Search Results (5,562)

The problem of chromium contamination, especially Cr(VI), in acidic wastewater has drawn significant attention, requiring effective and sustainable remediation measures. In this study, tannic-acid/Fe₃O₄-modified corn straw biochar (Fe-TA-CSB) is prepared by a grinding-calcination method to remove Cr(VI). The factors influencing the removal effect of Fe-TA-CSB are investigated through static adsorption experiments. The removal mechanism is explored by combining adsorption kinetics, isothermal adsorption, and thermodynamics, as well as characterization methods. The results show that the removal efficiency of Cr(VI) increases with the increase in pH, contact time (t), and solid–liquid ratio (m/v), but decreases with the increase in initial concentration (C₀). Under optimal conditions of TA/Fe₃O₄ mass ratio = 12.5%, pH = 3.0, m/v = 1.0 g/L, and C₀ = 10 mg/L, the removal efficiency value is 94.02%, which is approximately 81.44% after four adsorption–desorption cycles. The adsorption behavior is fitted well by the Sips isotherm model and Elovich kinetics model, suggesting the adsorption process of heterogeneous monolayer chemisorption. The removal mechanism of Cr(VI) by Fe-TA-CSB involves electrostatic interaction with Cr(VI), reduction in Cr(VI) to Cr(III) through C–O and Fe(II), and complexation of reduced Cr(III) with the introduced Fe–O and phenolic hydroxyl groups. Fe-TA-CSB is an environmentally friendly and renewable adsorbent with good potential for the treatment of acidic wastewater. Full article

With the expansion of ammonia energy applications, long-distance liquid ammonia pipelines are expected to support large-scale cross-regional ammonia transport. In the liquid ammonia pipeline commissioning process, gaseous ammonia purging involves ammonia–nitrogen mixing and possible liquefaction, while liquid ammonia injection may induce flashing and severe local cooling, all of which can affect commissioning safety. To characterize these thermodynamic phenomena, a transient gas–liquid two-phase flow model was established and validated using OLGA 2022.1.0 software for simulating the long-distance liquid ammonia pipeline commissioning. The model adopts the cross-sectionally averaged one-dimensional approach. A volume-corrected Soave–Redlich–Kwong (SRK) equation of state for ammonia was adapted, validated, and used to generate OLGA-compatible thermodynamic property tables. The results show that, during gaseous ammonia purging, a higher flowrate shortens the displacement time by accelerating nitrogen removal, and this effect is more pronounced at higher ambient temperatures due to enhanced molecular diffusion. Along the pipeline, pressure gradually decreases from frictional resistance, with a steeper drop near the outlet caused by gas acceleration, and temperature gradually approaches ambient through heat exchange with the pipe wall and surrounding soil. A high gaseous ammonia flowrate can cause partial liquefaction, regasification, and temperature fluctuations. During liquid ammonia injection, local condensation and slight liquid accumulation occur before the liquid front arrives, and the low-temperature region moves with the liquid front. The liquid ammonia mass flowrate has the strongest influence on the injection process, as it reduces the completion time but increases the outlet temperature, outlet pressure, and the low-temperature risk downstream of the valve. Therefore, it should be controlled within an appropriate range to balance efficiency and low-temperature safety risks. This work provides a rapid and efficient prediction model for key thermo-hydraulic parameters during liquid ammonia pipeline commissioning, and the overall analyses offer insights for on-site process design and safety control. Full article

The P(IA-HBP-AA-AM)/MMT composite was successfully synthesized via in situ polymerization and characterized using FTIR, XRD, TGA, and other techniques. The material was then applied as an adsorbent for the removal of heavy metals from simulated mining-contaminated water (prepared based on the typical ionic composition of real mining wastewater). Static adsorption experiments revealed that P(IA-HBP-AA-AM)/MMT composite could efficiently remove Pb(II) from contaminated water, and the adsorption behavior was well described by the pseudo-second-order kinetic model and the Langmuir isotherm model. Thermodynamic analysis indicated that the adsorption of Pb(II) onto the P(IA-HBP-AA-AM)/MMT composite was an endothermic and spontaneous process. At pH = 4.5 and T = 45 °C, the maximum adsorption capacity obtained from model fitting was 249.38 mg/g. The material exhibited strong selectivity for Pb(II), even in the presence of competing metal ions such as Cd(II), Zn(II), Al(III), Fe(III), K(I), and Na(I). Moreover, after five adsorption–desorption cycles, it still retained approximately 90% of its Pb(II) removal efficiency. Furthermore, dynamic adsorption experiments showed that the saturation adsorption capacity of Pb(II) reached 178.7 mg/g, with a column utilization efficiency of approximately 41%. These findings demonstrate the promising potential of P(IA-HBP-AA-AM)/MMT composite for the removal of Pb(II) from mining-contaminated water. Full article

