Search Results (259)

Understanding the dynamics of carbon (C), nitrogen (N), and phosphorus (P) stoichiometry and C stocks along a stand development chronosequence has been extensively studied in forest ecosystems. However, despite the global economic and ecological importance of apple orchards, such knowledge remains limited for these intensively managed perennial agroecosystems. We examined C, N, and P concentrations and stoichiometric ratios in tree tissues (root, stem, branch, foliage) and soils (0–100 cm depth), as well as ecosystem C stocks, across a chronosequence of 4, 8, 12, and 16 yr old Malus pumila orchards in the eastern Yan Mountains, Hebei Province, North China. The results showed that C concentrations exhibited no consistent age-dependent trend in tree tissues. In contrast, N and P concentrations in all tree tissues decreased significantly with stand age, while their C:N and C:P ratios increased. The leaf N:P ratios suggested progressive P limitation as orchards aged. In soil, C, N, and P concentrations first decreased and then increased along the chronosequence, with the highest values observed in the 16 yr stands. This U-shaped trajectory reflected the dynamic interplay between stand development and anthropogenic management. Intercropping and intensive fertilization in the 4 yr orchards initially elevated soil nutrient levels, while the cessation of intercropping and nutrient removal via fruit harvesting in the 8 yr stands led to a decline. Thereafter, accumulation of litter decomposition and root turnover, combined with continued organic matter inputs, progressively replenished soil nutrient pools in the 12 and 16 yr stands. The total ecosystem C stocks ranged from 70.80 to 136.13 Mg ha⁻¹, initially declining from 4 to 8 years and then increasing at 12 and 16 years, with soil contributing 84.7–99.7% of the total. Plant and soil nutrient concentrations showed predominantly negative correlations, indicating weak coupling between tree and soil nutrient pools. Our findings demonstrated that stand age profoundly influenced C:N:P stoichiometry and C stocks in apple orchard ecosystems and that prolonged orchard development enhanced both tree biomass C and soil C stocks. These results provide a scientific basis for nutrient optimization and sustainable management of apple orchards in temperate regions. Full article

In this work, a comprehensive analysis of the relationship between photoluminescent, thermo-oxidative, and photocatalytic (upon simulated sunlight exposure) properties of ZnO powders is performed. The correlation between the X-ray diffraction and microscopic data is studied. ZnO powders of various sizes and morphologies were used: pseudo-spherical nanoparticles (30–50 nm), submicron faceted crystallites (100–500 nm), and plate- and rod-like microstructures (up to 20 μm). The mean specific surface area values were 32 m²/g, 3.8 m²/g, and 2.6 m²/g for pseudo-spherical nanoparticles, submicron faceted crystallites, and plate- and rod-like microstructures, respectively. According to the XRD data, microstresses and carbon-based impurities were present in ZnO nanoparticles, which is characteristic of nanomaterials synthesized at low temperatures. According to the photoluminescence spectroscopy data, the emission in ZnO was reduced due to high defectiveness, and characteristic emission bands indicated the presence of organic impurities. Upon long signal registration times, an intensive luminescence band with an effective maximum at 579 nm occurred, which indicated the presence of long-term components exhibiting decay times τ ~300 μs. According to the XRD data, the crystal structure parameters of ZnO submicro- and microparticles were close, with no impurities present. In their photoluminescence spectra, pronounced UV and defect-related bands were present with intensity ratios of 11.6 and 6.88, respectively. The decrease in the UV and defect-related luminescence band intensity ratios indicates deviation from the stoichiometry toward an increased Zn over oxygen content. At long signal registration times, in submicron ZnO particles, a luminescence band with maxima at 425 and 490 nm is present, which decays rapidly. An emission band in the 530 nm region is also present, which decays for ≤80 μs, and a weak long-wavelength emission decaying for ~100 μs. At long delay and strobe times (up to milliseconds), only an emission in the 460 nm region is observed, which we connect to the triplet–singlet transition of a defect center (F*, F⁺*). At lower intensities, an emission connected to the surface contamination by organic impurities is observed. In photoluminescence spectra of ZnO microparticles, no long-wavelength emission components are observed. However, upon immersing into methylene blue solution, a modification of the surface and UV region of the spectra is observed with signs of charge carrier recombination rate acceleration. It is shown that the catalytic action of ZnO powders in polyethylene thermo-oxidation processes is determined by a combination of factors. In addition to dispersity and concentration, which are the key parameters, the morphology of ZnO particles, the presence of impurities, the surface state, and the distribution of active sites have a significant influence on catalysis. It has been experimentally demonstrated that these secondary factors can markedly affect the rate of radical formation in polyethylene films and alter their resistance to oxidation. ZnO nanoparticles exhibited low catalytic activity in both photocatalysis (rate constant 0.146 min⁻¹) and thermocatalysis due to the high defect density of the crystallites and the presence of carbon-containing impurities. Submicron ZnO particles, owing to a high carrier generation rate and suppressed recombination (via trapping), demonstrated the highest photoactivity (rate constant 0.729 min⁻¹). Submicron ZnO particles exhibit a catalytic effect on the thermo-oxidation of polyethylene (PE films); however, at concentrations above 8 wt.% a transition to an inhibiting effect is observed. ZnO microparticles catalyzed the oxidation of PE films over a broader concentration range (1–12 wt.%), with oxidation inhibition observed only at 18 wt.%. At the same time, they demonstrated moderate photocatalytic activity (rate constant 0.256 min⁻¹). These characteristics of the samples correlate with data obtained by microscopy, photoluminescence spectroscopy, and X-ray diffraction analysis. Full article

