Effect Of Surface Heterogeneity Research Articles

Effects of horizontal grid resolution on evapotranspiration partitioning using TerrSysMP

Biotic leaf transpiration (T) and abiotic evaporation (E) are the two major pathways by which water is transferred from land surfaces to the atmosphere. Earth system models simulating the terrestrial water, carbon and energy cycle are required to reliably embed the role of soil and vegetation processes in order to realistically reproduce both fluxes including their relative contributions to total evapotranspiration (ET). Earth system models are also being used with increasing spatial resolutions to better simulate the effects of surface heterogeneity on the regional water and energy cycle and to realistically include effects of subsurface lateral flow paths, which are expected to feed back on the exchange fluxes and their partitioning in the model.Using the hydrological component of the Terrestrial Systems Modeling Platform (TerrSysMP), we examine the uncertainty in the estimates of T/ET ratio due to horizontal model grid resolution for a dry and wet year in the Inde catchment (western Germany). The aggregation of topography results in smoothing of slope magnitudes and the filtering of small-scale convergence and divergence zones, which directly impacts the surface-subsurface flow. Coarsening of the grid resolution from 120 m to 960 m increased the available soil moisture for ground evaporation, and decreased T/ET ratio by about 5% and 8% for dry and wet year respectively. The change in T/ET ratio was more pronounced for agricultural crops compared to forested areas, indicating a strong local control of vegetation on the ground evaporation, affecting the domain average statistics.

Ion Dynamics and Electrosorption in Carbon Electrodes with Bimodal Porosities and Heterogeneous Interfaces

Electrochemical capacitors offer high reliabilities and power densities and demonstrate exceptional promise in a broad range of energy storage and management applications. However, research efforts have not, to date, properly explored the influence of electrode interfaces’ heterogeneity and disorder on charge storage and dynamics of electrosorbed ions. Surface functional groups and structural carbon defects contribute quantum capacitance.[1] Specific surface functional groups, which must appropriately match the chemistries of electrosorbed ions, develop favorable interfaces that reduce impedance and improve cyclabilities.[2] Finally, ionophilic surfaces draw ions away from pore surfaces and improve electrosorption during charge and discharge processes.[3] However, these effects strongly depend on electrode pore dimensions and behaviors of ions in confinement. Furthermore, standard materials characterization and electrochemical testing techniques cannot properly assess interactions at electrode/electrolyte interfaces. Subsequently, in-depth studies must rely on combinations of well-tailored experimental model systems, in-depth X-ray and neutron scattering techniques, and computational modeling to assess the influences of disordered interfaces on capacitance. Our research investigated the effect of electrode surface heterogeneity and disorder in complex pore architectures and electrolytes with large, non-idealized electrolytes. The approach used carbide-derived carbons (CDCs) synthesized from a Mo2C precursor at 800 °C. This electrode material offered bimodal pore size distributions (0.8 nm and 2.6 nm diameter pores, shown in Figure 1a), and 1300 °C vacuum annealing or 400 °C air oxidation yielded, respectively, defunctionalized or oxidized pore surfaces. We filled these pores with 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([OMIm+][TFSI-]) room-temperature ionic liquid (RTIL). QENS measurements on these systems determined that the ions were significantly more mobile in oxidized pores than in defunctionalized pores (Figure 1b). A Cole-Cole model derived mobility information, and the RTIL diffusion coefficient in oxidized pores (2.71*10-10 m2 s-1) was more than twice as large as the one for the same RTIL in defunctionalized pores (1.05*10-10 m2 s-1) due to lower ion densities in oxidized pores. Electrochemical impedance analysis showed that electrochemically driven ionic mobility was higher in oxidized pores. On the other hand, defunctionalized pores demonstrated contained higher ion densities, and, subsequently, featured higher charge storage densities (Figure 3f). However, cyclic voltammograms suggested charge saturation and pore de-filling behaviors at low potentials; surface chemistry influenced the magnitude of this effect. Molecular dynamic (MD) simulations showed similar strong affinities of oxidized surfaces for RTIL ions, which lowered their charge storage densities in 2.6 nm diameter pores. X-ray Pair Distribution Function (PDF) analysis showed differences in ion-ion correlations between bulk and confined states and further underscored the influence of pore and ion diameter on electrode/electrolyte interactions at heterogeneous interfaces. [1] Dyatkin, B. & Gogotsi, Y. Effects of Structural Disorder and Surface Chemistry on Electric Conductivity and Capacitance of Porous Carbon Electrodes. Faraday Discussions172, 139-162, (2014). [2] Dyatkin, B., et al. Capacitance, Charge Dynamics, and Electrolyte-Surface Interactions in Functionalized Carbide-Derived Carbon Electrodes. Progress in Natural Science - Materials International25, 631–641, (2015). [3] Dyatkin, B., et al. Influence of Surface Oxidation on Ion Dynamics and Capacitance in Porous and Non-Porous Carbon Electrodes. The Journal of Physical Chemistry C, (2016). Figure 1

