spectroscopy (SEM/EDS). The findings demonstrate that the combined use of technogenic raw materials and a carbonaceous reductant enables the production of a Cr- and Mn-enriched metallic phase under satisfactory slag-forming conditions. Overall, the results confirm the potential of a resource-saving approach for valorizing fine technogenic wastes in the production of complex ferroalloys and for improving the recovery of target elements through optimization of the charge composition and smelting parameters. Full article

Amidst rapid urbanization, fine particulate matter (PM_2.5) has emerged as a critical environmental challenge in China, posing substantial health risks due to its complex composition and diverse sources. This study provides a seasonally resolved analysis of PM_2.5 composition and multi-faceted toxicity in Hefei, a major Chinese manufacturing center. PM_2.5 samples collected across four seasons were chemically characterized for water-soluble ions, carbonaceous components, metals, and polycyclic aromatic hydrocarbons (PAHs) and derivatives. Their toxicological effects were evaluated through oxidative potential (OP), cytotoxicity, and reactive oxygen species (ROS) generation in the human bronchial epithelial cell line BEAS-2B. The results reveal significant seasonal variations in PM_2.5 concentration and composition. Winter exhibited the highest PM_2.5 levels (68.31 ± 17.12 μg/m³), with enrichment of secondary inorganic aerosols (SIAs), toxic metals (Pb, Cd, As), and high-molecular-weight PAHs. Spring showed elevated crustal elements (Al, Fe, Mn), while summer had the lowest pollutant concentrations. Toxicity assays reflected the following patterns: winter PM_2.5 demonstrated the highest OP (0.1423 ± 0.0368 nmol DTT/min/μg), strongest cytotoxicity (51.85% cell viability), and greatest ROS induction (2.28-fold increase). Statistical analyses identified distinct toxicity drivers: OP was associated with SIA (NO₃⁻, NH₄⁺) and redox-active metals (Cu, Zn); cytotoxicity correlated with toxic metals and PAHs; whereas ROS showed weaker compositional correlations. This integrated “composition–toxicity” assessment reveals that the elevated health risk in winter stems from a synergistic mix of secondary aerosols and combustion-derived toxicants, urging a shift toward component-specific, risk-based air quality management strategies. Full article

Porous ceramic oxides have gained significant interest as components in a wide variety of energy storage devices. Their use, however, is limited by long and high-temperature processing methods. We recently demonstrated Porogen-integrated Rapid Oxidation (PiRO) as a new method to manufacture porous aluminum oxide in significantly shorter times and with substantial manufacturing cost savings, but challenges remain with the resultant porous matrices. First, carbonaceous residue remains in the films after the combustion event, which is necessary to minimize for electronic applications. Second, the porous structure is not stable at elevated temperatures (>250 °C), which are often required for nanocomposite applications of the matrices where filling with a second phase is achieved through high-temperature annealing. Here, we address these challenges by using post-processing treatments, including UV/Ozone, high-temperature nitrogen oven anneals, and oxygen plasma. First, we characterize the treatments’ efficacy in carbon removal using FTIR and measure bulk carbon removal with XPS. Second, we characterize the matrices’ thickness collapse and porosity changes after treatments with ellipsometry. Finally, we use nanoindentation to understand changes in stiffness resulting from the various treatments. By understanding the treatments’ roles in removing carbon from the films and stabilizing the matrix structure, we are able to select optimal post-processing treatments for designing a stable platform for further applications of the mesoporous oxide. Full article