Magnesium–rich environments are frequently encountered in cementitious systems, including the use of high–Mg raw materials in clinker production, cement–clay interfaces relevant to nuclear waste disposal, and exposure of cement–based materials to seawater, where progressive decalcification can substantially alter the structure and durability of calcium aluminosilicate hydrate (C–A–S–H) phases. In this study, density functional theory (DFT) calculations were employed to investigate the combined effects of interlayer and intralayer partial decalcification, Mg²⁺ substitution, and reinforcement with epoxy– and hydroxyl–functionalized reduced graphene oxide (rGO) on the structural stability and elastic properties of alkali charge–balanced C–A–S–H under dry and hydrated conditions. Adsorption–energy calculations reveal thermodynamically favorable interactions between functionalized rGO and silicate hydrate species in the presence of Mg²⁺, with hydroxyl/rGO promoting stronger interfacial stabilization and epoxy/rGO preserving greater graphene lattice integrity. The results demonstrate that Mg²⁺ substitution together with rGO intercalation generally enhances the mechanical response of partially decalcified structures through structural densification and interfacial cohesion. Relative to dry systems, hydration further improves elastic performance, increasing Young’s modulus and bulk modulus by 1–11% and 4–19%, respectively, for interlayer decalcified nanocomposites, while intralayer configurations exhibit stronger but model–dependent enhancements of up to ≈22% and ≈33%. Compared with untreated systems, rGO–treated nan–composites exhibit enhanced stiffness, with Young’s modulus and bulk modulus increasing by up to ≈22% and ≈15%, respectively. Overall, these findings provide atomistic insights into stabilization mechanisms in partially decalcified alkali charge–balanced C–A–S–H systems and identify Mg²⁺–rGO incorporation as a promising strategy for mitigating decalcification–induced degradation in durable low–carbon cementitious nanocomposites. Full article

Based on liquid chromatography quadrupole time-of-flight mass spectrometry (LC-Q-TOF/MS), a high-throughput method was developed and validated for the simultaneous detection of 270 pesticides and two quality markers (Q-markers)—ferulic acid and ligustilide—in Angelica sinensis (AS) decoction. Among 50 batches of commercial samples, 15 pesticides were detected. This study dynamically monitored the effects of processing on the content of these 15 pesticides and the two Q-markers. The results showed that distinct differences were observed in the transfer behaviors of the pesticides and Q-Markers during soaking and the first and secondary boiling stages. The decoction transfer rates were calculated and incorporated to establish a risk assessment model applicable to AS. During the decoction, density functional theory (DFT) analysis, combined with LC-Q-TOF/MS confirmation, was employed to elucidate the thermal degradation mechanism of chlorpyrifos. DFT-based thermodynamic analysis was used to explain the significant differences in thermal loss between ferulic acid and ligustilide. Full article