Asymmetric Conformational Transitions in AAA+ Biological Nanomachines Modulate Direction-Dependent Substrate Protein Unfolding Mechanisms.

Powerful AAA+ biological nanomachines, such as ClpY, form hexameric ring structures, which selectively process abnormal proteins targeted for degradation by unfolding and threading them through a narrow central channel. The molecular details of this process are not yet fully understood. We perform Langevin dynamics simulations using a coarse-grained model of substrate proteins (SPs), Titin I27 and its V13P variant, threading through the ClpY pore. We probe the effect of ClpY surface heterogeneity and changes in pore width on SP orientation and the direction of applied force during SP unfolding. We contrast mechanisms of SP unfolding in a restrained geometry, as in single-molecule force spectroscopy experiments, and in an unrestrained geometry, as in the in vivo degradation process. In open pore configurations, unfolding of unrestrained SPs occurs via an unzipping mechanism, which involves force application along a weak mechanical direction. In the partially closed pore, unfolding occurs via a shearing mechanism, with force application along a strong mechanical direction. By contrast, unfolding of the restrained I27 is limited to a shearing mechanism due to application of force along the strong mechanical direction. We propose that Clp nanomachine plasticity underlies direction-dependent pulling mechanisms that enable versatile SP remodeling actions.

Effect of surface heterogeneity on phosphorus adsorption onto mineral particles: experiments and modeling

Adsorptive interaction at the solid-water interface plays an important role in the fate and behavior of phosphorus (P) in rivers and lakes and the resulting eutrophication. This study aims to investigate the contributions of heterogeneous morphology to P adsorption onto mineral particles. The dominant minerals in Yellow River sediment, quartz, k-feldspar, and calcite are investigated with adsorption experiments and microscopic examinations. Taylor expansion is applied to quantitatively characterize the heterogeneous surface morphology. The results reveal that locally concave or convex micro-morphology characterized by the second derivative term of the Taylor expansion, F 2, can be related to adsorption capacity due to its effect on surface-charge density and distribution. The distribution of adsorbed P as a function of F 2 was determined for selected particles composed of each of the pure minerals and was fit to a Weibull distribution. Each mineral was characterized by F 2a , the weighted average value of F 2, and Weibull distribution factors, and correlated with sorption isotherms. The developed relationships were used to accurately predict adsorption onto individual particles as well as pure mineral samples. Mineral particles have complex surface morphology, which affects the interface P adsorption. Micro-morphological characterization of F 2 and F 2a can be used to predict adsorption onto the pure minerals, and this study provides physical basis for predicting adsorption on sediment particles composed of these minerals.