Seasonal fluctuations in the chemical composition of fine particulate matter (PM_2.5) are known to influence its toxicological properties; however, their integrated biological effects remain incompletely understood. In this study, PM_2.5 was continuously collected over two consecutive years at a single urban site in Japan and classified by season. The samples were comprehensively characterized for ionic species, metals, carbonaceous fractions, and polycyclic aromatic hydrocarbons (PAHs), and their pulmonary effects were evaluated in vivo following intratracheal administration in mice. Seasonal PM_2.5 exhibited pronounced compositional differences, with higher levels of secondary inorganic aerosol components in summer and enrichment of PAHs and mineral-associated components in winter. These seasonal differences translated into distinct biological responses. Reactive oxygen species (ROS) production (1.6–2.7-fold increase) and bronchoalveolar lavage (BAL) neutrophil infiltration were strongly associated with PAH-rich PM_2.5, whereas interleukin-1α (IL-1α) showed robust positive correlations with mineral components, including K⁺, Ca²⁺, and Mg²⁺, which were predominantly enriched in winter PM_2.5. In contrast, secondary inorganic aerosol species displayed a limited capacity to induce IL-1α. Compared with summer samples, winter PM_2.5 induced significantly higher levels of ROS production and IL-1α (approximately 1.5–2.6-fold increase). Using TLR2- and TLR4-deficient mice, we further demonstrated that PM_2.5-induced increases in BAL cell counts, ROS, IL-6, and TNF-α were partially attenuated in TLR4 knockout mice, indicating a contributory but not exclusive role for TLR4 signaling in PM_2.5-driven pulmonary inflammation. Collectively, these findings demonstrate that seasonal variations in PM_2.5 composition, not particle mass alone, critically shape oxidative stress and innate immune responses in the lungs. In particular, winter PM_2.5 enriched in mineral-associated components preferentially activates IL-1α-mediated alarmin pathways, underscoring the importance of the particle composition in determining seasonal air pollution toxicity. Full article

This study examines the structural, chemical, and thermal properties of biochars from slow pyrolysis of hardwood (HW), corn cob (CC), and wheat straw (WS) at 400 °C and 700 °C, evaluating their potential in environmental and industrial applications. A combination of spectroscopic, crystallographic, thermal, and microscopic techniques was employed to monitor the degradation of biomass components and the development of the carbonaceous matrix. The results show that pyrolysis temperature has a significant impact on the properties of biochar. Higher temperatures (700 °C) increased the pH (up to 10.3 for WS700), the carbon content (e.g., 89.8% for HW700), the ash content (up to 24.8% for WS700), and the specific surface area (e.g., 306.87 m²/g for CC700) while decreasing polar functional groups and volatile matter (as confirmed by FTIR). SEM showed enhanced porosity at 700 °C, which was supported by BET analysis. XRD and Raman showed increased graphitization and structural order with temperature, especially for HW and CC biochars, while WS biochars retained mineral components like SiO₂ and CaCO₃. TGA analysis showed improved thermal stability at 700 °C only for biochar derived from wheat straw, while HW and CC biochars showed similar total mass loss regardless of pyrolysis temperature. These biochars exhibit high potential for soil remediation (high pH), water purification (large surface area), and carbon storage (high aromaticity), with HW700 and CC700 also suitable for high-temperature industrial applications due to their stability. Full article

This study, based on global AERONET observation data from 2023, employs a synergistic inversion algorithm that integrates aerosol optical, microphysical, and chemical properties to retrieve the global distribution of aerosol parameters. We find that the global annual mean aerosol optical depth (AOD), fine-mode AOD (AOD_f), coarse-mode AOD (AOD_c), absorbing aerosol optical depth (AAOD), single scattering albedo (SSA) are 0.20, 0.15, 0.04, 0.024, and 0.87, respectively. From the perspective of spatial distribution, in densely populated urban areas, AOD is mainly determined by AOD_f, while in the areas dominated by natural sources, AOD_c contributes more. Combined with the optical and microphysical properties, fine-mode aerosols dominate optical contributions, whereas coarse-mode aerosols dominate volume contributions. In terms of chemical components, fine-mode aerosols at most global sites are primarily carbonaceous. The mass concentrations of black carbon (BC) exceed 10 mg m⁻² in parts of South Asia, Southeast Asia, and the Arabian Peninsula, while the mass fraction of brown carbon (BrC) accounts for more than 16% in regions such as the Sahara, Western Africa, and the North Atlantic Ocean reference areas. The dust (DU) dominates in coarse mode, with the annual mean DU fraction reaching 86.07% in the Sahara. In coastal and humid regions, the sea salt (SS) and water content (AW_c) contribute significantly to the aerosol mass, with fractions reaching 13.13% and 34.39%. The comparison of aerosol properties in the hemispheres reveals that the aerosol loading in the Northern Hemisphere caused by human activities is higher than in the Southern Hemisphere, and the absorption properties are also stronger. We also find that the uneven distribution of global observation sites leads to a significant underestimation of aerosol absorption and coarse-mode features in global mean values, highlighting the adverse impact of observational imbalance on the assessment of global aerosol properties. By combining analyses of aerosol optical, microphysical, and chemical properties, our study offers a quantitative foundation for understanding the spatiotemporal distribution of global aerosols and their emission contributions, providing valuable insights for climate change assessment and air quality research. Full article

