Search Results (568)

The role of soil microbial communities in soil organic matter (OM) decomposition, transformation, and the global nitrogen (N) and carbon (C) cycles has been widely investigated. However, a comprehensive understanding of how specific agricultural practices and OM inputs shape microbial-driven processes across different European pedoclimatic conditions is still lacking, particularly regarding their effectiveness in mitigating greenhouse gas (GHG) emissions. This systematic review synthesizes current knowledge on the biotic mechanisms underlying soil C sequestration and GHG reduction, emphasizing key microbial processes influenced by land management practices. A rigorous selection was applied, resulting in 16 eligible articles that addressed the targeted outcomes: soil microorganism biodiversity, including microbiome composition and other common Biodiversity Indexes, C sequestration and non-CO₂ GHG emissions (namely N₂O and CH₄ emissions), and N leaching. The review highlights that, despite some variations across studies, the application of OM enhances soil microbial biomass (MB) and activity, boosts soil organic carbon (SOC), and potentially reduces emissions. Notably, plant richness and diversity emerged as critical factors in reducing N₂O emissions and promoting carbon storage. However, the lack of methodological standardization across studies hinders meaningful comparison of outcomes—a key challenge identified in this review. The analysis reveals that studies examining the simultaneous effects of agricultural management practices and OM inputs on soil microorganisms, non-CO₂ GHG emissions, and SOC are scarce. Standardized studies across Europe’s diverse pedoclimatic regions would be valuable for assessing the benefits of OM inputs in agricultural soils. This would enable the identification of region-specific solutions that enhance soil health, prevent degradation, and support sustainable and productive farming systems. Full article

The continuous tightening of emission regulations and the escalating costs of palladium (Pd) and rhodium (Rh) have renewed interest in platinum (Pt)-based three-way catalysts (TWCs) as cost-effective alternatives for gasoline aftertreatment. However, despite extensive studies on Pt/CeO₂ and Pt/Ba-based formulations, the cooperative roles of Ba and Ce and, in particular, the fundamental influence of the Ba/Ce ratio on oxygen mobility, NO_x storage behavior, and Pt–support interactions remain poorly understood. In this work, we address this gap by systematically tuning the Ba/Ce molar ratio in a series of Pt–Ba–Ce/Al₂O₃ catalysts prepared from Ba(CH₃COO)₂ and CeO₂ precursors, and evaluating their structure–function relationships in both fresh and hydrothermally aged states. Through comprehensive characterization (N₂ physisorption, XRD, XPS, H₂-TPR, NO_x-TPD, SEM, CO pulse adsorption, and dynamic light-off testing), we establish previously unrecognized correlations between Ba/Ce ratio–dependent structural evolution and TWC performance. The results reveal that the Ba/Ce ratio exerts a decisive control over catalyst textural properties, Pt dispersion, and interfacial Pt–CeO₂ oxygen species. Low Ba/Ce ratios uniquely promote Pt–Ce interfacial oxygen and O₂ spillover—providing a new mechanistic basis for enhanced low-temperature oxidation and reduction reactions—while higher Ba loading selectively drives BaCO₃ formation and boosts NO_x storage capacity. A clear volcano-type dependence of NO_x storage on the Ba/Ce ratio is demonstrated for the first time. Hydrothermal aging at 850 °C induces PtO_x decomposition, BaCO₃–Al₂O₃ solid-state reactions forming inactive BaAl₂O₄, and Pt sintering, collectively suppressing Pt–Ce interactions and reducing TWC activity. Importantly, an optimized Ba/Ce ratio is shown to mitigate these degradation pathways, offering a new design principle for thermally durable Pt-based TWCs. Overall, this study provides new mechanistic insight into Ba–Ce cooperative effects, establishes the Ba/Ce ratio as a critical and previously overlooked parameter governing Pt–support interactions and NO_x storage, and presents a rational strategy for designing cost-effective, hydrothermally robust Pt-based alternatives to Pd/Rh commercial TWCs. Full article

