Heterogeneous Surface Research Articles

Characteristics and regulatory mechanisms of net ecosystem CO2 exchange at the water-air interface in coastal aquaculture ponds

Coastal aquaculture ponds represented a biogeochemical hotspot in the global carbon cycle. However, there was a limited understanding of their dynamics. In this study, the eddy covariance (EC) technique was applied to quantify the net ecosystem CO2 exchange (NEE) over coastal aquaculture ponds in the Liaohe River estuary in northern China during 2020, aiming to investigate and quantify the carbon exchange characteristics of this region. The results showed that (a) a predominant “U” shaped diurnal NEE pattern throughout the year. During the sea cucumber monoculture phase, the ponds exhibited a consistent daytime carbon sink and nighttime carbon source pattern. In contrast, during the shrimp and sea cucumber polyculture phase, the ponds mostly remained in a net carbon sink state. (b) NEE was negatively correlated with photosynthetically active radiation (PAR), air temperature (Tair), and wind speed (WS), while showing a positive correlation with atmospheric pressure (AP). (c) Overall, the entire study area (complex underlying surfaces) functioned as a carbon sink in 2020, with a total net carbon sequestration of 281.533 g C·m−2. This was approximately four times greater than the restored wetlands that naturally formed from decommissioned coastal aquaculture ponds. Adjusting for surface heterogeneity revealed that the complex surfaces led to a 34.28 % underestimation of the aquaculture region's unit area carbon sequestration capacity. This study was crucial for assessing the carbon cycling and sequestration functions of coastal aquaculture pond ecosystems and provided a scientific basis for related ecological restoration projects.

A preliminary observational study on the characteristics of surface turbulent fluxes over the South China Sea Islands

AbstractIn recent years, there has been a rise in human activities in oceanic areas, making the land–atmosphere interactions over islands a major scientific concern on a global scale. Examining the observation data from offshore areas enables a more comprehensive understanding of the turbulent fluxes in offshore atmospheric environments, patterns of momentum, energy and material exchange between the atmosphere and underlying surface in an oceanic boundary layer, and development of a heterogeneous atmospheric boundary layer. The related findings will assist in developing theoretical models and parameterization schemes to simulate the influence of heterogeneous surfaces on land–atmosphere interactions on the South China Sea Islands. Existing studies on the turbulent fluxes over the South China Sea Islands were mainly conducted on the Nansha Islands, whereas studies on the waters of the South China Sea are scarce. In this study, we used 10 Hz high‐frequency turbulence measurements to calculate the latent and sensible heat fluxes over the South China Sea Islands using the eddy correlation method. These findings were then compared with data from the Dunhuang Gobi, Ordos desert, and Xilingol grassland regions in inland China, along with the observed net radiation and surface heat fluxes. The findings indicate that the energy fluxes over the South China Sea in summer exhibit prominent diurnal variations. The magnitude of either latent or soil heat flux is low, and the net radiation is predominantly transformed into sensible heat flux, which warms the atmosphere. Furthermore, the daily variation curves of sensible and latent heat fluxes are influenced by intermittent turbulence on the islands and reefs, resulting in a less smooth pattern compared with soil heat flux. Although the South China Sea Islands have small land areas and are surrounded by the sea, the land–atmosphere interactions over the underlying surface of this region are similar to those over the underlying surface of grasslands in inland China during summer. The daily mean sensible heat flux on the islands is higher than that in an inland area, and the time lag in its response to sunrise is longer than that in inland areas by approximately 1 h. The overall energy balance ratio is approximately 0.75, c which is in line with the average level, but an energy balance residual of approximately 25% still exists. Furthermore, extreme weather conditions, such as typhoons, can disrupt the diurnal variations of sensible and latent heat fluxes, and the cyclical patterns are subsequently restored.