Waste-to-energy (WtE) systems are frequently proposed as complementary waste-management strategies; however, their climate performance depends on the interaction between thermodynamic efficiency, material circularity, and electricity-system characteristics. Existing life-cycle assessments generally provide static comparisons between landfill and WtE but rarely identify the operating conditions under which WtE remains environmentally competitive. To address this gap, a parametric life cycle–energy framework was developed by integrating attributional LCA with an analytical energy model capable of evaluating critical efficiency thresholds under varying recovery rates and electricity-grid conditions. Four representative thermoplastics (PET, HDPE, PP, and LDPE) were evaluated using ReCiPe 2016 Midpoint (H) in SimaPro under Mexican electricity conditions ($E{F}_{\mathrm{grid}}=0.444$ kg CO₂eq/kWh). Results indicate that total life-cycle climate impacts are dominated by upstream polymer production, whereas end-of-life management contributes only marginally to overall GWP. Critical-efficiency analysis revealed strong sensitivity to both recovery rate and electricity-grid carbon intensity. For PET, the minimum efficiency required for WtE to outperform landfill increased from 13.1% to 73.5% across the evaluated scenarios, whereas HDPE remained competitive at efficiencies below 1.3%. Monte Carlo simulations (10,000 realizations) further demonstrated that avoided emissions decline systematically with increasing recovery rates, with LDPE exhibiting the highest mean avoided emissions (1735 kg CO₂eq) and PET the lowest (811 kg CO₂eq). These results demonstrate that WtE climate performance is governed primarily by residual waste availability and electricity-system evolution rather than thermodynamic efficiency alone. Consequently, WtE should be interpreted as a transitional residual-waste management strategy whose long-term climate relevance decreases as material circularity and electricity-grid decarbonization advance. Full article

In gas-condensate reservoirs, the phase behavior of reservoir fluids is inherently dynamic during pressure depletion. When the rate of external pressure decline exceeds the intrinsic relaxation rate governing phase equilibrium, the system deviates from thermodynamic equilibrium and exhibits pronounced non-equilibrium effects. These transient behaviors significantly influence fluid properties; meanwhile, conventional equilibrium models neglect phase transition lag, resulting in inaccurate phase behavior and biased production predictions. In this study, a non-equilibrium dynamic phase transition model is developed to quantitatively couple the pressure depletion rate with the relaxation kinetics of the system. This model, established based on controlled non-equilibrium phase transition experiments performed on the condensate-gas fluid investigated in this work, provides an analytical framework for describing the temporal evolution of phase behavior under dynamic conditions. Model validation through integrated experimental measurements and numerical simulations shows good agreement between calculated and measured results for the studied condensate-gas system, with average relative errors below 5%. Results reveal that accelerated pressure depletion strengthens non-equilibrium effects. At a rate of 15 MPa/h, the relative volume and retrograde condensate saturation decrease by 9.09% and 5.38%, respectively, while condensate recovery improves by 13.85%. Moreover, the characteristic relaxation time toward equilibrium exhibits a strong dependence on the depletion rate, increasing as the depletion rate rises. This work provides an experimentally constrained analytical framework for describing rate-dependent non-equilibrium phase behavior during pressure depletion and for interpreting its impact on condensate recovery in the specific condensate-gas system studied. Although the governing framework may be transferable to other rate-sensitive hydrocarbon systems after fluid-specific recalibration, the parameterized analytical model and validation presented in this study are limited to the investigated condensate-gas fluid, and its applicability to other hydrocarbon fluid types remains to be evaluated in future studies. Full article

In the context of the circular bioeconomy and environmental protection trends, the efficient use of renewable resources has become a driving force for industry, and lignin represents precisely a renewable carbon resource, abundant in terrestrial biomass that could become a sustainable substitute for fossil resources, under conditions of full exploitation. This study systematically evaluates the biosorption of Manganese (Mn(II)) from aqueous media using unmodified Tripidium bengalense (Sarkanda grass) lignin. Under optimal operating conditions (adsorbent dosage of 5 g/L, pH 6.5, and 20 °C), a highly competitive experimental adsorption capacity of 12.52 mg/g was achieved. Kinetic studies revealed exceptionally rapid uptake rates, with thermodynamic equilibrium established within the first 30 min, fitting perfectly with the pseudo-second-order (Ho-McKay) model (R² ≥ 0.9998). Equilibrium data were best described by the Freundlich isotherm (R² ≥ 0.9886), confirming chemisorption via preferential inner-sphere complexation on a heterogeneous surface. Thermodynamic analysis verified that the process is spontaneous (ΔG ranging from −13.24 to −26.19 kJ/mol) and endothermic (ΔH from 11.21 to 14.83 kJ/mol). FTIR, SEM-EDX, and TG/DTG analyses confirmed successful Mn–O coordination involving phenolic hydroxyl and carboxylic groups. Furthermore, the lignin showed excellent recyclability, maintaining a retention efficiency over 70% (70.7–85.8%) after three desorption-resorption cycles using 1N HCl. Ecotoxicological validation via Sorghum bicolor L. germination tests confirmed the complete detoxification of the post-adsorption filtrates (up to 100% germination capacity), while the Mn(II)-loaded lignin completely suppressed seed germination (0%), proving secure metal immobilization. These findings establish raw Sarkanda grass lignin as an efficient, scalable, and ecologically sustainable biosorbent for heavy metal remediation. Full article