Gibbs free energy values obtained from quantum-chemical calculations were used to determine the formation constants of homo- and heteroligand copper(II) complexes with various ligands (amino acids, diimines, and phosphorylated dithiocarbamates) in an aqueous medium. A computationally robust, yet moderately expensive, level of theory—B3LYP/def2-TZVPPD—was employed. Solvent effects were accounted for using two models: C-PCM and SMD. A key prerequisite for obtaining reliable results is the use of a reference complex with a known formation constant that is structurally and solvation-wise similar to the compound under study. In this context, “similarity” implies identical stoichiometry, the same coordination number, the same number of water molecules in the inner coordination sphere; matching charges, however, is considerably less critical. The importance of considering conformers and isomers to obtain the most accurate values is demonstrated. The more rigid the structure and the greater the degree of similarity between the studied and reference compounds, the better the agreement between calculated and experimental data; the discrepancy can be as low as 0.1–0.2 logarithmic units. When an appropriate reference is selected, the average deviation of the calculated stability constants is less than 1 logarithmic unit. Full article

Soil microbial carbon use efficiency (CUE) and nitrogen use efficiency (NUE) are fundamental parameters governing organic matter turnover in terrestrial ecosystems, yet how forest type-driven variation in litter quality propagates through the litter–soil–microbe continuum to regulate these efficiencies remains poorly resolved. Across three forest types in the Funiu Mountains, central China—a Larix gmelinii (LG) plantation, a Quercus aliena var. acuteserrata (QA) secondary forest, and a mixed Quercus aliena var. acutiserrata and Pinus armandii (QP) forest—we quantified litter chemistry, soil physicochemical properties, microbial biomass, extracellular enzyme activities, and microbial nutrient use efficiencies (MUE: NUE, and phosphorus use efficiency, PUE) derived from a modified saturation kinetics model. Principal coordinate analysis revealed significant multivariate differentiation among forest types across litter, soil, microbial biomass, and enzyme modules (Adonis R² = 0.198–0.427; all p < 0.05). Compared with LG and QA, QP exhibited a pronounced stoichiometric imbalance: it supported the highest litter organic carbon and total nitrogen, the lowest lignin-to-cellulose ratio, the largest soil C and N pools (SOC and STN), and the greatest microbial biomass carbon (MBC). However, despite this resource-rich environment, microbial biomass C:N:P ratios exhibited constrained variation, while soil C:P (SCP) and N:P ratios (SNP) in QP reached extreme values (112.3 and 7.25, respectively), generating severe stoichiometric imbalance. Vector analysis indicated that all forests were under relative nitrogen limitation (vector angle < 45°), with QP showing the strongest limitation (41.6 ± 0.4°). Critically, QP exhibited the highest NUE (0.47 ± 0.03) but the lowest CUE (0.95 ± 0.01), and CUE and NUE were nearly perfectly negatively correlated across all sites (R = −0.98, p < 0.001). Random forest analysis identified extracellular enzyme stoichiometry as the dominant proximate predictor of MUE. Partial least squares structural equation modeling (GOF = 0.673–0.674; R² = 0.592–0.603) revealed that litter and soil properties had no significant direct effects on CUE or NUE; instead, soil nutrients exerted strong indirect association through a cascade—soil → microbial biomass → enzyme activity—with opposite total effects on CUE (−0.731, p < 0.001) versus NUE (+0.755, p < 0.001). These findings reveal that the same soil nutrient enrichment that accompanies mixed-species afforestation drives divergent microbial metabolic responses—suppressing CUE while promoting NUE—through a shared cascading structure, with implications for predicting soil carbon and nutrient retention under shifting forest compositions. Full article