Tuning surface Mn defects on LaMnO3 perovskite oxides by selective dissolution strategy for enhanced phosphate removal

Selective dissolution is widely used to adjust the surface state of LaMnO3 perovskite oxides. In this study, LaMnO3(LMO) with B-Site vacancies was synthesized using ascorbic acid to selectively remove Mn cations and enhance phosphate adsorption. The optimized LMO with Mn defects (LMO-AA3) presented large surface area, plenty of mesoporosity and suitable electronic structure. Particularly, the adsorption capacity (113.48 mg/g) of LMO-AA3 was about10 times that of LMO. Adsorption experiments showed adsorption occurred both chemically and physically on the heterogeneous adsorption surfaces, as the pseudo-second-order kinetic model and the Redlich-Peterson isotherm model predicted. The stimulated mechanism of LMO-AA3 achieved phosphate absorption through enhancing electrostatic attraction and ligand exchange by –OH groups. Regeneration testing showed that LMO-AA3 can be used for both high and low-concentration purification of phosphate. The selectively remove Mn cations method may offer an appropriate choice for enhancing the material characteristics of effective phosphate capture.

Efficient removal of organophosphate insecticide employing magnetic chitosan-derivatives

Herein, this work reports an efficient acephate adsorption using chitosan (CS) incorporating varying amounts of magnetite. A co-precipitation methodology was employed for the functionalization of chitosan with iron nanoparticles, using Fe2+ as the sole iron source and with a low energy requirement. The adsorbents were characterized by FTIR, XRD, VSM, and nitrogen porosimetry techniques. The CS∙Fe3O4 1:1 NPs showed the highest acephate removal percentage (74.96 %) at pH 9 and ambient temperatures. The adsorption process exhibited high dependencies on pH, adsorbent dosage, initial concentration of adsorbate, and ionic strength. Sips and pseudo-second-order kinetics models best adjusted the experimental data, suggesting that the process occurs on a heterogeneous surface. Thermodynamic evaluation showed that the adsorption was exothermic, favorable, and predominately through chemical interactions. Finally, the CS∙Fe3O4 showed no significant decrease after several cycles of adsorption/desorption, avoiding centrifugation-filtration steps.

Effect of Fe2O3 on CeO2 films in the photocatalytic evaluation towards the degradation of brilliant green and oxytetracycline

This paper presents a photochemical synthesis method for producing pure CeO2 deposits and CeO2 deposits loaded with varying proportions of Fe2O3. The deposits were calcined at 950 °C and characterized structurally, compositionally, and morphologically using XRD, XPS, SEM, FT-IR, and Raman spectroscopy techniques. Cerianite and hematite phases were identified in CeO2/Fe2O3 samples, indicating heterogeneous surface deposits. Photocatalytic testing under UV–Vis illumination for 5 h demonstrated promising results. For the degradation of bright green dye, efficiencies of 78.9 % and 90.1 % were achieved for pure CeO2 and CeO2 samples loaded with 1.0 mol% Fe2O3, respectively. Similarly, for oxytetracycline drug degradation, performance rates of 35.3 % and 67.0 % were observed for CeO2 and CeO2 samples loaded with 1.0 mol% Fe2O3, respectively. Recyclability tests showed a gradual decline in photocatalytic performance over successive cycles due to by-product accumulation contaminating the catalyst.

A pore-scale lattice Boltzmann model for solute transport coupled with heterogeneous surface reactions and mineral dissolution

In this paper, we propose a pore-scale lattice Boltzmann model to simulate fluid flow coupled with heterogeneous surface reactions and mineral dissolution. The primary innovation lies in the transformation of surface reactions, originally treated as a boundary condition, into a volume-source term through dimensional augmentation within the framework of sharp liquid–solid interfaces. This significantly simplifies the implementation, particularly for reactions occurring in porous media with intricate geometric structures. Several benchmark tests were performed to validate the accuracy of this model, including a reaction–diffusion problem in a rectangular domain, a two-dimensional reaction and dissolution of a circular grain, as well as a three-dimensional calcite crystal dissolution in a micro-channel. All the obtained simulation results agree well with the reference solutions. In addition, a dissolution problem in a three-dimensional porous medium built with the sand pack is then investigated. Cases with different Péclet numbers (Pe) and Damköhler numbers (Da) were simulated, and five dissolution modes were obtained, which were finally summarized in a diagram of Pe and Da.

