Transport coefficient approach for characterizing nonequilibrium dynamics in soft matter.

Nonequilibrium states in soft condensed matter require a systematic approach to characterize and model materials, enhancing predictability and applications. Among the tools, X-ray photon correlation spectroscopy (XPCS) provides exceptional temporal and spatial resolution to extract dynamic insight into the properties of the material. However, existing models might overlook intricate details. We introduce an approach for extracting the transport coefficient, denoted as [Formula: see text], from the XPCS studies. This coefficient is a fundamental parameter in nonequilibrium statistical mechanics and is crucial for characterizing transport processes within a system. Our method unifies the Green-Kubo formulas associated with various transport coefficients, including gradient flows, particle-particle interactions, friction matrices, and continuous noise. We achieve this by integrating the collective influence of random and systematic forces acting on the particles within the framework of a Markov chain. We initially validated this method using molecular dynamics simulations of a system subjected to changes in temperatures over time. Subsequently, we conducted further verification using experimental systems reported in the literature and known for their complex nonequilibrium characteristics. The results, including the derived [Formula: see text] and other relevant physical parameters, align with the previous observations and reveal detailed dynamical information in nonequilibrium states. This approach represents an advancement in XPCS analysis, addressing the growing demand to extract intricate nonequilibrium dynamics. Further, the methods presented are agnostic to the nature of the material system and can be potentially expanded to hard condensed matter systems.

Effects of Hydrostatic Pressure and Cation Type on the Chloride Ion Transport Rate in Marine Concrete: An Experimental Study.

The effect of hydrostatic pressure and cation type on chloride ion transport in marine underwater concrete cannot be ignored. The study of the chloride ion transport behavior of concrete under the effect of hydrostatic pressure and cation type coupling can provide a basis for durability design and the protection of marine concrete. In this work, the chloride ion transport behavior of marine concrete in four common chloride salt solutions under different hydrostatic pressures is studied by a hydrostatic pressure test device developed by the authors. The results show that hydrostatic pressure and its action time significantly influence the chloride ion transport behavior in marine concrete; the higher the hydrostatic pressure of concrete, the faster the chloride ion transport rate. The longer the time, the more chloride ions accumulated in the same position, and the farther the chloride ion transport distance. Cation type has a certain influence on the transport process of chloride ions. Under the same test conditions, the chloride ion transport rate in a divalent cation solution is about 5% higher than that in a monovalent cation solution. The results also show that the chloride ion binding capacity under hydrostatic pressure is only 10~20% of that under natural diffusion. Using the test results, a predictive model of a chloride ion apparent transport coefficient based on the hydrostatic pressure and hydrostatic pressure action time corrected by a cation type influence coefficient is established.

[Effects of Four Amendments on Cadmium Bioavailability and Enzyme Activity in Purple Soil].

In this study, the effects of four types of amendments on effective Cd and Cd content in different parts of prickly ash soil and soil enzyme activity were studied, which provided scientific basis for acidification improvement of purple soil and heavy metal pollution control. A field experiment was conducted. Six treatments were set up:no fertilizer (CK), only chemical fertilizer (F), lime + chemical fertilizer (SF), organic fertilizer + chemical fertilizer (OM), biochar + chemical fertilizer (BF), and vinasse biomass ash + chemical fertilizer (JZ). Soil pH; available Cd (DTPA-Cd); Cd content in branches, leaves, shells, and seeds of Zanthoxylum; as well as the activities of catalase (S-CAT), acid phosphatase (S-ACP), and urease (S-UE) in different treatments were studied, and their relationships were clarified. The results showed following:① The two treatments of vinasse biomass ash + chemical fertilizer and lime + chemical fertilizer significantly increased soil pH (P < 0.05) to 3.39 and 2.25 units higher than that in the control, respectively. Compared with that in the control treatment, the content of available Cd in soil under vinasse biomass ash + chemical fertilizer and lime + chemical fertilizer treatment decreased by 28.91 % and 20.90 %, respectively. ② The contents of Cd in leaves, shells, and seeds of Zanthoxylum were decreased by 31.33 %, 30.24 %, and 34.01 %, respectively. The Cd enrichment ability of different parts of Zanthoxylum was different, with the specific performances being leaves > branches > seeds > shells. Compared with that of the control, the enrichment coefficient of each part of Zanthoxylum treated with vinasse biomass ash + chemical fertilizer decreased significantly(P < 0.05)by 27.54 %-40.0 %. ③ The changes in catalase and urease activities in soil treated with amendments were similar. Compared with those in the control group, the above two enzyme activities were significantly increased by 191.26 % and 199.50 %, respectively, whereas the acid phosphatase activities were decreased by 16.45 %. Correlation analysis showed that soil available Cd content was significantly negatively correlated with soil pH value(P < 0.01), S-CAT and S-UE enzyme activities were significantly positively correlated with soil pH(P < 0.01), and the soil available Cd content was significantly negatively correlated (P < 0.01); the S-ACP enzyme showed the complete opposite trends. The application of lime and vinasse biomass ash to acidic purple soil had the most significant effect on neutralizing soil acidity. It was an effective measure to improve acidic purple soil and prevent heavy metal pollution by reducing the effective Cd content in soil and improving the soil environment while inhibiting the absorption and transfer of Cd in various parts of Zanthoxylum.