Volcanic rocks of the Qi’eshan Group, which are widely distributed in the Dananhu arc of the Eastern Tianshan, NW China, have long been debated in terms of their formation age and tectonic setting. In this study, we conducted an integrated study of U-Pb apatite geochronology, whole-rock major and trace element geochemistry, in situ major element analyses of clinopyroxene, and “Rhyolite-MELTS” thermodynamic modeling on the basalts from the Qi’eshan Group. Geochronological data show that the weighted mean of ²⁰⁶Pb/²³⁸U ages of apatite is 329 ± 10 Ma. The basalts belong to the tholeiitic series and are characterized by enrichment in large ion lithophile elements (LILEs), depletion in high field strength elements (HFSEs), and enrichment of light rare earth elements (LREEs) relative to heavy rare earth elements (HREEs) with weak negative Eu anomalies. They were derived by partial melting of garnet-spinel lherzolite in a depleted mantle source metasomatized by subduction-related fluids, followed by fractional crystallization of spinel, olivine, and clinopyroxene. Clinopyroxene is dominated by augite, characterized by high Mg and Ca contents and low Al and Na contents. Machine-learning-based thermobarometry indicates that clinopyroxene crystallized at temperatures of 1027–1033 °C and pressures of 1.1–1.6 kbar. “Rhyolite-MELTS” isobaric crystallization simulations suggest that mantle-derived magma, with an initial water content of 4 wt.% and oxygen fugacity of FMQ, can generate melts compositionally similar to the volcanic rocks of the Qi’eshan Group through fractional crystallization at a pressure of 1.5 kbar. Combined with previous studies, we propose that the Qi’eshan Group basalts formed in an extensional arc setting related to southward rollback of the northward-subducting Kanguer oceanic slab, which caused asthenosphere upwelling and lithospheric extension, thereby promoting partial melting of the subduction-metasomatized mantle. Our data provide new insights into the Carboniferous rollback of the Kanguer oceanic slab in the northern part of the Eastern Tianshan. Full article

The Santiago River is a highly anthropogenically impaired lotic system globally, yet the mechanisms governing its contaminant transport remain poorly understood under static monitoring paradigms. This study evaluates how hydrological forcing dictates the mobilization and bioavailability of trace metals by integrating a 15-year public hydrochemical database from 10 monitoring nodes with SAR-derived discharge estimates and thermodynamic metal modeling (PHREEQC). To validate the structural integrity of the mass load estimates against hydrometric uncertainties, a deterministic boundary-sensitivity analysis was conducted. Results empirically refute the classical dilution paradigm, introducing the “Anthropogenic Pulse” to describe the non-linear acceleration of pollutant export during high-flow events (discharge Q surging from 36.62 to 286.13 m³/s). While climate-driven parameters follow seasonal cycles, industrial stressors (COD, Pb, Cd) remain in a chronic steady state, decoupling from volumetric dilution. Based on coupled × CQ × C (discharge × concentration) estimates, this dynamic induces a synchronized flushing of toxic burdens, exporting monthly peak loads exceeding 51,000 kg of Zinc, 6500 kg of Lead, and 3100 kg of Cadmium. Thermodynamic simulations reveal that this hydrological flushing functions as a chemical activator; the seasonal dilution of natural Alkalinity and Hardness suppresses the river’s theoretical buffered pH (from 8.5 to 7.0), maintaining metals in their uncomplexed free-ion states (Me²⁺). Modeling indicates that nearly 90% of the exported Cadmium remains in this highly labile, toxic form due to a dual coupling with both river Discharge (r_s = 0.87) and pH (r_s = 0.79). The identification of stochastic arsenic peaks 100 times above regulatory limits at Paso de Guadalupe (RS-08) underscores the failure of concentration-based monitoring. Our findings suggest that restoration strategies should shift toward mass-loading-based regulatory frameworks and targeted sediment management at critical nodes to mitigate the chronic export of bioavailable industrial waste. Full article