Coupled Effects of Ionic Strength, Particle Size, and Flow Velocity on Transport and Deposition of Suspended Particles in Saturated Porous Media

In this study, the coupled effect of ionic strength, particle size, and flow velocity on transport and deposition of suspended particles (SP) in saturated sand was undertaken. Three polydispersive SP populations (silt particles with the median of 3.5, 9.5 and 18.3 \(\upmu \)m) were investigated using a pulse injection technique. High ionic strengths were used and vary from 0 to 600 mM (NaCl). Two high velocities were tested: 0.15 and 0.30 cm/s. Suspended particles recovery and deposition kinetics were strongly dependent on the solution chemistry, the hydrodynamics, and the suspended particles size, with greater deposition occurring for increasing ionic strength, lower flow velocity, and larger ratios of the median diameter of the SP to the median sand grain diameter. A shift between the extended Derjaguin–Landau–Verwey–Overbeek theory prediction (the particles and sand grain surfaces are considered chemically and topographically homogeneous) and the experimental results for certain ionic strength was observed. So, as reported in recent literature, effects of surface heterogeneities should be considered. The residence time of the non-captured particles is dependent on ionic strength and hydrodynamic. A relationship between the deposition kinetics, particle and grain sizes, flow velocity, and ionic strength is proposed.

Effects of the surface heterogeneities on the local climate of a fragmented landscape in Amazonia using a tile approach in the Eta/Noah‐MP model

This study evaluates the use of tiles to estimate the effects of surface heterogeneities in simulations of local climate in a landscape‐fragmented region of Amazonia. Three experiments using the Eta/Noah‐MP model were designed as follows: two experiments with a spatial resolution of 5 km with and without the use of the tile approach. The third experiment used a finer spatial resolution of 2 km without the use of the tile approach (high‐resolution experiment). Simulations were carried out for the rainy and dry seasons, which correspond to the months of March and September 2003, respectively. In general, the magnitude of surface fluxes is significantly affected by the introduction of tiles. In the dry season, the use of tiles in the simulation increases the magnitude of precipitation (about 7 mm day−1), skin temperature (about 4 °C), sensible heat flux (about 80 W m−2) and surface albedo (about 0.7). It reduces the latent heat flux (about 30 W m−2) and net radiation (about 40 W m−2). On the other hand, in the rainy season, the model produces excessive precipitation. This may have partly masked the signs of the land fragmentation impact. The tile experiment generates a warmer and drier boundary layer during the dry season. The impact of the surface heterogeneity representation is higher in the dry season than in the rainy season. The results suggest that the degree of impact of the subgrid process representation on the local climate is related to the spatial scale of the fragmentation. The use of the tile approach improves the representation of the effects of landscape heterogeneity on the spatial distribution of surface flux variability in fragmented areas. Comparison against measured data from flux towers in the region show that the model can simulate diurnal and seasonal variations in the local fluxes, despite the biases.

Influence of metal impregnants on adsorption of dimethylsulfide vapors by activated carbons

In this paper, effect of metal impregnation was studied on the textural and sorptive properties of activated carbon cloth towards adsorption of dimethyl sulfide (DMS) vapors. The activated carbon was impregnated by three different transition metal ions (Ag+, Cr6+, Cu2+). Isotherms of dimethyl sulfide were measured gravimetrically at different temperatures. The results show that the adsorption capacity of activated carbon for DMS decreased after impregnation with metals. The variation in adsorbed amount of DMS vapors on the activated carbon impregnated with different metals was discussed on the basis of the hard-soft acid base (HSAB) principle. Kinetics of adsorption has been studied by using the Linear driving force model (LDF) and Empirical diffusion model. The kinetic parameters such as rate constant (k), diffusional exponent (n), adsorbate-adsorbent interaction constant (K) and activation energy (Ea) have also been determined. The trends in isosteric heats of adsorption indicated the effect of surface heterogeneity and lateral interactions. On the basis of equilibrium, kinetics and thermodynamic studies, the suitable mechanisms for the adsorption processes occurring on impregnated carbons have been suggested.

Surfactants adsorption on crossing stripes and steps.