Theoretical analysis of the effect of isotropy on the effective diffusion coefficient in the porous and agglomerated phase of the electrodes of a PEMFC.

In polymer membrane fuel cells (PEMFC), the pore microstructure and the effective diffusion coefficient ( D eff ) of the catalytic layer have a significant impact on the overall performance of the fuel cell. In this work, numerical methods to simulate PEMFC catalytic layers were used to study the effect of isotropy ( I xy ) on the D eff . The proposed methodology studies reconstructed systems by Simulated Annealing imaging with different surface fractions of microstructures composed by two diffusive phases: agglomerates and pores. The D eff is determined numerically by the Finite Volume Method solved for Fick's First Law of Diffusion. The results show that the proposed methodology can effectively quantify the effect of isotropy on the D eff for both diffusion phases. Two trends were obtained in the magnitude of the D eff concerning the change in isotropy: (1) an analytical equation is proposed in this article for D eff ≥ 5 % D 0 and (2) numerical solutions are determined for D eff < 5 % D 0 . In our analytical equation are both a lineal and a logarithmic sweep. When the surface fraction is ∅ = 50%, the D eff decreases more linearly than ∅ = 10 % at the beginning of the isotropy change, which indicates that small changes in isotropy in the particulate material modify it drastically; under these conditions the diffusion coefficient in the pore is predominant. (3) When the surface fraction is less than 50%, the D eff decreases more exponentially at the beginning and more linearly at the end of the isotropy change, which shows that small isotropy changes in the bar-aligned material drastically alter it. In this trend, diffusion in the agglomerate is less affected by isotropy. The proposed methodology can be used as a design tool to improve the mass transport in porous PEMFC electrodes.

Anisotropic molecular diffusion in confinement II: A model for structurally complex particles applied to transport in thin ionic liquid films.

HYPOTHESIS: Diffusion in confinement is an important fundamental problem with significant implications for applications of supported liquid phases. However, resolving the spatially dependent diffusion coefficient, parallel and perpendicular to interfaces, has been a standing issue and for objects of nanometric size, which structurally fluctuate on a similar time scale as they diffuse, no methodology has been established so far. We hypothesise that the complex, coupled dynamics can be captured and analysed by using a model built on the 2-dimensional Smoluchowski equation and systematic coarse-graining. METHODS AND SIMULATIONS: For large, flexible species, a universal approach is offered that does not make any assumptions about the separation of time scales between translation and other degrees of freedom. The method is validated on Molecular Dynamics simulations of bulk systems of a family of ionic liquids with increasing cation sizes where internal degrees of freedom have little to major effects. FINDINGS: After validation on bulk liquids, where we provide an interpretation of two diffusion constants for each species found experimentally, we clearly demonstrate the anisotropic nature of diffusion coefficients at interfaces. Spatial variations in the diffusivities relate to interface-induced structuring of the ionic liquids. Notably, the length scales in strongly confined ionic liquids vary consistently but differently at the solid-liquid and liquid-vapour interfaces.