Site heterogeneity and broad surface-binding isotherms in modern catalysis: Building intuition beyond the Sabatier principle

Learning the science of heterogeneous catalysis and electrocatalysis always starts with the simple case of a flat, uniform surface with an ideal adsorbate. It has of course been recognized for a century that real catalysts are more complicated. For the increasingly complex catalysts of the 21st century, this Perspective argues that surface heterogeneity and non-ideal binding isotherms are central features, and their implications need to be incorporated in current thinking. A variety of systems are described herein where catalyst complexity leads to broad, non-Langmuirian surface isotherms for the binding of hydrogen atoms – and this occurs even for ideal, flat Pt(111) surfaces. Modern catalysis employs nanoscale materials whose surfaces have substantial step, edge, corner, impurity, and other defect sites, and they increasingly have both metallic and non-metallic elements MnXm, including metal oxides, chalcogenides, pnictides, carbides, doped carbons, etc. The surfaces of such catalysts are often not crystal facets of the bulk phase underneath, and they typically have a variety of potential active sites. Catalytic surfaces in operando are often non-stoichiometric, amorphous, dynamic, and impure, and often vary from one part of the surface to another. Understanding of the issues that arise at such nanoscale, multi-element catalysts is just beginning to emerge. Yet these catalysts are widely discussed using Brønsted/Bell-Evans-Polanyi (BEP) relations, volcano plots, Tafel slopes, the Butler-Volmer equation, and other linear free energy relations (LFERs), which all depend on the implicit assumption that the active sites are “similar” and that surface adsorption is close to ideal. These assumptions underly the ubiquitous intuition based on the Sabatier Principle, that the fastest catalysis will occur when key intermediates have free energies of adsorption that are not too strong nor too weak. Current catalysis research often aims to minimize the complexity of non-ideal isotherms through experimental and computational design (e.g., the use of single crystal surfaces), and these studies are the foundation of the field. In contrast, this Perspective argues that the heterogeneity of binding sites and binding energies is an inherent strength of these catalysts. This diversity makes many nanoscale catalysts inherently a high-throughput screen wrapped in a tiny package. Only by making the heterogeneity part of the foundation of catalysis models, sorting the types of active sites and dissecting non-ideal binding isotherms, will modern catalysis learn to harness the inherent diversity of real catalysts. Controlling and exploiting diversity rather than avoiding it will help to optimize complex modern catalysts and catalytic conditions.

Enhanced adsorption of Cr(VI) pollutants using CaFe2O4@rGO modified-biochar derived from mixture of black soldier flier exuviae and durian peel

To solve the problem of hexavalent chromium (Cr(VI))-polluted water sources, mixed black soldier flier exuviae (BSFE) and durian peel (DP)-derived biochar modified with CaFe2O4@rGO (BC-CFr) was synthesized to remove Cr(VI) from wastewater. Our findings indicated that the adsorption of Cr(VI) on BC-CFr reached a maximum at a pH of 2.0, biochar dosage of 0.3 g/100 mL, and initial Cr(VI) concentration of 50 mg/L, with a Cr(VI) adsorption capacity of 30.8 mg/g, which was approximately two times greater than that on pristine biochar (PBC). The characterization results showed that the as-prepared modified biochar was rich in surface functional groups, including amine groups (−NH2) and active sites. Cr(VI) adsorption followed the Elovich kinetic and Freundlich isotherm models, illustrating the adsorption process involved multilayer on the heterogeneous surface. The thermodynamic study confirmed the adsorption process was endothermic. The proposed adsorption mechanisms included adsorption-coupled reduction, electrostatic attraction, and pore filling. This study provided a simple method to prepare compositing biochar using abundantly available agricultural by-products that dealt with the dual problems of Cr(VI)-contaminated water and agricultural solid waste. Besides, the BC-CFr exhibited high desorption performance and recyclability over five consecutive adsorption-desorption cycles, suggesting the BC-CFr is a feasible nanocomposite biochar for effectively removing Cr(VI) from wastewater in practice.