Using coarse-grained dissipative particle dynamics (DPD) simulations, we systematically study the effect of surface heterogeneity on surfactant adsorption. Here we investigate the adsorption and aggregation of surfactants on hydrophobic stripes crossing each other perpendicularly (i.e., crossing stripes) and on hydrophobic steps. The results are compared with those obtained for isolated stripes. We find that on crossing stripes of moderate stripe widths (e.g., L = 0.61LS, 1.22LS and 1.83LS, where LS is the length of one surfactant molecule) the crossing region hinders the formation of defect-free adsorbed surfactant structures. By increasing the stripe width and/or by increasing the length of one of the two perpendicularly crossing stripes (i.e., lowering the surface density of defects/intersections), the crossing region is found to have a weaker effect on the features of the adsorbed structures. Regarding surfactant adsorption on steps, our simulation results show that the self-assembled aggregates can be stretched along the step corner, and the resultant elastic deformation can hinder adsorption. This qualitative observation can facilitate a description of surfactant adsorption that takes into consideration also the deformation of the self-assembled film. As suggested by such a general model, increasing the convex angle of the step, increasing the size of the surfactant head groups, and changing other physical parameters can reduce the elastic energy penalty, and yield larger amounts of surfactants adsorbed. The results presented could assist in understanding and sometimes predicting surfactant adsorption on heterogeneous surfaces, suggest methods to formulate surfactant mixtures to control surface coverage on heterogeneous surfaces, and perhaps facilitate new methods for the fabrication of nano-structured surfaces.

Effect of surface and subsurface heterogeneity on the hydrological response of a grassed buffer zone

Grassed buffer zones are an effective method to reduce contaminant impacts on aquatic environments. The general objective of this study is to explore the impact of both surface and subsurface heterogeneity on the hydrological responses of a vegetative buffer strip. Heterogeneity is described by two variables, microtopography and saturated hydraulic conductivity. Numerous surface and subsurface heterogeneity scenarios were simulated with a physically-based numerical model of coupled surface/subsurface processes. The scenarios were evaluated relative to data from an experimental vegetative filter in a Beaujolais vineyard, France. The subsurface scenarios show that conductivity heterogeneity plays a key role on the buffer strip’s capacity to infiltrate incoming surface runoff and on the ensuing runoff pathways. The conjunctive surface and subsurface scenarios indicate that microtopography variability is comparatively less influential on the hydrological interactions and pathways within the buffer strip, and that representing this heterogeneity via appropriate statistical distributions can be a good assumption in practice.

Upscaling methane emission hotspots in boreal peatlands

Abstract. Upscaling the properties and effects of small-scale surface heterogeneities to larger scales is a challenging issue in land surface modeling. We developed a novel approach to upscale local methane emissions in a boreal peatland from the micro-topographic scale to the landscape scale. We based this new parameterization on the analysis of the water table pattern generated by the Hummock–Hollow model, a micro-topography resolving model for peatland hydrology. We introduce this parameterization of methane hotspots in a global model-like version of the Hummock–Hollow model that underestimates methane emissions. We tested the robustness of the parameterization by simulating methane emissions for the next century, forcing the model with three different RCP scenarios. The Hotspot parameterization, despite being calibrated for the 1976–2005 climatology, mimics the output of the micro-topography resolving model for all the simulated scenarios. The new approach bridges the scale gap of methane emissions between this version of the model and the configuration explicitly resolving micro-topography.

Evaluation of atmosphere–land interactions in an LES from the perspective of heterogeneity propagation

Atmosphere–land interactions simulated by an LES model are evaluated from the perspective of heterogeneity propagation by comparison with airborne measurements. It is found that the footprints of surface heterogeneity, though as 2D patterns can be dissipated quickly due to turbulent mixing, as1D projections can persist and propagate to the top of the atmospheric boundary layer. Direct comparison and length scale analysis show that the simulated heterogeneity patterns are comparable to the observation. The results highlight the model’s capability in simulating the complex effects of surface heterogeneity on atmosphere–land interactions.