The increasing demand for higher efficiency and lower emissions in aircraft gas turbines motivates investigation of alternative thermodynamic cycle architectures. This study assesses the performance and nitrogen oxides (NOx) emission behavior of a triple-spool, separate-exhaust turbofan engine equipped with an interstage turbine burner (ITB). A baseline engine representative of the RB211 Trent 892 is first modeled at maximum takeoff, sea-level static conditions and verified against publicly available takeoff reference data. The cycle is then modified by introducing an isobaric secondary combustion process between the high-pressure and intermediate-pressure turbines. The effects of fan pressure ratio, bypass ratio, overall pressure ratio, high-pressure turbine inlet temperature, and ITB exit temperature are examined using two-parameter response surface sweeps. Main combustor NOx is estimated using an RQL-type cycle correlation, while the ITB contribution is represented using an engineering source–sink model accounting for new NOx formation and partial reburning of upstream NOx. The baseline model predicts specific thrust, thrust-specific fuel consumption (TSFC), and NOx emission index (EINOx) within ±8% of reference values. At a selected ITB operating point, specific thrust increases by 1.98%, TSFC increases by 9.84%, thermal efficiency decreases by 2.56%, and the adopted engineering source–sink model predicts a 20.03% reduction in fuel flow-weighted EINOx. The corresponding takeoff-mode NOx-per-thrust indicator decreases by approximately 12.1%. These results indicate that ITB integration introduces a coupled performance–emissions trade-off and should not be evaluated solely as a thrust augmentation method. Full article

The nucleation and growth mechanisms of copper electrodeposition from Cu(I)-containing-reline, a deep eutectic solvent, were investigated through a combination of electrochemical techniques and surface characterization. Cyclic voltammetry revealed the characteristic nucleation loop associated with an overpotential-driven electrocrystallization process, from which the equilibrium potential of the Cu(I)/Cu(0) redox couple was determined to be −0.35 V vs. a Ag quasi-reference electrode. Experimental potentiostatic current density transients were analyzed using nucleation models capable of accounting for both adsorption and three-dimensional (3D) diffusion-controlled growth, thereby allowing deconvolution of the individual contributions to the overall current response. The kinetic parameters, including the nucleation frequency and the number density of active sites, exhibited an exponential dependence on the applied overpotential, thus indicating enhanced nucleation kinetics at greater driving forces, while determining a Cu(I) diffusion coefficient of (3.39 + 0.09) × 10⁻⁷ cm² s⁻¹. Thermodynamic analysis showed that the Gibbs free energy of the formation of the critical nucleus decreases with increasing overpotential and follows the expected dependence on the inverse square of the overpotential, in agreement with classical nucleation theory. The estimated critical nucleus size was found to be smaller than one atom, suggesting that nucleation occurs at highly active surface sites. Furthermore, an exchange current density of (3 ± 1) μA cm⁻² was estimated for the Cu(I) electrochemical reduction. Scanning electron microscopy revealed a high density of copper nanoparticles (~20 nm) distributed across the electrode surface, along with larger aggregates (~100 nm) formed by coalescence and growth, consistent with a progressive nucleation mechanism. X-ray photoelectron spectroscopy confirmed that the deposits consist exclusively of metallic copper, with no evidence of oxidized species. These results demonstrate that copper electrodeposition in reline is governed by a complex interplay between the thermodynamic driving force, the interfacial kinetics, and mass transport, comprehensively providing fundamental insight into the electrocrystallization processes in deep eutectic solvents. Full article