Carbonaceous aerosols represent a significant component of atmospheric aerosol, with implications for climate and human health. The recent EU Directive 2024/2881 highlights the need to monitor emerging pollutants like black carbon more effectively. This study presents an brief field campaign at an urban background site aimed at characterizing carbonaceous aerosols. Daily samples of PM₁₀ and PM_2.5 were analyzed using a Sunset thermal-optical analyzer to determine organic and elemental carbon (OC, EC), while real-time equivalent black carbon (eBC) was measured with three independent instruments: MAAP, AE33, and Giano BC1. Total carbon (TC) was monitored using an online TCA08 thermo-catalytic analyzer. The average concentration of PM₁₀ was 17.1 µg/m³ and 10.4 µg/m³ for PM_2.5. On average, OC and EC represented 16.5% and 3.6% of PM₁₀ mass, and 22.6% and 5.5% of PM_2.5. SOC accounted for 36% of OC. The in situ Mass Absorption Cross-section (MAC), recalculated for the ECO site, was between 8.0 and 12.2 m²/g. eBC concentrations were modulated by the daily evolution of the planetary boundary-layer height and combustion sources. The apportionment of eBC was 65% from fossil fuel and 35% from biomass burning. Biomass-burning emissions were further confirmed by optical measurements, with BrC contributing 35% of absorption at 370 nm. Full article

High-temperature proton exchange membrane fuel cells (HT-PEMFCs) offer distinct advantages over their low-temperature counterparts. However, their commercial viability is significantly hampered by durability challenges stemming from electrocatalyst support degradation in the corrosive phosphoric acid environment. This review provides a comprehensive analysis of advanced strategies to overcome this critical durability issue. Two main research directions are explored. The first involves engineering more robust carbon-based materials, including graphitized carbons, carbon nanostructures (nanotubes and graphene), and heteroatom-doped carbons, which enhance stability by modifying the carbon’s intrinsic structure and surface chemistry. The second direction focuses on replacing carbon entirely with intrinsically stable non-carbonaceous materials. These include metal oxides (e.g., TiO₂, SnO₂), transition metal carbides (e.g., WC, TiC), and nitrides (e.g., Nb₄N₅). For these non-carbon materials, a key focus is on overcoming their typically low electronic conductivity through strategies such as doping and the formation of multi-component composites. The analysis benchmarks the performance and durability of these advanced supports, concluding that rationally designed composite materials, which combine the strengths of different material classes, represent the most promising path toward developing next-generation, long-lasting catalysts for HT-PEMFCs. Full article