On the Representation of Heterogeneity in Land-Surface–Atmosphere Coupling

A realistic representation of processes that are not resolved by the model grid is one of the key challenges in Earth-system modelling. In particular, the non-linear nature of processes involved makes a representation of the link between the atmosphere and the land surface difficult. This is especially so when the land surface is horizontally strongly heterogeneous. In the majority of present day Earth system models two strategies are pursued to couple the land surface and the atmosphere. In the first approach, surface heterogeneity is not explicitly accounted for, instead effective parameters are used to represent the entirety of the land surface in a model’s grid box (parameter-aggregation). In the second approach, subgrid-scale variability at the surface is explicitly represented, but it is assumed that the blending height is located below the lowest atmospheric model level (simple flux-aggregation). Thus, in both approaches the state of the atmosphere is treated as being horizontally homogeneous within a given grid box. Based upon the blending height concept, an approach is proposed that allows for a land-surface–atmosphere coupling in which horizontal heterogeneity is considered not only at the surface, but also within the lowest layers of the atmosphere (the VERTEX scheme). Below the blending height, the scheme refines the turbulent mixing process with respect to atmospheric subgrid fractions, which correspond to different surface features. These subgrid fractions are not treated independently of each other, since an explicit horizontal component is integrated into the turbulent mixing process. The scheme was implemented into the JSBACH model, the land component of the Max Planck Institute for Meteorology’s Earth-system model, when coupled to the atmospheric general circulation model ECHAM. The single-column version of the Earth system model is used in two example cases in order to demonstrate how the effects of surface heterogeneity are transferred into the atmosphere, influencing local stability and the turbulent mixing process. Furthermore, a simple flux-aggregation scheme was implemented into the JSBACH model. By comparing single-column simulations utilizing the VERTEX scheme and the simple flux-aggregation scheme, it can be shown that the horizontal disaggregation of the turbulent mixing process has a substantial impact on the simulated mean state of a grid box. Here, the differences between simulations with the two schemes may, in certain cases, be even larger than the differences between simulations with the simple flux-aggregation scheme and simulations in which surface heterogeneity is not explicitly accounted for (i.e., a parameter-aggregation scheme).

The effect of electrode size and surface heterogeneity on electrochemical properties of ultrananocrystalline diamond microelectrode.

We report here the effect of electrode size on electrochemical properties of boron-doped ultrananocrystalline diamond (UNCD) microelectrodes using electrochemical impedance spectroscopy (EIS). By reducing microelectrode size from 250-μm to 10-μm diameter (D), the shape of impedance spectra changes from linear line to two-arcs. The fitting of experimental data to electrochemical circuit model suggests that each arc likely corresponds to UNCD grains and grain boundary phases. The two phases become separable as a result of microelectrode size reduction. In addition, for D ≤ 100-μm, microstructural and morphological defects/heterogeneities of grain boundaries and the presence of surface oxygen are also revealed in the spectra. The microelectrode size reduction specifically affect the impedance of the grain boundaries, e.g. for ultramicroelectrodes, UMEs (D ≤ 25-μm), as the grain boundary impedance increases by ~30-fold. Thus, at UMEs, the grain-grain boundary properties are revealed more sensitively in the spectra. Atomic force microscopy, scanning electron microscopy, Raman spectroscopy and surface profilometry measurements were performed to study the influence of microfabrication on surface properties. A significant increase in surface roughness after microfabrication shows that heterogeneities as observed in the spectra are not only due to intrinsic UNCD properties but also arises from microfabrication.

Pinning of the Contact Line during Evaporation on Heterogeneous Surfaces: Slowdown or Temporary Immobilization? Insights from a Nanoscale Study.

The question of the effect of surface heterogeneities on the evaporation of liquid droplets from solid surfaces is addressed through nonequilibrium molecular dynamics simulations. The mechanism behind contact line pinning which is still unclear is discussed in detail on the nanoscale. Model systems with the Lennard-Jones interaction potential were employed to study the evaporation of nanometer-sized cylindrical droplets from a flat surface. The heterogeneity of the surface was modeled through alternating stripes of equal width but two chemical types. The first type leads to a contact angle of 67°, and the other leads to a contact angle of 115°. The stripe width was varied between 2 and 20 liquid-particle diameters. On the surface with the narrowest stripes, evaporation occurred at constant contact angle as if the surface was homogeneous, with a value of the contact angle as predicted by the regular Cassie-Baxter equation. When the width was increased, the contact angle oscillated during evaporation between two boundaries whose values depend on the stripe width. The evaporation behavior was thus found to be a direct signature of the typical size of the surface heterogeneity domains. The contact angle both at equilibrium and during evaporation could be predicted from a local Cassie-Baxter equation in which the surface composition within a distance of seven fluid-particle diameters around the contact line was considered, confirming the local nature of the interactions that drive the wetting behavior of droplets. More importantly, we propose a nanoscale explanation of pinning during evaporation. Pinning should be interpreted as a drastic slowdown of the contact line dynamics rather than a complete immobilization of it during a transition between two contact angle boundaries.