Valorisation of bamboo stalk waste: eco-friendly synthesis and characterisation of activated carbon monolith

ABSTRACT In contemporary waste management, the escalating volumes of bamboo stalk waste present a pressing environmental challenge, necessitating innovative and sustainable solutions. This research examined the properties of activated carbon monolith (ACM) derived from bamboo stalk (BS) using a facile method. Polystyrene resin and KOH were employed as an eco-binder and activator in the monolith synthesis, respectively. Analytical methods were employed to characterise the mechanical, morphological, elemental, and textual profiles of the monolith obtained. The study's results indicated the creation of a monolith characterised by a rough, amorphous shape firmly secured by the binder. It revealed a BET surface area measuring 265 m2/g and a pore diameter of 2.8 nm. The monolith displayed various irregular void pores, forming a mesoporous morphological network, along with sporadically distributed slivery-white dot-like particles on its heterogeneous surface. EDX analysis also revealed the BS-ACM is largely composed of carbon (77%), potassium (11%), oxygen (8%), and trace amounts of aluminium, gold, iron, and plutonium. The compressive strength test indicated a peak force of 21,536 N before any significant signs of appreciable deformation were observed, with the subsequent estimation of Young's modulus at 8.34 MPa. Beyond advancing bamboo waste valorisation, the research aligns with circular economy principles and sustainable practices, presenting a promising pathway for developing eco-friendly materials and contributing to a more sustainable and resource-efficient future.

Theoretical model of dynamics and stability of nanobubbles on heterogeneous surfaces

Surface nanobubbles have revealed a new mechanism of gas–liquid–solid interaction at the nanoscale; however, the nanobubble evolution on real substrates is still veiled, because the experimental observation of contact line motions at the nanoscale is too difficult. HypothesisThis study proposes a theoretical model to describe the dynamics and stability of nanobubbles on heterogeneous substrates. It simultaneously considers the diffusive equilibrium of the liquid–gas interface and the mechanical equilibrium at the contact line, and introduces a surface energy function to express the substrate’s heterogeneity. ValidationThe present model unifies the nanoscale stability and the microscale instability of surface bubbles. The theoretical predictions are highly consistent to the nanobubble morphology on heterogeneous surfaces observed in experiments. As the nanobubbles grow, a lower Laplace pressure leads to weaker gas adsorption, and the mechanical equilibrium can eventually revert to the classical Young-Laplace equation above microscale. FindingsThe analysis results indicate that both the decrease in substrate surface energy and the increase in gas oversaturation are more conducive to the nucleation and growth of surface nanobubbles, leading to larger stable sizes. The larger surface energy barriers result in the stronger pinning, which is beneficial for achieving stability of the pinned bubbles. The present model is able to reproduce the continual behaviors of the three-phase contact line during the nanobubble evolution, e.g., “pinning, depinning, slipping and jumping” induced by the nanoscale defects.

Impacts of forest canopy heterogeneity on plot-scale hydrometeorological variables - Insights from an experiment in the humid boreal forest with the Canadian Land Surface Scheme

High latitude regions, including the circumpolar boreal biome, are experiencing important changes in the availability of usable surface water because of climate change. In this context, an adequate representation of the land-atmosphere interaction is critical to ensure optimal management of current and future water resources, forest management, and climate prediction. However, the task is particularly intricate in high-latitude boreal forest, as land surface model faces several challenges due to the unique environmental conditions and ecological characteristics. The objective of this study is to quantify the impact of forest landscape heterogeneity, specifically stand leaf-area index (LAI), soil texture, and drainage regime, on surface water and energy balance in a small boreal high-latitude sub-catchment. To this end, hydrometeorological conditions at seventeen 20×20 m plots in a 1-km2 boreal forest sub-basin are simulated using the Canadian Land Surface Scheme (CLASS), a land surface model, at the point scale. The subplot-scale soil texture, drainage regime, and vegetation characteristics and type are based as closely as possible on field measurements and observations for the 17 plots. The model-driven experiment comprises two sets of simulations using CLASS, each employing the same model setup and run for the 17 experimental plots. The main set employs meteorological forcing from a local micrometeorological tower within the sub-basin to investigate the plot-to-plot variability of albedo, energy fluxes, and soil state variables. A second set of simulations is conducted using meteorological forcing from the ERA5-Land reanalysis, which spans from 1986 to 2022. This data provides a longer time series, enabling a more accurate representation of the interannual climatic variability in the sub-basin. The results of the main and secondary sets of CLASS simulations are used to assess the plot-to-plot and temporal variability of several key hydrometeorological variables by calculating a monthly spread. In brief, the following conclusions and broader implications can be drawn from the findings: i) The simulated total annual evapotranspiration remains relatively uniform between plots despite notable variation in its partitioning from plot to plot. ii) In the presence of a full snowpack, the albedo exhibits substantial heterogeneity at the subplot scale, linked to the canopy's LAI. iii) Local soil properties, drainage regime, and vegetation structure and type exhibit substantial influence on the plot-to-plot variability in soil water content. iv) When parameterized with localized observations and measurements, CLASS can represent and be responsive to the complex dynamics of energy and water fluxes at the plot scale within the heterogeneous surface of boreal forests.