Forest fine root litter enters agricultural soils in some cases and its decomposition would change the soil’s properties. However, how this process further influences the ammonia (NH₃) volatilization and nitrous oxide (N₂O) emission from agricultural soil receiving fertilizer nitrogen (N) is unknown. Here, we conducted a soil pot experiment to investigate the responses of the aforementioned gaseous N losses during wheat season to fine root litters derived from Populus deltoides (RP) and Metasequoia glyptostroboides (RM) incorporations. The results showed that two forest fine root litters reduced total NH₃ losses by 30.6−31.9% from 180 kg N ha⁻¹ applied to farmland soil, and this effect was attributed to decreased soil urease activity and ammonium-N during the basal N fertilization period. Whether receiving fertilizer N or not, N₂O emissions from farmland soil were significantly (p < 0.05) mitigated by 62.8–68.2% and 43.0−50.0% following the RP and RM incorporation, respectively. Lower N₂O emission was ascribed to increased soil pH but decreased soil nitrate-N and bulk density. In addition, less AOA and AOB amoA but more nosZ gene abundances explained the fine root litter-induced N₂O mitigation effect. Neither forest fine root litter exerted a negative effect on wheat grain yield and crop N use efficiency in N-added agriculture soil. In conclusion, forest fine root litter incorporation could help to mitigate gaseous N losses via NH₃ volatilization and N₂O emission from fertilizer-N-applied agricultural soils, and without crop production loss. Full article

Single-season legume green manuring is widely promoted for soil fertility restoration in degraded agricultural lands, yet its effectiveness in alkaline semi-arid soils remains poorly understood. This study investigated the impact of first-year sweet clover (Melilotus officinalis (L.)) green manuring on soil microbiome structure and agrochemical properties in southern carbonate chernozem soils of Northern Kazakhstan. Using shotgun metagenomics, we analyzed microbial communities from sweet clover-amended soils, clean fallow, and virgin steppe reference sites. Contrary to expectations, sweet clover green manuring did not enhance soil nitrogen availability, with nitrate-N content (9.1 mg/kg) remaining lower than clean fallow (10.5 mg/kg), likely due to temporary immobilization during initial decomposition. While sweet clover significantly increased archaeal diversity (p = 0.01) and enriched nitrogen-cycling taxa, including Nitrospirae and Thaumarchaeota, overall microbial richness remained unchanged (ACE index, p > 0.05). Surprisingly, functional analysis revealed only five significant metabolic differences between sweet clover and fallow systems, indicating functional convergence of agricultural microbiomes regardless of management practice. Correlation analysis identified phosphorus as the master regulator of microbial metabolism (r = 1.0, p < 0.0001), while elevated pH (9.0), K₂O (>1000 mg/kg), and $\mathrm{N}{\mathrm{O}}_3^{-}$ showed strong negative correlations with essential metabolic pathways, revealing previously unrecognized nutrient toxicity thresholds. Virgin steppe maintained 69 unique metabolic pathways lost in agricultural systems, highlighting the ecological cost of cultivation. These findings demonstrate that sweet clover green manuring in alkaline steppe soils induces selective rather than comprehensive microbiome restructuring, with limited immediate benefits for soil fertility. This study provides critical insights for developing sustainable agricultural practices in the world’s extensive semi-arid regions facing similar edaphic constraints. Full article

Activated carbon has shown good catalytic performance in water treatment, but its wide application is limited by its high price. Activated coke exhibits functional groups and is low-cost. However, there is limited research on activated coke as a catalyst. In our previous study, powdered activated coke (PAC) exhibited good catalytic performance in NH₃-N treatment with ozonation. Increasing nitrogen selectivity is the key to harmless degradation of NH₃-N, which has received little attention. In this paper, manganese-loaded powdered coke (Mn–PAC) was prepared, aiming to further improve the nitrogen selectivity. Under the same conditions, the PAC/O₃ system achieved 92.16% NH₃-N removal and 49.46% nitrogen selectivity, while the Mn–PAC/O₃ system achieved almost 100% NH₃-N removal and 79.31% N₂ selectivity. When Mn–PAC was reused for the sixth time, the system achieved about 70% and 46% NH₃-N removal and N₂ selectivity, both of which were about 10% higher than those of PAC. Complex redox and synergistic interactions existed in the Mn–PAC/O₃ system. The Mn–PAC surface contains reactive sites such as C=C, C=O, π–π bonds, ArOH, and various MnO_x. These components collectively facilitate ozone decomposition into ·OH, ·O₂⁻, and ¹O₂. The ¹O₂ may play a significant role in converting NH₃-N to N₂. Full article