Associated gas in the Permian Basin is a methane-rich but spatially fragmented and intermittently available feedstock. Methane pyrolysis can convert hydrocarbons to hydrogen and solid carbon without forming process CO₂ in the reactor, but its practical value depends on the captured-gas capacity factor, feed composition, high-temperature heat supply, product purification, continuous carbon withdrawal, carbon offtake, and transparent greenhouse-gas accounting. This study presents an implemented screening model for a modular 1 million standard cubic feet per day (MMSCFD) Permian associated-gas unit. A representative Permian composition is evaluated with hydrocarbon cracking stoichiometry, catalytic and thermal conversion envelopes, a net hydrogen recovery assumption, an energy-duty allocation, a levelized-cost model, and a well-to-gate carbon-intensity model. The catalytic base case produces 3.78 t/d of saleable H₂ after 90% pressure-swing adsorption (PSA) recovery and 14.27 t/d of solid carbon; the thermal near-complete conversion bound produces 4.31 t/d of saleable H₂ and 16.15 t/d of solid carbon. At a 0.85 capacity factor, $10 million installed capital expenditure (CAPEX), 8% real discount rate, 20-year life, 10 kWh per kg H₂ energy intensity, and $0.06 per kWh electricity, the deterministic plant-gate levelized cost of hydrogen (LCOH) is $1.81 per kg H₂ at zero carbon value and $1.05 per kg H₂ at a net realized carbon value of $0.20 per kg C. Monte Carlo analysis over capacity factor, CAPEX, energy intensity, electricity price, carbon value, feed/capture cost, and yield uncertainty gives levelized cost of hydrogen values at the 10th, 50th, and 90th percentiles (P10/P50/P90) of $1.32/$1.91/$2.57 per kg H₂. The corresponding screening carbon-intensity distribution is 2.34/4.11/5.89 kg carbon dioxide equivalent (CO₂e) per kg H₂, dominated by electricity carbon intensity and upstream methane loss. Geothermal or waste-heat preheat is treated quantitatively as a partial offset to low- and mid-temperature duties, not as a replacement for high-grade 900–1200 °C trim heat. The pathway is benchmarked against steam methane reforming, autothermal reforming with carbon capture and storage, electrolysis, small-scale liquefied natural gas, and gas-to-liquids conversion. Reported LCOH values are plant-gate production costs; separate hydrogen-logistics and negative-carbon-value stress tests identify conditions under which remote delivery or carbon disposal can erode the apparent economic advantage. Full article

Understanding responses of soil organic carbon (SOC) fractions to variable hydrological conditions is essential to clarify carbon stabilization in subtropical lake wetlands. This study examined vertical and spatial variations of particulate organic carbon (POC), mineral-associated organic carbon (MAOC) and nutrient stoichiometry across four sites in Dongting Lake (0–200 cm depth, five layers). SOC and total nitrogen (TN) showed significant decreasing trends with depth from the surface to 60 cm (p < 0.05), with the highest values in the 0–40 cm layer and significantly lower values below 60 cm. In contrast, total phosphorus (TP) was vertically stable but differed greatly among sites. C/N, C/P and N/P ratios showed distinct regional disparities (p < 0.05). The proportions of POC/SOC and MAOC/SOC exhibited highly significant regional differences (p < 0.05) but no significant vertical variation or interaction effects (p > 0.05). The POC/MAOC ratio exceeded 1 only at Tuanzhou (1.62–2.20), indicating a vulnerable POC-dominated pool; other sites were MAOC-dominated (ratio < 1). Site-specific nutrient regulation further differentiated carbon pool characteristics: nutrients dominated carbon fraction variation at Tuanzhou and Huanghua, co-functioned with soil texture at Junshan, and reduced carbon stability under nutrient enrichment at West Dongting Lake. The texture control effect intensified with soil depth, and deep soil exhibited the strongest mineral protection capacity. We conclude that relative proportions of POC and MAOC in total SOC are region-specific, while their absolute concentrations decrease with depth. We recommend that wetland restoration prioritizes maintaining natural hydrological regimes and soil texture integrity, with future validation across multiple floodplain wetlands. Full article