A coupled hand and surface hygiene criterion on heterogeneous surface touch networks

Contaminated hands of people and contaminated surfaces of inanimate objects (fomites) can spread microbes that cause enteric and respiratory infections. Thus, hand hygiene and surface hygiene are probably the most widely adopted public health interventions for controlling such infections. However, conclusions of studies on the effectiveness of these interventions are often inconsistent, likely because such studies have examined these interventions separately and thus not detected their interactions, leading to differing conclusions about their individual impact. In this study, it is proposed that hand and environmental surface hygiene (including disinfection) should be coupled to control contamination spread between surfaces, especially within heterogeneous surface touch networks. In these networks, surfaces and individuals have varying contact frequencies and patterns, reflecting the diverse and non-uniform interactions that typically occur in real-world environments. Accordingly, we propose a new theoretical framework to delineate the relationships between hand hygiene and surface hygiene. In addition, the performance of a model based on this framework that used real-world behavioural data from a graduate student office is reported. Moreover, a coupled hygiene criterion for heterogeneous networks is derived. This criterion stipulates that the product of the pathogen-removal rates for hands and surfaces must exceed a cleaning threshold to ensure the exponential decay of contamination. Failure to meet this threshold results in a non-zero steady prevalence of contamination. Furthermore, the cleaning threshold increases as the numbers of surfaces and hands increase, highlighting the significant impact of network structures on hygiene practices. Thus, extensive cleaning may be necessary in crowded indoor environments with many surfaces and occupants, such as cruise ships, to prevent super-large outbreaks of, for example, noroviral infections. Overall, the findings of this study reveal how improved and integrated hygiene control can prevent fomite transmission.

Improved WRF simulation of surface temperature and urban heat island intensity over Metro Manila, Philippines

Accurate representation of the land use/land cover (LULC) in the Weather Research and Forecasting (WRF) model has been shown to be crucial for improved simulation of surface variables and urban heat island (UHI) phenomenon. In this study, a ground truthed LULC dataset over Metro Manila (MM) was integrated in the WRF model to assess and quantify the relative contributions of using an updated land use/land cover (ULULC), activating the single-layer urban canopy model (WSLUCM) and anthropogenic heat (WAH), and consideration of urban surface heterogeneity (LIR) representation on simulated Surface Temperature (ST) relative to the default model settings (CTRL) of the WRF model. Additionally, the study examines the daytime and nighttime UHI features over MM, using a reference simulation where urban grids were replaced with cropland (CRP). Numerical simulations were carried out for April 2018, a typical dry month without monsoonal influence over MM to get a clear UHI characterization. Data from nine weather stations distributed across MM was used for performance evaluation. Results show negligible daytime biases in ST for CTRL, ULULC, and WAH, and underestimated ST for WSLUCM. At night, CTRL and ULULC (WSLUCM and WAH) tend to overestimate (underestimate) ST. Of the four factors analyzed, updating LULC, using SLUCM, including AH, and accounting for urban surface heterogeneity can change daytime ST by 0.3 °C, -0.6 °C, 0.3 °C, and 0 °C, respectively, and nighttime ST by 0.5 °C, -1.2 °C, 0.3 °C, and 0.4 °C, respectively. Widespread daytime warming and a distinct nocturnal UHI following urbanization were confirmed for MM when the LULC accounted for urban heterogeneity. While data limitations for MM limit the specification of the SLUCM, its UHI features are best represented in WRF when an updated land cover dataset is used.