Ureteral stents should be soaked for several minutes before placement.

PurposePlacement of ureteral stents (DJ-stents) may lead to complications. Inappropriate friction properties of the implant are, inter alia, made responsible for primary injuries, injury-related inflammation and a cascade of consecutive side effects. Hydrophilicity is considered to be related to low friction. The question arises, whether the various products on the market show their respective maximum hydrophilicity directly after unwrapping or a pre-use moistening, as already routinely done with the guide wire, is necessary.MethodsThe surface wettability of commercial and experimental DJ-stents was determined by water contact angle (WCA) measurements using the sessile drop method. One reference surface and 11 different stent surface types were tested. In order to determine the influence of moistening on the stents’ surface wettability, WCAs were measured twice, with dry, and soaked (30 min, 0.9%-NaCl) specimens. Each sample of a surface type was tested at three different positions to avoid effects of surface heterogeneities. Up to six samples of the same surface type were examined.ResultsMean WCAs on fresh and soaked stent surfaces ranged from 75°–103° and 71°–99°. In every case the WCAs on soaked surfaces were lower. On average the WCAs decrease by 7%, the individual decreases differ considerably, from 2 to 16%. For 7/12 of the examined surface types, the decrease in contact angle is statistically significant with p ≤ 0.01.ConclusionsDJ-stents freshly unwrapped show less hydrophilic properties compared to DJ-stents soaked in saline. To obtain maximum hydrophilicity at stent placement, DJ-stents should be soaked. The results may advocate a similar approach for other urological equipment.

ATR-FTIR measurements of albumin and fibrinogen adsorption: Inert versus calcium phosphate ceramics.

Arthritis, bone fracture, bone tumors and other musculoskeletal diseases affect millions of people across the world. Nowadays, inert and bioactive ceramics are used as bone substitutes or for bone regeneration. Their bioactivity is very much dictated by the way proteins adsorb on their surface. In this work, we compared the adsorption of albumin and fibrinogen on inert and calcium phosphates ceramics (CaPs) using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) to follow in situ protein adsorption on these materials. To this effect, we developed a sol-gel technique to control the surface chemistry of an ATR-FTIR detector. Hydroxyapatite adsorbed more albumin and β-tricalcium phosphate adsorbed more fibrinogen. Biphasic calcium phosphate presented the lowest adsorption among CaP for both proteins, illustrating the effect of surface heterogeneities. Inert ceramics adsorbed a lower amount of both proteins compared with bioactive ceramics. A significant change was observed in the conformation of the adsorbed protein versus the surface chemistry. Hydroxyapatite produced a larger loss of α-helix structure on albumin and biphasic calcium phosphate reduced β-sheet percentage on fibrinogen. Inert ceramics produced large α-helix loss on albumin and presented weak interaction with fibrinogen. Zirconia did not adsorb albumin and titanium dioxide promoted huge denaturalization of fibrinogen.

Effects of surface roughness and electrokinetic heterogeneity on electroosmotic flow in microchannel

In this paper, a hybrid lattice-Boltzmann and finite-difference (LB-FD) model is applied to simulate the effects of three-dimensional surface roughness and electrokinetic heterogeneity on electroosmotic flow (EOF) in a microchannel. The lattice-Boltzmann (LB) method has been employed to obtain the flow field and a finite-difference (FD) method is used to solve the Poisson-Boltzmann (PB) equation for the electrostatic potential distribution. Numerical simulation of flow through a square cross-section microchannel with designed roughness is conducted and the results are critically analysed. The effects of surface heterogeneity on the electroosmotic transport are investigated for different roughness height, width, roughness interval spacing, and roughness surface potential. Numerical simulations reveal that the presence of surface roughness changes the nature of electroosmotic transport through the microchannel. It is found that the electroosmotic velocity decreases with the increase in roughness height and the velocity profile becomes asymmetric. For the same height of the roughness elements, the EOF velocity rises with the increase in roughness width. For the heterogeneously charged rough channel, the velocity profile shows a distinct deviation from the conventional plug-like flow pattern. The simulation results also indicate locally induced flow vortices which can be utilized to enhance the flow and mixing within the microchannel. The present study has important implications towards electrokinetic flow control in the microchannel, and can provide an efficient way to design a microfluidic system of practical interest.