Extracellular enzyme stoichiometry is a key indicator for assessing nutrient limitation experienced by soil microorganisms. Yet, the characteristics of enzyme-inferred microbial nutrient limitation in rhizosphere soil under the combined agricultural practices of intercropping and straw retention remain unclear. Here, we conducted a field experiment in the black soil region of Northeast China to quantify the effects of intercropping and straw retention on soil nutrients, microbial biomass, extracellular enzyme activities, and their C:N:P stoichiometry in the rhizosphere of maize and peanut. Our results showed that compared with sole cropping, intercropping increased soil organic carbon (SOC) by 6.21–13.57%, total nitrogen (TN) by 8.57–12.49%, and total phosphorus (TP) by 12.01–40.29% in the rhizosphere. The vector analysis revealed an average vector length (VL) of 1.68 and 1.57 for extracellular enzymes in the rhizosphere soil of maize and peanut, with a vector angle (VA) of 37.80° and 34.67°, respectively. These values suggest that soil microorganisms in the rhizosphere of both crops experienced C limitation, and that the degree of enzyme-inferred N limitation was modulated by microbial C acquisition strategies, with a dynamic trade-off between the two. This N limitation was more pronounced in the peanut rhizosphere. Notably, the combined treatment of intercropping and full straw retention increased the VA of peanut by 5.38%, corresponding to a partial alleviation of enzyme-inferred N limitation in the rhizosphere soil. The extracellular enzyme C:N:P stoichiometry in the rhizosphere soil of maize and peanut was 1.33:1.29:1.00 and 0.89:1.29:1.00, respectively. Microbial biomass nitrogen (MBN) was the primary factor affecting enzyme-inferred microbial nutrient limitation (explaining 54.6% of variation). The extracellular enzyme stoichiometric characteristics of rhizosphere soil differed significantly between the two crops. Intercropping had a stronger impact on rhizosphere microbial nutrient limitation than straw retention, and their synergistic effect was associated with a partial alleviation of rhizosphere enzyme-inferred N limitation by enhancing extracellular enzyme activity. These findings demonstrate that integrated intercropping and straw retention can support sustainable soil management in black soil agroecosystems. Full article

Sodium hypochlorite (NaOCl) remains the gold standard irrigant in endodontics due to its proteolytic and antimicrobial properties, whereas hydrogen peroxide (HP) is widely used for internal bleaching because of its oxidative capacity. Both agents have been associated with chemical and structural alterations in dentin; however, the impact of their sequential application on the organic–mineral balance has not been fully elucidated. Objective: To evaluate whether the isolated and sequential application of 5.25% NaOCl and 37.5% HP induces chemical alterations in dentin by analyzing changes in the organic matrix and mineral phase using Fourier-transform infrared spectroscopy (FTIR) and Energy-dispersive X-ray spectroscopy (EDX). Methods: Twenty-four independent dentin sections (n = 6 per group) from six human third molars were distributed using a tooth-balanced allocation into four groups: Control, NaOCl (5.25%, 15 min), HP (37.5%, 30 min), and sequential NaOCl+HP. FTIR assessed organic (amide I, II, III, CH₂) and inorganic (phosphate, carbonate) components through baseline-corrected integrated areas, Full Width at Half Maximum (FWHM), and molecular ratios. Surface elemental composition and the calculated Ca/P atomic ratio were determined by EDX. Multiple sub-measurements per specimen were averaged before statistical analysis. Data were analyzed using Kruskal–Wallis and Mann–Whitney U tests with Bonferroni correction (p < 0.05). Results: FTIR revealed treatment-dependent modifications. NaOCl reduced absorbance in organic-associated bands, indicating collagen degradation, whereas HP altered the mineral phase. The NaOCl+HP group exhibited increased numerical values for integrated band areas, with differences detected in carbonate, phosphate, and amide III bands (p < 0.05), reflecting structural disorganization and modified spectral signal rather than tissue preservation. No differences were detected across the calculated infrared ratios (p > 0.05). EDX showed decreased absolute atomic percentages of Ca, P, and O in the NaOCl+HP group (p < 0.05), indicating structural demineralization, while its stoichiometric Ca/P ratio remained at 1.56. Isolated HP shifted the mineral stoichiometry to the highest numerical Ca/P ratio (1.69; range 1.58–1.80). Fluorine decreased across all treated groups (p < 0.001). Conclusions: Sequential NaOCl and HP application triggers distinct chemical alterations compared to individual treatments, inducing severe structural disorganization of the organic network and absolute mineral depletion of Ca and P. This multi-agent sequence alters dentin stoichiometry, which may compromise the biomechanical integrity of the tissue. Full article