The application of Rumex Abysinicus derived activated carbon/bentonite clay/graphene oxide/iron oxide nanocomposite for removal of chromium from aqueous solution

Rapid industrialization has significantly boosted economic growth but has also introduced severe environmental challenges, particularly in water pollution. This study evaluates the effectiveness of a nanocomposite composed of Rumex Abyssinicus Activated Carbon/Acid Activated Bentonite Clay/Graphene Oxide, and Iron Oxide (RAAC/AABC/GO/Fe3O4) for chromium removal from aqueous solutions. The preparation of the nanocomposite involved precise methods, and its characterization was performed using Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Brunauer–Emmett–Teller (BET) surface area analysis, and the point of zero charge (pHpzc). Batch adsorption experiments were designed using Design Expert software with a central composite design under response surface methodology. The factors investigated included pH (3, 6, and 9), initial Cr (VI) concentration (40, 70, and 100 mg/L), adsorbent dose (0.5, 0.75, 1 g/200 mL), and contact time (60, 90, and 120 min). Adsorption isotherms were analyzed using nonlinearized Langmuir, Freundlich, and Temkin models, while pseudo-first-order and pseudo-second-order models were applied to adsorption kinetics. Characterization revealed a pHpzc of 8.25, a porous and heterogeneous surface (SEM), diverse functional groups (FTIR), an amorphous structure (XRD), and a significant surface area of 1201.23 m2/g (BET). The highest removal efficiency of 99.91% was achieved at pH 6, with an initial Cr (VI) concentration of 70 mg/L, a 90 min contact time, and an adsorbent dose of 1 g/200 mL. Optimization of the adsorption process identified optimal parameters as pH 5.84, initial Cr (VI) concentration of 88.94 mg/L, contact time of 60 min, and adsorbent dose of 0.52 g/200 mL. The Langmuir isotherm model, with an R2 value of 0.92836, best described the adsorption process, indicating a monolayer adsorption mechanism. The pseudo-second-order kinetics model provided the best fit with an R2 value of 0.988. Overall, the nanocomposite demonstrates significant potential as a cost-effective and environmentally friendly solution for chromium removal from wastewater.

Cytologic Findings and Ancillary Tests Results of Sclerosing Pneumocytoma: Our Institutional Experience.

Sclerosing pneumocytoma (SP) is a rare benign tumor and a potential diagnostic pitfall. Our aim was to review the cytologic features of our surgically diagnosed SP cases including the clinical, immunohistochemical and available molecular findings. A computerized search from 2013 to 2020 for surgical cases with corresponding cytology specimens diagnosed as SP was performed. The clinical data, cytology, and surgical specimens were collated for analysis. Six cytology specimens were collected. All were female (mean age = 35). Three have incidental lung nodules and three with cough. Cytologic findings showed variable architectural pattern (papillary, solid, singly scattered, acinar/rosette-like) and cellular heterogeneity (surface, stromal, epithelioid, plasmacytoid cells). Atypia was identified in 4/6 cases. The original cytology diagnoses were negative = 1, SP = 2 and adenocarcinoma = 3. The latter diagnoses were amended to SP after review of the surgical specimens. The three false positive cases on review have cytologic features mimicking adenocarcinoma. Immunohistochemical stains showed tumor cells (surface and stromal) were positive for TTF-1, and EMA with only the surface cells positive for pancytokeratin and Napsin A. Though two cases sent for molecular testing were negative for AKT1 or CTNNB1 exon 3 mutation, our panel did not evaluate AKT1 exon 4. SP is a diagnostic pitfall with 50% initially misdiagnosed as adenocarcinoma. Integrating the clinical/radiologic findings, cytologic features, and performance of immunohistochemistry on cell block are helpful in avoiding misdiagnosis. Molecular testing for recurrent mutations, if present, could be helpful for diagnosis and possible therapy options. However, routinely used molecular testing may not always capture relevant molecular markers for SP.