The strategic engineering of metal–organic frameworks (MOFs) through integration with clay minerals offers a promising route to tailor their functional properties and expand their application scope. In this study, a series of clay-MOF composites was constructed by introducing MOFs onto the surfaces of different clay minerals. By varying the type of clay mineral, the nature and strength of surface-active sites could be effectively modulated. Notably, the Kaolinite-based MOFs (Ka-MOF) composite exhibited superior sensitivity for the detection of aspartic acid (AA), outperforming other composite nanozymes using o-phenylenediamine (OPD) and hydrogen peroxide (H₂O₂) as substrates, with a linear detection range of 0–37.56 μM and a low detection limit of 55.7 nM. The enhanced peroxidase-like activity is attributed to the substitution of silicon in the kaolinite structure by MOF components, which increases the density of Lewis acid–base sites. These sites facilitate H₂O₂ adsorption and promote its decomposition to generate singlet oxygen (¹O₂), thereby enhancing the catalytic oxidation process. Furthermore, the probe yielded satisfactory recoveries of aspartic acid (94.2% to 98.5%) in different real water samples through spiking recovery experiments. This work not only elucidates the influence of crystal surface engineering on the optical and catalytic properties of nanozymes but also provides a robust platform for tracing amino acids and studying their environmental chemical behaviors. Full article

Polymer matrix composites (PMCs) have been prepared having a polyethersulfone (PES) matrix loaded with polytetrafluoroethylene (PTFE) particles coated with negative thermal expansion zirconium tungstate (ZT) with an aim to reduce the thermal mismatch stresses at the PES/PTFE interfaces and, thus, reduce wear rate when sliding against a ball bearing AISI 52100 steel counterpart at elevated temperatures. The zirconium tungsten particles were synthesized using thermal decomposition from hydrothermally prepared precursors. The PMCs have been obtained using compression molding at 370 °C and contained, according to XRD, only the hexagonal α-ZrW₂O₈ phase. Wear testing was carried out at 25, 120, and 180 °C using a ball-on-disk scheme at 5 N and 0.3 m/s. The resulting wear tracks’ radial profiles were registered by means of profilometry, which was then used for calculating the wear rate. It was shown that both wear rate and friction reduced in testing the PES/PTFE/ZT samples at 180 °C compared to those of PES/PTFE containing only neat PTFE particles. Wear mechanism transitions have been observed from low-temperature generation of the tribological layer by the PTFE smearing to flow and abrasion wear at high temperatures. Full article

This paper reports an assessment of the photocatalytic activity of TiO₂ nanotubes (TNTs) doped with strontium titanate (SrTiO₃) and sulfur (S) with respect to the decomposition of methylene blue (MB). TNT was obtained by the double anodizing method with further doping of strontium titanate by the hydrothermal method and additional annealing in an atmosphere of N₂ (95%) + H₂S (5%) at 450–550 °C. The photocatalytic activity was evaluated using MB as a pollutant and this study was conducted using an Osram Vita-Lux lamp with a power of 300W as a visible light source. The photocatalytic abilities of the synthesized materials were investigated, and characterized by methods such as SEM, TEM, XRD, EDS, and UV–Vis spectroscopy. Our study showed that the SrTiO₃/TiO₂NT@S composite has a better photocatalytic decomposition ability for the dye under consideration compared to pure TNT and SrTiO₃/TiO₂NT. These results clearly demonstrate the potential of synthesized SrTiO₃/TiO₂NT@S material for applications in water purification and photocatalysis. Full article

The photocatalytic reduction of CO₂ in aqueous media offers a sustainable route for solar-to-fuel conversion, yet remains challenged by CO₂’s thermodynamic stability and kinetic inertness, low solubility, and competitive hydrogen evolution. Here, we investigate the interplay between ionic liquids (ILs), photocatalyst supports, and additive composition in directing product selectivity among CO, CH₄, and H₂. Using imidazolium acetate as a benchmark, we demonstrate that ILs not only pre-activate CO₂ but can also undergo decomposition pathways under illumination, notably Kolbe-type reactions leading to methane formation from acetate rather than from CO₂. Comparative studies of Pd-decorated TiO₂ and g-C₃N₄ nanosheets reveal distinct behaviors driven by their interfacial interactions with the imidazolim-based ionic liquid: weak interaction with TiO₂ strongly promotes hydrogen evolution, whereas strong coupling with g-C₃N₄ synergizes with C₁C₄ImOAc to trigger acetate-derived Kolbe reactivity. The systematic evaluation of alternative salts confirms the determinant role of anion basicity and medium-pH-basic anions facilitate CO₂ activation, whereas weakly basic or non-coordinating anions favor water splitting. Overall, these results clarify the dual role of ionic liquids as both CO₂ activators and sacrificial agents, and highlight design principles for improving product selectivity and efficiency in aqueous CO₂ photoreduction systems. Full article