Anthropogenic disturbances and climate warming threaten the rare paleoendemic species Tetracentron sinense. To identify the divers of its latitudinal adaptation, we integrated functional trait differentiation, environmental filtering, and phylogenetic conservatism. We measured 35 functional traits (leaf morphology, nutrient stoichiometry, stomatal traits, whole-plant architecture) across four natural populations spanning the species’ latitudinal range: BMXS (Baima Snow Mountain), DFD (Dafengding), FP (Foping), LGS (Leigong Mountain). Using correlation analysis, principal component analysis, and phylogenetic community metrics, we found that T. sinense dominated all communities. Populations exhibited divergent strategies: DFD expanded leaf area for light capture under high rainfall and shaded conditions; FP increased height and crown width to compete for light; LGS enhanced nutrient-use efficiency under phosphorus limitation; BMXS promoted phosphorus uptake under nitrogen limitation (N/P < 14). Trait variation correlated significantly with elevation, solar radiation, and temperature. PCA explained 90.44% of total variance, and standardized effect size (SES) values for phylogenetic signals range from −2.031 to 1.973; Phylogenetic signals were stronger in co-occurring taxa than in T. sinense. T. sinense populations in BMXS and FP are structured by competitive exclusion, while those in LGS and DFD by habitat filtering. We conclude that T. sinense achieves latitudinal adaptation by overcoming phylogenetic niche conservatism through phenotypic plasticity. While leaf economic traits remain evolutionarily conserved and niches in glacial refugium are relatively stable, populations adjust trait syndromes via metabolic shifts and structural trade-offs in response to heterogeneous environmental filters. Identifying these adaptive strategies can guide seed sourcing for restoration efforts under climate change. Full article

Vegetation mosaics characterize mountainous agroforestry ecosystems, yet how their spatial configuration shapes soil microbial assembly and functions remains unresolved. This study investigated how mosaic elements (monocultures, shrublands, and ecotones) drive microbial communities and enzyme activities across a forest–shrubland–farmland mosaic in western Hunan, China. Nutrient stoichiometry, microbial biomass (PLFA), and six enzyme activities were analyzed via variance partitioning, partial least squares regression, and ordination analysis. Fungal biomass dominated, peaking in ecotones and showing the lowest values in monocultures and shrublands. Microbial assembly was regulated by soil nutrients (31%) rather than soil texture (15%). Fungi (variable importance in projection, VIP = 1.287) and bacteria (VIP = 1.003) were key drivers, indicating distinct functional compartmentalization: fungi drove oxidative enzymes, whereas bacteria mediated nutrient cycling. Actinomycetes and total PLFA acted as secondary drivers, with VIP values of 0.932 and 0.939, respectively. Soil organic matter, dissolved organic carbon, silt content, and available nitrogen were key abiotic predictors. Collectively, vegetation configuration regulates soil functioning via nutrient-mediated microbial assembly and functional differentiation across mosaic elements. These findings underscore the role of landscape heterogeneity in sustaining soil fertility, suggesting that protecting ecotones and maintaining mosaic complexity should be prioritized in mountainous agroforestry management to enhance soil ecological functioning under global land-use change. Full article