Feasibility of electrodeionization for phosphate removal.

In this study, electrodeionization (EDI) in bath mode was tested regarding its capability to remove phosphate (PO4 3- ) ions from aqueous solutions. Various parameters affecting the phosphate removal rate via EDI were determined. The results showed that the phosphate removal rate depends on the applied voltage and that the optimum potential was 15 V, corresponding to a phosphate removal rate of 97%. Changing the stream rate of the phosphate-containing solution also affected the phosphate removal rate. Changing the pH of the phosphate-containing solution from 2 to 6 enhanced the phosphate removal rate from 80% to 97%. The presence of Cl- , NO3 - , and SO4 2- ions did not affect the phosphate removal rate. The highest mass transfer coefficient (k) of phosphate was calculated to be 7.85 × 10-4  m/s, and the flux was calculated to be 3.72 × 10-4  mol/m2  s1 at a flow velocity of 3 L/h. Thus, the study results showed the feasibility of EDI as an alternative membrane process for removing phosphate from aqueous solutions. PRACTITIONER POINTS: Electrodeionization was employed for the removal of phosphate. The removal of phosphate exhibited dependence on applied potential. EDI demonstrated a remarkable 97% efficiency in phosphate removal. The pH of the solution was found to influence the removal rate.

Anisotropic molecular diffusion in confinement I: Transport of small particles in potential and density gradients.

HYPOTHESIS: Diffusion in confinement is an important fundamental problem with significant implications for applications of supported liquid phases. However, resolving the spatially dependent diffusion coefficient, parallel and perpendicular to interfaces, has been a standing issue. In the vicinity of interfaces, density fluctuations as a consequence of layering locally impose statistical drift, which impedes the analysis of spatially dependent diffusion coefficients even further. We hypothesise, that we can derive a model to spatially resolve interface-perpendicular diffusion coefficients based on local lifetime statistics with an extension to explicitly account for the effect of local drift using the Smoluchowski equation, that allows us to resolve anisotropic and spatially dependent diffusivity landscapes at interfaces. METHODS AND SIMULATIONS: An analytic relation between local crossing times in system slices and diffusivity as well as an explicit term for calculating drift-induced systematic errors is presented. The method is validated on Molecular Dynamics simulations of bulk water and applied to simulations of water in slit pores. FINDINGS: After validation on bulk liquids, we clearly demonstrate the anisotropic nature of diffusion coefficients at interfaces. Significant spatial variations in the diffusivities correlate with interface-induced structuring but cannot be solely attributed to the drift induced by local density fluctuations.

[Effects of Sulfamethazine in Soil on Rice Growth].

For the sake of investigating the effects of residual antibiotics in soil on plant growth, sulfamethazine, which is commonly detected in soil, was selected in this project. In general, the growth index of rice at the seedling and mature stages, physiological/biochemical characteristics of roots and leaves, antibiotic residues, enrichment factors, and transport coefficients in various rice organs were respectively tested and analyzed to evaluate the ecological effects of sulfamethazine residues on rice. The results revealed that the inhibitory effect of sulfamethazine on plant height and biomass was maintained during the whole growth cycle. Moreover, the effect at the seedling stage was greater than that at the growth maturity stage, and the root part was more easily influenced than the seedling section. The root activity, nitrate reductase activity, and leaf chlorophyll content at the seedling stage were hindered by the increase in antibiotic content. By contrast, the antioxidant enzyme change showed a different tendency, in which the superoxide was activated, and the catalase and peroxidase were firstly activated and then inhibited. The sulfamethazine accumulation in various rice organs was in the order of root>leaf>sti>grain. The results of antibiotic risk assessment of rice grains exhibited that EDI/ADI was less than 0.1, indicating no health risk. The effect of sulfamethazine on enrichment factors and transport coefficients at the growth maturity stage was more obvious than that at the seedling stage. Considering the adverse effects of sulfamethazine on rice, we need to take the ecological effects of sulfamethazine on plants into consideration when applying livestock manure as organic fertilizer or using aquaculture water for irrigation, to ensure crop production safety.