The health impacts of atmospheric fine particulate matter (PM_2.5) in plateau regions have attracted concerns, along with local population growth and rapid urbanization. This study collected PM_2.5 samples at summer and winter in Xining, a city located in the northeastern Tibetan Plateau. The chemical composition of PM_2.5 and its cytotoxicity on human lung epithelial cells (A549) are characterized, and composition–cytotoxicity correlation is discussed. The toxic mechanisms of PM_2.5 in different seasons were further investigated through metabolomic analysis using high-resolution mass spectrometry. The average PM_2.5 mass concentration in Xining during winter was 2.10 times higher than that during summer. The carbonaceous components in PM_2.5 were dominated by OC, while the main water-soluble ions were SO₄²⁻, NO₃⁻, and NH₄⁺, with Mg, Al, Fe, and Ca also present in high concentrations in metal elements. LDH and ROS emerged as the most PM_2.5-affected toxicity indices in summer (34.59 ± 4.86 ng/L, 1.19× control) and winter (8.62 ± 1.25 ng/mL, 1.77× control), respectively. OC, Cl⁻, F⁻, Sn, Cr, SO₄²⁻, Pb, Zn, Mg, NO₃⁻, and NH₄⁺ may synergistically exacerbate oxidative stress and inflammatory responses on A549 cells in Xining. Furthermore, glutathione metabolism, amino acid metabolism, and sphingolipid metabolism were identified as key pathways influencing cellular oxidation and inflammation. Thimonacic, 9-(2,3-dihydroxypropoxy)-9-oxononanoic acid, and hypoxanthine were common metabolites in both seasons. Our findings greatly enhance the understanding of health risks associated with PM_2.5 in the plateau city. Full article

In this study, a correlative approach using Raman spectroscopy and scanning electron microscopy (SEM) is introduced to meet the challenges of identifying impurities, especially carbon-related compounds in metal injection-molded (MIM) Mg-0.6Ca specimens designed for biomedical applications. This study addresses, for the first time, the issue of carbon residuals in the binder-based powder metallurgy (PM) processing of Mg-0.6Ca materials. A deeper understanding of the material microstructure is important to assess the microstructure homogeneity at submicron levels as this later affects material degradation and biocompatibility behavior. Both spectroscopic and microscopic techniques used in this study respond to the concerns of secondary phase distributions and their possible stoichiometry. Our micro-Raman measurements performed over a large area reveal Raman modes at ~1370 cm⁻¹ and ~1560 cm⁻¹, which are ascribed to the elemental carbon, and at ~1865 cm⁻¹, related to C≡C stretching modes. Our study found that these carbonaceous residuals/contaminations in the material microstructure originated from the polymeric binder components used in the MIM fabrication route, which then react with the base material components, including impurities, at elevated thermal debinding and sintering temperatures. Additionally, using evidence from the literature on thermal carbon cracking, the presence of both free carbon and calcium carbide phases is inferred in the sintered Mg-0.6Ca material in addition to the Mg₂Ca, oxide, and silicate phases. This first-of-its-kind correlative characterization approach for PM-processed Mg biomaterials is fast, non-destructive, and provides deeper knowledge on the formed residual carbonaceous phases. This is crucial in Mg alloy development strategies to ensure reproducible in vitro degradation and cell adhesion characteristics for the next generation of biocompatible magnesium materials. Full article