Nanoporous carbons from hydrothermally pre-treated avocado waste: experimental design, hydrogen storage behavior, and energy distribution analysis

AbstractAvocado waste, which includes the peel and seed, is a promising biomass source for highly porous materials crucial to establishing an economical and efficient hydrogen economy. Hydrothermally pre-treated avocado waste was explored as a precursor for biocarbon optimized for hydrogen storage, employing the design of experiment to vary activation temperature and impregnation ratio. The resulting optimized biocarbon, synthesized at 800 °C with a 1:3 impregnation ratio, exhibited appreciable hydrogen uptake at 77 K and 1 bar, surpassing some reported literature values. Notably, the optimized biocarbon (AC200), hydrothermally pretreated at 200 °C, demonstrated a remarkable 3.07 wt% hydrogen uptake, attributed to its narrower micropores facilitating extensive adsorption. The study employed a modified Langmuir model incorporating homotattic patch approximation for a universal isotherm model, providing insights into the surface characteristics of the optimized biocarbon in terms of adsorption site availability and energy distribution. The modeling offers insight into the heterogeneous surface characteristics, specifically regarding the availability of adsorption sites, elucidating the distinct behavior exhibited by each optimized biocarbon.

Of flippers and wings: The locomotor environment as a driver of the evolution of forelimb morphological diversity in mammals

Abstract The early diversification of tetrapods into terrestrial environments involved adaptations of their locomotor apparatus that allowed for weight support and propulsion on heterogeneous surfaces. Many lineages subsequently returned to the water, while others conquered the aerial environment, further diversifying under the physical constraints of locomoting through continuous fluid media. While many studies have explored the relationship between locomotion in continuous fluids and body mass, none have focused on how continuous fluid media have impacted the macroevolutionary patterns of limb shape diversity. We investigated whether mammals that left terrestrial environments to use air and water as their main locomotor environment experienced constraints on the morphological evolution of their forelimb, assessing their degree of morphological disparity and convergence. We gathered a comprehensive sample of more than 800 species that cover the extant family‐level diversity of mammals, using linear measurements of the forelimb skeleton to determine its shape and size. Among mammals, fully aquatic groups have the most disparate forelimb shapes, possibly due to the many different functional roles performed by flippers or the relaxation of constraints on within‐flipper bone proportions. Air‐based locomotion, in contrast, is linked to restricted forelimb shape diversity. Bats and gliding mammals exhibit similar morphological patterns that have resulted in partial phenotypic convergence, mostly involving the elongation of the proximal forelimb segments. Thus, whereas aquatic locomotion drives forelimb shape diversification, aerial locomotion constrains forelimb diversity. These results demonstrate that locomotion in continuous fluid media can either facilitate or limit morphological diversity and more broadly that locomotor environments have fostered the morphological and functional evolution of mammalian forelimbs. Read the free Plain Language Summary for this article on the Journal blog.

Effect of heat treatment on chemical durability and TL dosimetric properties of Na2O-SrO-B2O3 glass system

Na2O-SrO-B2O3 glass system prepared by the known melting-quenching method was applied to a progressive heat treatment (HT) at 600 °C for 4, 6, 8 and 10 h. Glass (G) and its corresponding heat treated (HT) samples were characterized by density, molar volume and XRD technique that revealed the complete amorphous structure of the glassy matrix and the coexistence of two crystalline phases in the corresponding glass ceramics; monoclinic phase of NaSrBO3 and the triclinic phase of sodium strontium pentaborate Na3SrB5O10. Testing chemical durability of G and HT samples at 95 °C for 24 h, revealed higher chemical stability in aqueous (H2O) and acidic (H2SO4) solutions, while the highest leachability was detected in the alkaline medium (NaOH). pH of leaching solution was found to control the leaching process and displayed rising behavior with time of immersion. The progressive rising of leaching solution temperature; 25, 40, 60 and 95 °C, revealed a quiet leachable enhancement as well. SEM photographs represented rough and heterogeneous surface morphology with continual leaching and the formation of colloidal layers at the later stages of corrosion.The TL-dosimetric properties indicated extremely higher thermoluminescence properties of HT samples than the untreated glass. The analysis of the exhibited TL signals revealed the composition of the glow curves of the treated and untreated samples of eight TL components. The obtained results recommend the acceptable chemical durability of the heat treated samples especially in the neutral medium that displayed no more than 8.5% leachability rate yearly, besides their promising TL-dosimetric features, accordingly their possible application in the field of radiation dosimetry.