In this study, we report the preparation of platinum nanoparticles (Pt NPs) deposited on HTiNbO₅ and the application of the resultant material in the catalytic decomposition of sodium borohydride (NaBH₄) to generate hydrogen. The starting material, KTiNbO₅, was prepared through a solid-state process involving Nb₂O₅, K₂CO₃, and TiO₂. The subsequent treatment with HNO₃ resulted in the exchange of potassium by protons, rendering HTiNbO₅. This material served as support for Pt nanoparticles (3.6 ± 0.7 nm), producing Pt NPs/HTiNbO₅. All compounds were characterized using TGA, FTIR, XRD, Raman, SEM-EDS, and HRTEM. The influence of different factors on the reaction kinetics was evaluated, resulting in a hydrogen generation rate (HGR) of 22,790.18 $\mathrm{m}\mathrm{L} {\mathrm{m}\mathrm{i}\mathrm{n}}^{-1}{\mathrm{g}}_{\mathrm{c}\mathrm{a}\mathrm{t}}^{-1}$ at 50 °C. The activation energy (41.83 kJ mol⁻¹) was also determined. A mechanistic study with deuterated water revealed a kinetic isotopic effect (KIE) value of 1.27, indicating the dissociation of B-H from BH₄⁻ as the rate-determining step of the process. Furthermore, the reuse and durability of the material were evaluated, revealing a catalyst performance close to 100% over the 10 tested cycles. Therefore, it can be concluded that the synthesized material, Pt-nanoparticles dispersed on HTiNbO₅, exhibits excellent performance and is suitable for hydrogen evolution from NaBH₄. Full article

Mercury adsorption/oxidation plays a crucial role in mercury transformation during coal combustion. To gain an intuitive understanding of the adsorption/oxidation mechanisms between mercury and fly ash, changes in mercury speciation of fly ash before and after Hg adsorption were investigated using temperature-programmed decomposition–atomic fluorescence spectroscopy (TPD-AFS). The results directly reveal that the primary adsorption/oxidation mechanism between mercury and fly ash is the heterogeneous oxidation reaction of Hg⁰ to HgCl₂. The mercury adsorption capacity exhibits a strong positive correlation with both the unburned carbon (UBC) content and the specific surface area (SSA) of the fly ash, whereas the presence of metal oxides has a negligible effect on mercury adsorption. Higher inlet concentrations of Hg⁰ enhance mercury adsorption, while flue gas components such as N₂, O₂, and CO₂ have minimal influence on mercury adsorption. Full article

Photoactivatable nitric oxide donors (photoNORMs) are promising agents for controlled NO release and real-time optical tracking in biomedical theranostics. Here, we report a comprehensive density functional theory (DFT) and time-dependent DFT (TDDFT) study on a series of hybrid ruthenium–gold nanocluster systems of the general formula [(L)Ru(NO)(SH)@Au₂₀], where L = salen, bpb, porphyrin, or phthalocyanine. Structural and bonding analyses reveal that the Ru–NO bond maintains a formal {RuNO}⁶ configuration with pronounced Ru → π*(NO) backbonding, leading to partial reduction of the NO ligand and an elongated N–O bond. Natural Bond Orbital (NBO), Natural Energy Decomposition Analysis (NEDA), and Extended Transition State–Natural Orbitals for Chemical Valence (ETS–NOCV) analyses confirm that Ru–NO bonding is dominated by charge-transfer and polarization components, while Ru–S and Au–S linkages exhibit a delocalized, donor–acceptor character coupling the molecular chromophore with the metallic cluster. TDDFT results reproduce visible–near-infrared (NIR) absorption features arising from mixed metal-to-ligand and cluster-mediated charge-transfer transitions. The calculated zero–zero transition and reorganization energies predict NIR-II emission (1.8–3.8 μm), a region of high biomedical transparency, making these systems ideal candidates for luminescence-based NO sensing and therapy. This study establishes fundamental design principles for next-generation Ru-based photoNORMs integrated with plasmonic gold nanoclusters, highlighting their potential as multifunctional, optically trackable theranostic platforms. Full article