Comparative Analysis of Lead Removal from Liquid Copper by ICF and CCF Refining Technologies.

Innovative technologies require the use of materials that meet increasingly high requirements; one such requirement is the purity of metals. In the case of copper, this translates into a parameter related to electrical conductivity. Traditional metal refining technologies have some limitations that can be eliminated through the use of modern melting aggregates. Such solutions include vacuum induction furnaces, comprising an induction furnace with a cold crucible. As part of this work, the possibilities of refining copper and lead alloys were investigated. In addition, the research was carried out with the use of two induction vacuum aggregates, allowing us to compare their effectiveness. The tests were carried out in a pressure range of 10-1000 Pa and at temperatures of 1273-1473 K. The results obtained made it possible to determine the mass transport coefficient of lead from an alloy with copper, and to determine the share of resistance in individual stages of the process. For experiments conducted inside an induction crucible furnace, lowering the working pressure inside the furnace chamber from 1000 to 10 Pa while increasing the temperature from 1323 to 1473 K was accompanied by a drop in the lead concentration inside the alloy of 69 to 96%, compared to its initial mass. For experiments conducted inside a cold crucible furnace, approximate values of lead removal appeared for lower temperatures (1273 to 1323 K), confirming that the analyzed process happens faster in this aggregate.

Nitrogen application practices to reduce cadmium concentration in rice (Oryza sativa L.) grains.

Cadmium (Cd) pollution in paddy soils creates challenges in rice grain production, thereby threatening food security. The effectiveness of different base-tillering-panicle urea application ratios and the combined basal application of urea and Chinese milk vetch (CMV, Astragalus sinicus L.) in minimizing Cd accumulation in rice grains was explored in a Cd-contaminated acidic soil via a field experiment. The results indicated that under similar nitrogen (N) application rates, an appropriate amount of urea applied at the panicle stage or the combined basal application of urea and CMV decreased Cd absorption by rice roots and its accumulation in rice grains, as compared with that of conventional N application (control). Furthermore, under a 3:4:3 base-tillering-panicle urea application ratio or under a high basal application of CMV (37,500 kg hm-2), Cd concentrations in brown rice were significantly lower (40.7% and 34.1%, respectively) than that of control. Cadmium transport coefficient from root to straw was significantly higher than that of control when an appropriate amount of urea was applied at the panicle stage or when urea and CMV were applied basally, whereas the Cd transport coefficient from straw to brown rice was relatively lower. Moreover, soil pH, or the CEC and CaCl2-Cd concentrations under different N fertilizer treatment was not significantly different. However, the rice grain yield increased by 29.4% with basal application of a high CMV amount compared with that of control. An appropriate amount of urea applied at the panicle stage or the combined basal application of urea and CMV decreased Cd absorption by rice roots and inhibited its transport from straw to brown rice, thus reducing Cd concentration in brown rice. Therefore, combined with the key phase of Cd accumulation in rice, a reasonable urea application ratio or a basal application of high CMV amounts could effectively reduce Cd concentration in brown rice.

Quantitative Relationship Between Paddy Soil Properties and Cadmium Content in Tobacco leaves.

Tobacco readily accumulates cadmium (Cd), an unnecessary and poisonous element. A total of 107 soil and tobacco leaf samples were collected from South China, to clarify the quantitative relationship between soil properties and Cd content in tobacco leaves. The results showed that 86.9% of the total sampling points had soil cadmium in excess of standard value, and the ratio of active Cd content to total soil Cd content was 24.0%. The enrichment factor of tobacco Cd was 3.43. There was a significant positive correlation between Cd concentration in tobacco leaves and soil Cd content. Soil pH, organic matter and cation exchange amount were negatively correlated with the Cd enrichment factor of tobacco. This present study has provided a regression model of tobacco Cd content based on soil factors, which could accurately predict Cd content in different parts of tobacco.

Effect of An Image Resolution Change on the Effective Transport Coefficient of Heterogeneous Materials.