Atmospheric aerosols are recognized as a major air pollutant with significant impacts on human health, air quality, and climate. Yet, the chemical composition and seasonal variability of aerosols remain underexplored in several Western Mediterranean regions. This study presents a year-long investigation of PM_2.5 and PM₁₀ in Tetouan, Northern Morocco, where both local emissions and regional transport influence air quality. PM_2.5 and PM₁₀ samples were collected and analysed for total mass and comprehensive chemical characterization, including organic carbon (OC), elemental carbon (EC), water-soluble ions (WSIs), and sugar tracers (levoglucosan, arabitol, and glucose). Concentration-weighted trajectory (CWT) modelling and air mass back-trajectory analyses were used to assess potential source regions and transport pathways. PM_2.5 concentrations ranged from 4.2 to 41.8 µg m⁻³ (annual mean: 18.0 ± 6.4 µg m⁻³), while PM₁₀ ranged from 11.9 to 66.3 µg m⁻³ (annual mean: 30.8 ± 9.7 µg m⁻³), with peaks in winter and minima in spring. The PM_2.5-to-PM₁₀ ratio averaged 0.59, indicating a substantial accumulation of particle mass within the fine fraction, especially during the cold season. Carbonaceous aerosols dominated the fine fraction, with total carbonaceous aerosol (TCA) contributing ~52% to PM_2.5 and ~34% to PM₁₀. Secondary organic carbon (SOC) accounted for up to 90% of OC in PM_2.5, reaching 7.3 ± 3.4 µg m⁻³ in winter. WSIs comprised ~39% of PM_2.5 mass, with sulfate, nitrate, and ammonium as major components, peaking in summer. Sugar tracers exhibited coarse-mode dominance, reflecting biomass burning and biogenic activity. Concentration-weighted trajectory and back-trajectory analyses identified the Mediterranean Basin and Iberian Peninsula as dominant source regions, in addition to local urban emissions. Overall, this study attempts to fill a critical knowledge gap in Southwestern Mediterranean aerosol research by providing a comprehensive characterization of PM_2.5 and PM₁₀ chemical composition and their seasonal dynamics in Tetouan. It further offers new insights into how a combination of local emissions and regional transport shapes the aerosol composition in this North African urban environment. Full article

Carbonaceous aerosols exert significant impacts on human health and climate systems. This study investigates the seasonal variations of carbonaceous components in fine particulate matter (PM_2.5) in Qinhuangdao, a coastal city in northern China, throughout 2023. The mass concentrations of organic carbon (OC) and elemental carbon (EC) averaged 9.44 ± 4.57 μg m⁻³ and 0.84 ± 0.33 μg m⁻³, contributing 26.49 ± 8.74% and 2.81 ± 1.56% to total PM_2.5, respectively. OC exhibited a distinct seasonal trend: winter (12.02 μg m⁻³) > spring (11.96 μg m⁻³) > autumn (8.15 μg m⁻³) > summer (5.71 μg m⁻³), whereas EC followed winter (1.31 μg m⁻³) > autumn (0.73 μg m⁻³) > spring (0.70 μg m⁻³) > summer (0.63 μg m⁻³). Both OC and EC levels were elevated at night compared to daytime. Secondary organic carbon (SOC), estimated via the EC-tractor method, constituted 37.94 ± 14.26% of total OC. A positive correlation between SOC/OC ratios and PM_2.5 concentrations suggests that SOC formation critically influences haze events. In autumn and winter, SOC formation was higher at night, likely driven by aqueous-phase reactions, whereas in summer SOC formation was more pronounced during the day, likely due to enhanced photochemical reactions. Source apportionment analysis revealed that gasoline and diesel vehicles were major contributors to carbonaceous aerosols, accounting for 27.35–29.06% and 14.97–31.83%, respectively. Coal combustion contributed less (10.51–21.55%), potentially due to strict regulations prohibiting raw coal use for domestic heating in surrounding regions. Additionally, fugitive dust was found to have a high contribution to carbonaceous aerosols during spring and summer. Full article

This mini-review emphasizes the potential of biomass-derived materials as sustainable components for next-generation electrochemical energy storage systems. Biomass obtained from abundant and renewable natural resources can be transformed into carbonaceous materials. These materials typically possess hierarchical porosities, adjustable surface functionalities, and inherent heteroatom doping. These physical and chemical characteristics provide the structural and chemical flexibility needed for various electrochemical applications. Additionally, biomass-derived materials offer a cost-effective and eco-friendly alternative to traditional components, promoting green chemistry and circular resource utilization. This review provides a systematic overview of synthesis methods, structural design strategies, and material engineering approaches for their use in lithium-ion batteries (LIBs), lithium–sulfur batteries (LSBs), and supercapacitors (SCs). It also highlights key challenges in these systems, such as the severe volume expansion of anode materials in LIBs and the shuttle effect in LSBs and discusses how biomass-derived carbon can help address these issues. Full article