Adeno-associated viruses (AAVs) have emerged as promising vectors for gene therapy due to their non-pathogenic nature and ability to transduce various cell types efficiently. In recent years, there has been an increasing effort to optimize the production and purification of AAV to support clinical applications; however, challenges exist in affinity ligand design, synthesis, and characterization. Understanding the binding interactions of these viruses with functional molecules is pivotal for the development of affinity-based separation methods of AAVs. Classical methods to measure thermodynamic parameters such as Isothermal Titration Calorimetry (ITC) are challenging to employ in these scenarios, as the concentrations of the viral titers are significantly lower than those used in binding experiments with small biomolecules. Here, we present design principles that enable ITC-based determination of binding interactions between AAV2 and heparin. We observe increasing binding affinity with increasing molecular weight of heparin. We also elucidate the binding stoichiometry between AAV2 and heparins of varying molecular weights. Additionally, we report on the impact of buffer conditions and pH values on AAV2–heparin binding properties. Lastly, we also present the binding affinities and thermodynamic properties of interactions between the two species with heparin immobilized onto surfaces, namely, silica nanoparticles, as surface immobilization of the ligand is a common pathway for affinity-based separations. Overall, our results may provide key information for optimization of AAV-ligand binding protocols that are an essential step toward optimizing AAV capture and immobilization methods. Full article

The present study extends the investigation of thermodynamic properties of phases in the silver–magnesium binary system, with particular emphasis on the κ-Ag₂Mg₅ phase, for which available literature data remain scarce. The work is divided into two parts. The experimental section comprises the synthesis of the κ phase from high-purity Ag and Mg, followed by its characterisation using scanning electron microscopy (SEM) and X-ray diffraction (XRD). The synthesised material was subsequently used for calorimetric determination of the standard enthalpy of formation employing the drop solution method. Measurements were carried out in two experimental series (A and B), using two different metallic solvents (Al and Sn), at temperatures of 1020 K and 689 K. The enthalpy of formation obtained in both series was −14.4 ± 0.32 and −14.5 ± 0.42 kJ/mol at., respectively. In addition, the limiting partial enthalpy of solution of liquid Ag in liquid Al was determined calorimetrically and its average value is equal 7.1 ± 0.7 kJ/mol. The theoretical part of the study involved ab initio calculations of defect formation energies. The obtained results show good agreement with available literature data and provide a consistent interpretation of the observed non-stoichiometry of the κ-phase. Full article

The widespread use of herbicides in agriculture results in their accumulation in the environment, which has a negative impact on non-target biota. One way to reduce environmental risks while maintaining the effectiveness of plant protection products is to apply supramolecular chemistry principles to agricultural practices. Although pillar[n]arenes are used in the production of sensors and antidotes for pesticides, their influence on the herbicidal properties and ecotoxicity of herbicides toward aquatic organisms and higher plants has hardly been studied. The effect of pillar[5]arenes on the herbicidal activity of 2,4-dichlorophenoxyacetic acid (2,4-D) and glyphosate (Glyp), as well as the ecotoxicity of the resulting binary systems toward Ceriodaphnia affinis and Paramecium caudatum, was assessed for the first time. The association constants of pillar[5]arenes with Glyp (logK_a = 3.92–4.06) were an order of magnitude higher than the corresponding values for 2,4-D (logK_a = 2.66–3.06) with the stoichiometry of 1:1. The formation of stable associates (143–177 nm) with negative zeta potential values (from −20.9 to −7.8 mV) was demonstrated for the pillar[5]arene/herbicide systems. Low phytotoxicity of pillar[5]arenes against Chlorella vulgaris was shown. The addition of pillar[5]arenes to 2,4-D reduced the wheat (Triticum aestivum L.) germination index by 4.5-fold compared to the pure herbicide. Forming associates between decamethoxypillar[5]arene and Glyp increased the LC₁₀ by more than twofold compared to the individual herbicide against Paramecium caudatum and Ceriodaphnia affinis. It was demonstrated that combining pillar[5]arenes with Glyp can reduce ecotoxicity while partially preserving or selectively modifying phytotoxicity. The results obtained in this study are encouraging for the development of materials and supramolecular systems that could boost agricultural efficiency while reducing its environmental impact. Full article