Electrochemical electrodes comprise multiple phenomena at different scales. Several works have tried to model such phenomena using statistical techniques. This paper proposes a novel process to work with reduced size images to reconstruct microstructures with the Simulated Annealing method. Later, using the Finite Volume Method, it is verified the effect of the image resolution on the effective transport coefficient (ETC). The method can be applied to synthetic images or images from the Scanning Electron Microscope. The first stage consists of obtaining the image of minimum size, which contains at least 98% of the statistical information of the original image, allowing an equivalent statistical study. The image size reduction was made by applying an iterative decimation over the image using the normalized coarseness to compare the amount of information contained at each step. Representative improvements, especially in processing time, are achieved by reducing the size of the reconstructed microstructures without affecting their statistical behavior. The process ends computing the conduction efficiency from the microstructures. The simulation results, obtained from two kinds of images from different materials, demonstrate the effectivity of the proposed approach. It is important to remark that the controlled decimation allows a reduction of the processor and memory use during the reconstruction and ETC computation of electrodes.

Scenario analysis of the impacts of socioeconomic development on phosphorous export and loading from the Dongting Lake watershed, China.

Socioeconomic development in lake watersheds is closely related with lake nutrient pollution. As the second largest freshwater lake in China, the Dongting Lake has been experiencing an increase in nutrient loading and a growing risk of eutrophication. This study aimed to reveal the likely impacts of the socioeconomic development of the Dongting Lake watershed on the phosphorous pollution in the lake. We estimated the contributions from different sources and sub-watersheds to the total phosphorous (TP) export and loading from the Dongting Lake watershed under two most likely socioeconomic development scenarios. Moreover, we predicted the likely permissible and actual TP loadings to the Dongting Lake. Under both two scenarios, three secondary sub-watersheds-the upper and lower reaches of the Xiang River watershed and the Dongting Lake Area-are expected to dominate the contribution to the TP export from the Dongting Lake watershed in 2020. Three primary sub-watersheds-the Dongting Lake Area, the Xiang River, and the Yuan River watersheds-are predicted to be the major contributors to the TP loading from the entire watershed. The two scenarios are expected to have a slight difference in TP export and lake TP loading. Livestock husbandry is expected to be the predominant anthropogenic TP source in each of the sub-watersheds under both scenarios. Compared to 2010, permissible TP loading is not expected to increase but actual TP loading is predicted to grow significantly in 2020. Our study provides methodologies to identify the key sources and regions of lake nutrient loading from watersheds with complex socioeconomic context, and to reveal the potential influences of socioeconomic development on nutrient pollution in lake watersheds.

Transport in Proton Exchange Membranes for Fuel Cell Applications-A Systematic Non-Equilibrium Approach.

We hypothesize that the properties of proton-exchange membranes for fuel cell applications cannot be described unambiguously unless interface effects are taken into account. In order to prove this, we first develop a thermodynamically consistent description of the transport properties in the membranes, both for a homogeneous membrane and for a homogeneous membrane with two surface layers in contact with the electrodes or holder material. For each subsystem, homogeneous membrane, and the two surface layers, we limit ourselves to four parameters as the system as a whole is considered to be isothermal. We subsequently analyze the experimental results on some standard membranes that have appeared in the literature and analyze these using the two different descriptions. This analysis yields relatively well-defined values for the homogeneous membrane parameters and estimates for those of the surface layers and hence supports our hypothesis. As demonstrated, the method used here allows for a critical evaluation of the literature values. Moreover, it allows optimization of stacked transport systems such as proton-exchange membrane fuel cell units where interfacial layers, such as that between the catalyst and membrane, are taken into account systematically.

Assessment of Influence of Magnetic Forces on Aggregation of Zero-valent Iron Nanoparticles.

Aggregation of zero-valent nanoparticles in groundwater is influenced by several physical phenomena. The article shortly introduces preceding works in modeling of aggregation of small particles including influence of sedimentation, velocity profile of water, heat fluctuations, and surface electric charge. A brief description of inclusion of magnetic forces into the model of aggregation follows. Rate of influence of the magnetic forces on the aggregation depends on the magnitude of magnetization of the particles, radius of nanoparticles, size of the aggregates, and their concentration in the solution. Presented results show that the magnetic forces have significant influence on aggregation especially of the smallest iron particles.