In this work, two novel nanoscale zero-valent iron (nZVI) composites (nanoscale zero-valent iron and copper-intercalated montmorillonite (MMT-nFe⁰/Cu⁰) and carbon microsphere-supported sulfurized nanoscale zero-valent iron (CMS@S-nFe⁰)) were used to treat soil contaminated with both Cr(VI) and p-nitrophenol (PNP), and added persulfate (PMS). Experiments found that the pollutant removal effect has a great relationship with the ratio of water to soil, the amount of catalyst, the amount of PMS, and the pH value. When the conditions are adjusted to the best (water–soil = 2:1, catalyst 30 g/kg, PMS 15 g/kg, pH 7–9), both materials fix Cr(VI) well and decompose PNP. The removal rates of Cr(VI) and PNP by the MMT-nFe⁰/Cu⁰ system are 90.4% and 72.6%, respectively, while the CMS@ S-nFe⁰ system is even more severe, reaching 94.8% and 81.3%. Soil column leaching experiments also proved that the fixation effect of Cr can last for a long time and PNP can be effectively decomposed. Through detection methods such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS), we found that Cr(VI) was effectively reduced to Cr(III) by Fe⁰ and Fe²⁺ ions and subsequently transformed into stable FeCr₂O₄ spinel oxides, and the groups produced after the decomposition of PNP could also help fix the metal. This work provides a way to simultaneously treat Cr(VI) and PNP pollution, and also allows the use of multifunctional nZVI composites in complex soil environments. Full article

Textile dyeing effluents are characterized by recalcitrant organics and high salinity, requiring robust pretreatments prior to biological polishing. The heterogeneous Fenton-type (HFT) oxidation over Prussian Blue nanoparticles supported on γ-alumina (PBNP/γ-Al₂O₃) was investigated in a liquid batch-recycle packed-bed reactor treating a synthetic textile wastewater (STW) reproducing an industrial dye bath with the Reactive Black 5 (RB5) dye, together with simplified RB5 and RB5 + NaCl matrices. Hydrogen peroxide decay followed pseudo-first-order kinetics. Using fixed initial doses (11, 20, 35 mmol L⁻¹), the catalyst exhibited an early adaptation phase and then reproducible operation: from the fourth reuse onward, both the H₂O₂ decomposition rate constant and DOC removal varied by <10% under identical conditions. Among matrices, STW exhibited the highest oxidant efficiency. With an initial H₂O₂ dose of 11 mmol L⁻¹, the treatment enabled complete discoloration and produced effluents with negligible toxicity. Increasing the initial dose to 20 or 35 mmol L⁻¹ did not improve treatment and led to a decrease in the hydrogen peroxide decomposition rate with reuses and loss of PB ν(C≡N) Raman bands, indicating surface transformation. Overall, PBNP/γ-Al₂O₃ demonstrated reproducible activity and structural resilience in saline, dyeing-relevant matrices at H₂O₂ doses that preserve catalytic integrity, confirming its feasibility as a stable and reusable pretreatment catalyst for saline dyeing effluents, and supporting its integration into hybrid AOP–biological treatment schemes for dyeing wastewater. Full article

Brilliant blue, as a pigment food additive, has all the characteristics of printing and dyeing wastewater and belongs to persistent and refractory organic compounds. The photocatalysis–Fenton reaction system consists of two parts: photocatalytic reaction and Fenton reaction. Electrons promote the decomposition of H₂O₂ to produce •OH. In addition, the effective separation of e- and h⁺ by light strengthens the direct oxidation of h⁺, and h⁺ reacts directly with OH⁻ to produce •OH, which can further promote the removal of organic pollutants. In this paper, g-C₃N₄ and Fe/g-C₃N₄ photocatalysts were prepared by the thermal polycondensation method. Fe/g-C₃N₄ of 15 wt% can reach 98.59% under the best degradation environment, and the degradation rate of g-C₃N₄ is only 7.6% under the same conditions. The photocatalytic activity of the catalysts was further studied. Through active species capture experiments, it is known that •OH and •O₂⁻ are the main active species in the system, and the action intensity of •OH is greater than that of •O₂⁻. The degradation reaction mechanism is that H₂O₂ combines with Fe²⁺ in Fe/g-C₃N₄ to generate a large amount of •OH and Fe³⁺, and the combination of Fe-N bonds accelerates the cycle of Fe³⁺/Fe²⁺ and promotes the formation of •OH, thereby accelerating the degradation of target pollutants. •O₂⁻ can reduce Fe³⁺ to Fe²⁺, Fe²⁺ reacts with H₂O₂ to produce •OH, which promotes degradation, and •O₂⁻ itself also plays a role in degradation. In addition, under the optimal experimental conditions obtained by response surface experiments, the fitting degree of first-order reaction kinetics is 0.96642, and the fitting degree of second-order reaction kinetics is 0.57884. Therefore, this reaction is more in line with first-order reaction kinetics. The adsorption rate is only proportional to the concentration of Fe/g-C₃N₄. Full article