To elucidate the mechanisms of nutrient cycling in rhizosphere soil and microbial metabolism during the prolonged continuous cropping of lavender, this study examined the rhizosphere soil of lavender with different continuous cropping years (1, 4, 7, 10, 15, and 20 years) in the Ili River Valley of Xinjiang, China, measuring physicochemical properties, microbial biomass C/N/P, and eight extracellular enzyme activities. Microbial carbon use efficiency (CUE) and nutrient limitation were quantified using vector analysis, threshold elemental ratios (TERs), and two derived indices (TER_EEA and TER_L). Soil properties exhibited distinct nonlinear patterns: SOC peaked at 4 years (p < 0.05), TN was highest at 20 years, and TP was lowest at 4–7 years. MBC and MBN peaked at 20 years, whereas MBP was significantly lower than in 1-, 4-, and 10-year fields (p < 0.05). EEC and EEN were highest at 20 years, while EEP was lowest at 4 years (p < 0.05). The activity of carbon-related acquisition enzymes increases from 134.81 μmol/g·h in the first year to 393.86 μmol/g·h in the 20th year, an increase of 192%; the activity of nitrogen acquisition enzymes increases from 686.11 μmol/g·h in the first year to 1430.58 μmol/g·h in the 20th year, an increase of 108%. This indicates that the decomposition of organic matter and the nutrient cycling capacity continue to enhance. Vector analysis showed a mean VA of 46° and VL of 0.25, with VA > 45° (P limitation) at 1–4 years shifting to VA < 45° (N limitation) at 20 years. Critically, TEREEA and TERL produced opposite dominant limitations due to differing normalization frameworks—TEREEA scales by microbial biomass stoichiometry—while TERL normalizes against enzyme-derived thresholds. CUET and CUEE ranged from 0.42 to 0.56, with the minimum at 10 years and relatively high values at 15–20 years (p < 0.05). RDA identified CBH (26.2%) and NO₃⁻–N (19.8%) as primary drivers, with extractable phosphorus exhibiting the strongest regulatory effect (pseudo-F = 26.0). These results demonstrate that multi-model stoichiometric assessment is essential, as single indices may yield contradictory diagnoses. These results demonstrate that multi-model stoichiometric assessment is essential, as single indices may yield contradictory diagnoses, and the observed nonlinear shifts in dominant limitation type provide a mechanistic basis for targeted nutrient management in sustainable lavender cultivation. Full article

Designing materials with superior corrosion resistance is critical for seawater electrolysis systems to achieve efficient and long-term stable hydrogen production. In the current study, CrAlN coatings were deposited on TA1 titanium substrates by reactive magnetron sputtering with nitrogen flow ratios ranging from 40%–70% to investigate the effect of nitrogen stoichiometry on corrosion behavior in simulated alkaline seawater (pH ≈ 14, chloride-containing). Microstructural characterization (Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS), Grazing Incidence X-Ray Diffraction (GIXRD), Transmission Electron Microscopy (TEM), X-Ray Photoelectron Spectroscopy (XPS), Atomic Force Microscopy (AFM)) reveals that a 60% nitrogen ratio promotes grain refinement, improved CrN/AlN phase stoichiometry, and reduced oxygen-related defects, resulting in a dense columnar structure with minimized diffusion pathways. Electrochemical measurements show that this condition yields the lowest corrosion current density (0.297 μA·cm⁻²) and the highest polarization resistance (123.9 kΩ·cm²). Electrochemical impedance spectroscopy confirms enhanced charge transfer resistance and suppressed ionic transport at the coating/electrolyte interface. The results establish a clear correlation between nitrogen-controlled phase evolution, defect density, and passivation kinetics in highly alkaline chloride environments relevant to seawater electrolysis. This study targets the fabrication of protective coatings for alkaline seawater electrolysis via nitrogen flow ratio optimization. The optimized CrAlN coating achieves remarkably improved corrosion resistance compared with existing coatings, showing promising practical value for long-term stable seawater electrolysis. Full article