A need to revisit hydrologic responses to urbanization by incorporating the feedback on spatial rainfall patterns

This study highlights the changes in the hydrologic responses to urbanization under idealized spatial heterogeneity in rainfall distribution. The study builds off recent assessments which show that urban areas modify the spatial rainfall pattern in its vicinity. Numerical experiments were conducted over an idealized watershed by prescribing different spatial patterns of rainfall and impervious coverage. Hydrologic responses were characterized by four metrics: flow distribution, daily variation, frequency of floods, and interannual runoff variability, as well as relative changes in flood magnitudes under different scenarios. Results indicate that hydrological response depends on both the spatial extent of urban coverage and the spatial patterns of rainfall. The most noticeable hydrologic variations and relative changes of flood magnitudes occur when the watershed is moderately urbanized (with 20–30% impervious coverage in the watershed). A factor separation scheme was employed to determine the synergistic effect of land surface and rainfall heterogeneity on flood magnitudes. Increases in flood magnitudes induced by urbanization could be underestimated by as much as 50% if spatial rainfall patterns are ignored. This study highlights the need for considering urban meteorological feedback while examining hydrologic responses to urbanization with both the changes of impervious coverage and spatial rainfall patterns considered.

Model for Surface Diffusion of Adsorbed Gas in Nanopores of Shale Gas Reservoirs

Surface diffusion plays a key role in gas mass transfer due to the majority of adsorbed gas within abundant nanopores of organic matter in shale gas reservoirs. Surface diffusion simulation is very complex as a result of high reservoir pressure, surface heterogeneity, and nonisothermal desorption in shale gas reservoirs. In this paper, a new model of surface diffusion for adsorbed gas in shale gas reservoirs is established, which is based on a Hwang model derived under a low pressure condition and considers the effect of adsorbed gas coverage under high pressure. Additionally, this new model considers the effects of surface heterogeneity, isosteric sorption heat, and nonisothermal gas desorption. Results show that (1) the surface diffusion coefficient increases with pressure and temperature, while it decreases with activation energy and gas molecular weight; (2) contributions of viscous flow, Knudsen diffusion, and surface diffusion to the total gas mass transfer are varying during the development of shal...

Isotherms, kinetics and thermodynamics for adsorption of pyridine vapors on modified activated carbons

The adsorption isotherms of pyridine have been determined gravimetrically on different samples of granulated, fibrous and spherical activated carbons. Several chemical treatments such as oxidation, degassing and impregnation have been carried out on as-received activated carbon cloth (ACC) so as to modify the surface characteristics of the activated carbon. The porous and chemical structure of modified and unmodified activated carbons has been characterised by XRD, TGA–DTG, SEM and pore size distribution techniques. The adsorption increases on oxidation while decreases on degassing which can be correlated to increase and decrease in the concentration of surface oxygen groups. Loading with Ag+ and Cu2+ increases the adsorption of pyridine compared with the unloaded sample while loading with Cr6+ decreases the adsorption of these vapors. The adsorption–desorption branches of pyridine vapors on metal impregnated do not meet even at zero relative vapor pressure indicating the chemisorption or other specific interactions. The adsorption kinetics data has been examined using the linear driving force and empirical diffusion models. The initial decrease in isosteric enthalpy of adsorption for modified and unmodified ACC indicates the effect of surface heterogeneity and later increase indicates the influence of lateral interactions between adsorbate molecules. The results suggest that the adsorption of pyridine involves the physisorption as well as specific interactions with carbon oxygen functional groups and metal complexes present on the carbon surface.