Ultrasonic assisted adsorption of methylene blue using blood clam shell as a low-cost adsorbent

Methylene blue is a synthetic dye used in various industries, such as wood, linen, and silk. Generally, as much as 10–200 mg/L of methylene blue is released into the environment and potentially polluting the environment. One of methylene blue removal method from wastewater is adsorption, particularly using blood clam (Anadara granosa) shells adsorbent. Blood clam shells contain CaCO3 (up to 98.7 %) that can be utilized to adsorb methylene. Furthermore, methylene blue adsorption can be enhanced by employed the ultrasonic wave. This research aims to prepare, characterize, and employ blood clam shells as a low-cost adsorbent in the ultrasonic-assisted methylene blue adsorption. The parameters studied were the adsorbent preparation method, adsorbate pH, adsorbent mass, contact time, and initial concentration. The adsorbent preparation method affected the morphology, elemental composition, functional groups, and average particle size, which were confirmed using SEM-EDX, FTIR, and PSA, where this kind of investigation has never been conducted before. Optimum conditions for methylene blue adsorption were obtained for adsorbent A3, pH 12, adsorbent mass of 0.5 g, contact time of 60 min, and initial concentration of 10 ppm, with a removal percentage of 98.614 %. This removal percentage increased by 63.119 % (espescially in A3) compared to without ultrasonic waves, which could only remove methylene blue by 35.495 %. Ultrasonic-assisted adsorption of methylene blue using blood clam shells adsorbent proceeded according to the Sips isotherm model (R2 = 0.9953) and pseudo-second-order kinetics (R2 = 0.939). A3 shows an extraordinary performance, with reusability up to six cylces. The adsorption occurs by electrostatic interaction between adsorbent's surface and cations in methylene blue, chemisorption, and the formation of monolayer adsorbate in heterogenous A3's surface.

Adsorptive removal of cationic dyes from wastewater using a novel sodium alginate-based iron oxide nanocomposite hydrogel: DFT and advanced statistical physics modelling

A novel Sodium alginate-based hydrogel reinforced with varying Fe2O3 nanoparticles loading (NCH) was synthesized to remove cationic dyes methylene blue (MB) and crystal violet (CV). The NCH, with 5 % Fe2O3 loading, demonstrated optimal removal efficiency for both dyes. Detailed spectroscopic, microscopic, and spectrometric characterization techniques verified the nanocomposite structure and dye adsorption. Batch experiments revealed that at pH: 9, with a 20 mg 100 mL−1 adsorbent dose and times of 60 min for MB and 40 min for CV, with an initial concentration of 500 mg L−1, maximum adsorption capacities were achieved. MB and CV adsorption onto NCH showed distinct mechanisms: MB via physical interaction, CV via both physical and chemical interactions, including electrostatic forces and hydrogen bonding. Despite differences, the Langmuir-Freundlich model best fit the equilibrium isotherms, suggesting monolayer adsorption dominated, even with heterogeneous surface sites on NCH. A dual-site M2 statistical physics model revealed that MB and CV adsorption occurred via a multi-molecular vertical configuration on the binding sites, with heterogeneous adsorption sites contributing to dye uptake. Density functional theory demonstrated higher adsorption affinity for MB over CV, primarily due to hydrogen bonding and electrostatic interactions. NCH exhibited 80 % dye removal efficiency after five cycles, highlighting its potential for industrial effluent treatment.