The potency of urate, an abundant human plasma antioxidant, in preventing oxidative damage caused by the carbonate radical anion CO₃^•−, was studied using quantum chemical calculations. The influence of microhydration of CO₃^•−/CO₃²⁻ and urate⁻/urate^• couples on the thermodynamic and kinetics of the one-electron oxidation process was investigated. Depending on the degree of microhydration, the estimated rate constant for one-electron transfer is in the range of 2.0–7.3 × 10⁹ M⁻¹ s⁻¹, in good agreement with the experimental value of 1.3 × 10⁹ M⁻¹ s⁻¹. Modeling using vertical detachment energy and electron affinity, the driving forces of single electron transfer revealed urate(H₂O)₆⁻ and CO₃(H₂O)₉^•− clusters as the most likely existing species in water. Molecular docking revealed a favorable interaction of urate with the catalytic pocket of SOD1. Urate binds more strongly to the anionic active center of SOD1 than the reference inhibitor LSC-1, indicating its potency to prevent HCO₃⁻-supported CO₃^•− formation. In contrast, the known OGG1 inhibitor TH13264 shows substantially stronger binding than urate, indicating urate’s weaker affinity toward the DNA repair enzyme catalytic pocket. The molecular dynamics data indicate that urate binding does not destabilize either SOD1 or OGG1. In light of increasing evidence that the major source of oxidative stress could be CO₃^•−, rather than the commonly assumed hydroxyl radical HO^•, the obtained results indicate the inherent ability of plasma to combat oxidative stress induced by this selective, milder oxidant. Such an ability with respect to the non-selective, highly reactive HO^• does not exist in vivo. Full article

The rational design of mixed micellar systems has emerged as a cornerstone of modern nanomedicine, offering unprecedented control over the solubility and bioavailability of challenging therapeutic agents. This review provides a comprehensive analysis of the physicochemical principles governing the assembly of amphiphilic drugs and surfactants into synergistic nanostructures. By articulating the transition from traditional guest/host solubilization to “drug-as-component” models, we highlight the critical role of molecular interactions in achieving therapeutic precision. It further outlines the experimental methodologies used to investigate these systems and elucidates how they enhance the solubility, stability, and bioavailability of poorly water-soluble drugs. Special emphasis is placed on the practical applications of synergy in reducing systemic toxicity and optimizing drug release kinetics, providing a roadmap for the development of next-generation nano-pharmaceuticals. The functionality of these systems is significantly influenced by the molecular interactions among their constituents; thus, quantitative analysis of these interactions might enhance the formulation of more effective pharmaceuticals. This review outlines the key physicochemical principles of mixed micelle formation, including thermodynamics and synergistic interactions of amphiphiles, while emphasizing their relevance in current research and practical pharmaceutical applications. Various experimental methods, such as surface tension measurement, conductometric and calorimetric tests, and spectroscopic techniques, are compared in terms of their conditions of application and performance in understanding micelle formation and micelle structure. We clearly point out that the interpretation and evaluation of the properties of colloidal systems containing drug molecules solubilized by mixed micelles and an amphiphilic drug incorporated into micelles must be discussed and evaluated separately. Understanding the limitations and characteristics of the physical/chemical principles applied is essential for the rational design of mixed micelle carriers tailored to specific therapeutic needs. Full article

Focusing on the thermodynamic response of onboard liquid hydrogen tanks under dynamic sloshing conditions, this study investigates the flow-thermal coupling mechanism between the gas-phase space and the main chamber by establishing a numerical model that includes the gas-phase space. The results show that the gas-phase space enhances the initiative and efficiency of system pressure regulation through pressure-difference-driven mass transfer. The evolution of the gas–liquid two-phase temperature field sequentially undergoes four typical stages: pressure-difference-driven jet dominance, thermal stratification maintenance, turbulent mixing, and thermal stratification disappearance. The magnitude of the initial pressure difference significantly affects the temperature response and pressure equilibration time of the two chambers. The gas-phase space achieves thermal uniformity in approximately 4.1 s under sloshing, demonstrating its role as a “dynamic thermal buffer.” The research reveals the critical function of the gas-phase space in the dynamic thermal management of liquid hydrogen storage tanks, providing guidance for enhancing the safety and stability of the onboard hydrogen storage system. Full article